Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\\n\\n
Seeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\\n\\n
Over these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\\n\\n
We are excited about the present, and we look forward to sharing many more successes in the future.
\\n\\n
Thank you all for being part of the journey. 5,000 times thank you!
\\n\\n
Now with 5,000 titles available Open Access, which one will you read next?
Preparation of Space Experiments edited by international leading expert Dr. Vladimir Pletser, Director of Space Training Operations at Blue Abyss is the 5,000th Open Access book published by IntechOpen and our milestone publication!
\n\n
"This book presents some of the current trends in space microgravity research. The eleven chapters introduce various facets of space research in physical sciences, human physiology and technology developed using the microgravity environment not only to improve our fundamental understanding in these domains but also to adapt this new knowledge for application on earth." says the editor. Listen what else Dr. Pletser has to say...
\n\n\n\n
Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\n\n
Seeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\n\n
Over these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\n\n
We are excited about the present, and we look forward to sharing many more successes in the future.
\n\n
Thank you all for being part of the journey. 5,000 times thank you!
\n\n
Now with 5,000 titles available Open Access, which one will you read next?
\n'}],latestNews:[{slug:"intechopen-partners-with-ehs-for-digital-advertising-representation-20210416",title:"IntechOpen Partners with EHS for Digital Advertising Representation"},{slug:"intechopen-signs-new-contract-with-cepiec-china-for-distribution-of-open-access-books-20210319",title:"IntechOpen Signs New Contract with CEPIEC, China for Distribution of Open Access Books"},{slug:"150-million-downloads-and-counting-20210316",title:"150 Million Downloads and Counting"},{slug:"intechopen-secures-indefinite-content-preservation-with-clockss-20210309",title:"IntechOpen Secures Indefinite Content Preservation with CLOCKSS"},{slug:"intechopen-expands-to-all-global-amazon-channels-with-full-catalog-of-books-20210308",title:"IntechOpen Expands to All Global Amazon Channels with Full Catalog of Books"},{slug:"stanford-university-identifies-top-2-scientists-over-1-000-are-intechopen-authors-and-editors-20210122",title:"Stanford University Identifies Top 2% Scientists, Over 1,000 are IntechOpen Authors and Editors"},{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"}]},book:{item:{type:"book",id:"1992",leadTitle:null,fullTitle:"Recent Advances in Aircraft Technology",title:"Recent Advances in Aircraft Technology",subtitle:null,reviewType:"peer-reviewed",abstract:"The book describes the state of the art and latest advancements in technologies for various areas of aircraft systems. 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\r\n\tIdiopathic pulmonary fibrosis (IPF) is the most common and important type of Idiopathic interstitial pneumonia, characterized by progressive fibrosis. It is a serious disease of unknown etiology with a high fatality rate. Over the past two decades there has been a tremendous amount of research in this field, that has helped us better understand the epidemiology, risk factors, pathogenesis, diagnostic evaluation and management strategies of IPF. The incidence and prevalence of the disease increases with age.
\r\n
\r\n\tWorldwide IPF has known to affect more than 3 million people. In US the reported incidence of IPF is 6 to 94 cases per 100,000 person years and prevalence is 18-495 cases per 100,000 adults depending on the age of the cohort. IPF is a clinically heterogenous disease and the course and progression of IPF is highly variable with intermittent episodes of acute exacerbations with rapid decline in lung function. Patients present with dyspnea and hypoxemia which significantly affects their quality of life. IPF is an expensive disease and the direct treatment cost is around 25,000 USD per person year. The pathogenesis of the disease is complex, and it is important to rule out a number of other diseases that can lead to pulmonary fibrosis. The hallmark of this disease is usual interstitial pneumonia (UIP) pattern seen on HRCT and on histology.
\r\n
\r\n\tThe diagnosis requires a multidisciplinary team approach and several guidelines have been published in the recent years to help the clinicians diagnose this disease in a timely manner. After decades of research two antifibrotic drugs are now available which are not curative but has shown to significantly slow down the decline in lung function associated with this disease. There are newer and less invasive technologies, biomarkers that are being developed to diagnose IPF and novel targeted treatment strategies are on pipeline. Lung transplant still remains the cornerstone of management as despite the treatment with antifibrotic agents most of the patients with IPF will progress to advanced end-stage lung disease.
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\n
1. Introduction
\n
Constipation in children is a common problem and accounts for up to 25% of pediatric clinical consultation [1]. The most common cause of constipation is functional (without any organic etiology or anatomical malformation), with an estimated prevalence of 3% worldwide. Infants on an average pass four stools per day in the first day of life, which gradually decreases to an average of 1.7 stools per day at 2 years of age and 1.2 stools per day at 4 years of age [2]. Evidence suggests that dietary, lifestyle, cognitive, emotional/behavioral, and broader psychosocial factors may all play a role in the etiology, maintenance, and clinically effective treatment of functional GI disorders. Constipated children have more outpatient and emergency department visits for abdominal pain, and their overall annual medical cost is approximately twice as much as that of children without constipation. Diagnosis of functional constipation requires a careful history and thorough physical examination. Management includes initial disimpaction followed by maintenance therapy with dietary modification, toilet training, and oral laxative. Laxatives may be needed for several months and sometimes years [3]. Noncompliance to laxative is the commonest cause of recurrence. Refractory constipation is defined as nonresponse to optimal treatment for at least 3 months. This form of constipation may be diagnosed by colon transit time (CTT) study, which can be done by radio-opaque markers and by radionuclide scintigraphy. Antegrade continence enema is an option in patients with optimal CTT. Children with constipation having warning signs need further evaluation in the form of anorectal manometry barium/contrast enema and sometimes rectal biopsy. Absence of ganglion cells on rectal biopsy suggests Hirschsprung’s disease requiring surgical treatment [4].
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2. Definition of constipation
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Functional constipation is defined as presence of two or more of the following ROME III criteria in the absence of any organic etiology, and the duration of constipation should at least be 1 month in children <4 years of age, and at least once per week for at least 2 months in children ≥4 years of age [5] (Table 1).
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Child with age < 4 years
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Child with age ≥ 4 years
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≤2 defecations/week
One episode of incontinence per week after
Excessive stool retention
Painful or hard bowel movements
Presence of a large fecal mass in the rectum
Large-diameter stools that may obstruct the toilet
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≤2 defecations in the toilet per week
One episode of fecal incontinence per week
Retentive posturing or excessive volitional stool retention
Painful or hard bowel movements
Large fecal mass in the rectum
Large-diameter stools that may obstruct the toilet
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Table 1.
Diagnostic criteria for functional constipation in children.
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3. Etiology and pathogenesis of constipation
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Disruption of the normal physiology leads to constipation. Constipation may result from impaired propulsion of stools, sensation of rectum, and rectal outlet obstruction [6]. Disruption of the normal physiology leads to constipation. Constipation may, result from impaired propulsion of stools, sensation of rectum, rectal outlet obstruction. Conditions that lead to impaired propulsion are metabolic abnormalities such as hypo/hypercalcemia, hypothyroidism, cystic fibrosis, celiac disease, and genetic predisposition. Use of narcotics, psychotropics, and anticholinergic defective/impaired sensation may occur in spinal cord abnormalities or secondary sensory impairment due to megarectum from chronic fecal retention. Other anatomical and pathological causes of constipation include Hirschsprung’s disease, imperforate anus, pelvic or sacral mass, anal or colonic stricture, anteriorly displaced anus or Functional as in intentional fecal retention, and pelvic floor dyssynergia.
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Breastfed infants produce more frequent and larger stools than those fed standard infant formula until food is introduced at 5 months of age. Bowel movement frequency decreases with age. Stool production occurs more often in the first month of life and may be attributed to immaturity of the gastrointestinal tract. The passage of hard stool are perceived as painful leading to stool withholding, as the child becomes afraid to defecate. Furthermore, withholding creates a cycle of more pain on defecating (Figure 1). Signs of withholding behavior include arching the back, stiffening the legs, and unusual postures/crossing of legs in older children [7]. Parents may misinterpret withholding as straining or an attempt to defecate.
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Figure 1.
Viscous circle of constipation and pain. Painful defecation leads to voluntary withholding behavior and prolonged fecal stasis (stools becomes harder and larger). Passage of hard stools leads to more pain due to fissures which further aggravates constipation.
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It can be challenging for some parents to toilet train their children. Research supports that stool toileting refusal occurs in 1 of every 5 children. This leads to stool withholding behavior and incontinence [8]. Functional constipation is at times associated with autism and attention-deficit hyperactivity disorder (ADHD). However, the literature indicates that the rate of constipation does not differ significantly between children with or without ADHD [9]. Other causes diet changes such as the introduction of solids or cow’s milk, illness, and change in routine. In some situations, children defer the defecation by playing, operating computers, watching television, and nonavailability/unhygienic conditions of the toilet rooms. Moreover some children remain in hurry and do not spend enough time completely emptying the rectum of stool. Common pathological causes of constipation in childhood include, Hirschsprung’s disease, myopathy, congenital anomalies like anal stenosis, anteriorly located anus, spinal cord anomalies (meningomyelocele, myelomalacia, spina bifida), hypothyroidism, hypercalcemia, cerebral palsy, and mental retardation. Some drugs causing constipation include anticonvulsants, antipsychotic, codeine containing antidiarrheal [10] (Table 2).
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Anal achalasia
Colonic inertia
Anatomic malformations
Imperforate anus
Anal stenosis
Celiac disease
HSD
Dietary protein allergy
Vitamin D intoxication
Cystic fibrosis
Pelvic mass (sacrococcygeal teratoma)
Spinal cord anomalies, trauma, tethered cord
Abnormal abdominal musculature (prune belly, gastroschisis, Down syndrome)
Causes of constipation in infants/toddlers and children/adolescents.
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4. Sequelae of constipation
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Fecal retention contributes to dysfunctional voiding, vesicoureteral reflux, and urinary tract infections. Increased stool in the rectum can cause abnormal bladder pressure and function. Urinary tract infections and enuresis occur in 30% of constipated children [11]. Some patients with constipation present as abdominal pain, obstruction, loss of apetite, and poor school attendance.
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5. Evaluation of constipation
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A thorough history and examination is very essential part of complete evaluation of a child with constipation. Important information includes any history of delayed passage of meconium, duration of constipation, the frequency of bowel movements, the consistency and size of the stools, painful defecation, bleeding per rectum (blood present in the stool or the toilet paper), abdominal pain. Identification of alarm signs favors organic diseases, and these signs are given in Table 3 [13].
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Distented abdomen
Absent lumbosacral curve
Pilonidal sinus/dimple covered by a tuft of hair
Midline pigmentary abnormalities of the lower spine
Sacral agenesis
Flat buttocks
Anteriorly displaced anus
Patulous anus
Tight, empty rectum in presence of palpable abdominal fecal mass
Gush of liquid stool and air from rectum on withdrawal of finger
Occult blood in stool
Absent anal wink
Absent cremasteric reflex
Decreased lower limb tone and/or strength
Absence or delay in relaxation phase of lower extremity deep tendon reflex
Failure to thrive
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Table 3.
Alarm signs that favor organic diseases.
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The current evidence-based recommendations do not support digital examination of the anorectum, unless the diagnosis of functional constipation is uncertain, alarm signs are present, or there is intractable constipation. Abdominal radiograph is only recommended if fecal impaction is suspected clinically and physical examination is unreliable or not possible. Routine laboratory tests for hypothyroid, celiac disease, or hypercalcemia are not indicated, unless alarm symptoms are present [13] (Table 4).
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Condition
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Diagnostic evaluation
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Anatomic malformations of the colon and rectum
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Imperforate anus, anal or colonic stenosis, anteriorly displaced anus
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Physical examination, barium enema
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Spinal cord abnormalities
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Spinal magnetic resonance imaging, anorectal manometry, urodynamics
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Meningomyelocele, spinal cord tumor or trauma, tethered cord
Differential diagnosis and evaluation of constipation in children.
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Some children have a history of irregular bowel movements without clear history of constipation, and in these cases, colonic transit time (CTT) with radiopaque markers study can be useful. The history obtained may also be not as clear and in these patients, an evaluation can be helpful [14]. The CTT study provides objective evaluation of bowel movement.
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Younger the infant (less than 6 months) more are the chances of an organic etiology for constipation. Hirschsprung’s disease (HSD) must be suspected in infants with history delayed passage of meconium (more than 48 h after birth), constipation since birth, recurrent abdominal distention and enterocolitis. In infants, neonated HSD can present as enterocolitis, a potentially fatal complication that presents as fever, abdominal distension, and explosive, bloody diarrhea. Patients with suspected Hirschsprung’s disease should be referred to a pediatric surgeon. On examination, the position (anteriorly displaced anus) and patency of the anus should be assessed. Spinal examination should be done for spina bifida and tethered cord [13, 15].
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Further evaluation is indicated in older children with red flags or with intractable constipation despite strict adherence to therapy. Laboratory studies should be performed to exclude systemic diseases, such as hypothyroidism, celiac disease, or lead toxicity. Anorectal manometry can assess for sphincter abnormalities, such as Hirschsprung’s disease or a nonrelaxing internal anal sphincter (IAS). Magnetic resonance imaging is uses to evaluate for a tethered cord, spinal cord tumor, or sacral agenesis [16, 17].
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6. Treatment
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6.1. Education and behavior modification/dietary changes
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It is important to explain that overflow of stools leads to fecal pseudo-incontinence and is not an voluntary defiance. Regular toileting (for 5–10 min) after meals combined with a reward system is often helpful. Parents should expect gradual improvement with occasional relapses and encourage to maintain a positive and supportive attitude throughout the treatment. Although behavior modification may help in occasional cases, intensive behavior therapy does not seem to add to treatment success. Studies have shown that children with constipation have a lower fiber intake than other children. Too early and vigorous toilet training may be detrimental for the child. The child is encouraged to sit on the toilet for 5–10 min, 3–4 times a day immediately after major meals for initial months [11].
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Dietary changes are often advised in children with constipation. Some authors suggest that increased intake of fluids and carbohydrates (e.g., sorbitol in prune, pear, and apple juice) can help soften stools, particularly in infants. A well-balanced diet that includes whole grains, fruits, and vegetables is recommended for children with constipation [12]. Guidelines do not support the following therapies for the treatment of childhood functional constipation: fiber supplements, extra fluid intake, routine use of pre- or probiotics, or alternative treatments such as acupuncture or chiropractic therapy. Child with cow’s milk intolerance may respond to a trial of a cow’s milk-free diet, especially in young children with anal fissures [13].
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6.2. Management of children with functional constipation
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6.2.1. Initial treatment with disimpaction
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Fecal impaction is diagnosed on per abdomen examination, digital rectal examination, or excessive stool in the colon identified by abdominal radiography. Disimpaction can either be performed by oral or rectal routes; studies have shown no significant differences between the two routes. Evidence shows that PEG and enemas are equally effective for fecal disimpaction. Polyethylene glycol is ideal for oral disimpaction at a dose of 1.5 g/kg/day for 3–6 days; maximum dose 100 g/day. Rectal disimpaction has also been effectively performed with glycerin suppositories in infants and bisacodyl suppositories in older children. Use of soap suds, tap water, and magnesium enemas is not recommended because of their potential toxicity [17].
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6.2.2. Follow-up maintenance therapy
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Lactulose is considered to be safe for all ages. Evidence shows that PEG is more effective compared with lactulose, milk of magnesia, mineral oil, or placebo.
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Lactulose is recommended in case PEG is not available (JPGN). Some authors suggest medical therapy should be continued for at least the time since a child had constipation. Regular follow-up (by reviewing stool records and repeating abdominal and (if required) rectal examination) is a key to the success of functional constipation. As mentioned above, dosage adjustment may be needed. Once a regular bowel habit is established, the laxative dosage is to be decreased gradually before stopping [18]. Parents should maintain a daily record (stool diary) of bowel movements, fecal soiling, pain or discomfort, consistency of stool, and the laxative dose. This helps in modification of dosage of laxatives (Table 5). About 50% will recover, and will be without laxatives after 6–12 months. Approximately, an additional 10% is well while taking laxatives, and 40% will still be symptomatic despite the use of laxatives. Children with early age of presentation (<4 years), associated with fecal incontinence, and history of longer duration of symptoms (>6 months) have poor outcome [3].
Refractory constipation is defined when there is no response to optimal conventional treatment for at least 3 months. The refractory constipation has a prevalence of 20–30%, but the prevalence is much higher in underdeveloped countries like India [19]. While managing a case of refractory constipation common organic causes (Hirschsprung disease, hypothyroidism, celiac disease, hypercalcemia, spinal cord abnormalities) should be ruled out first. Motility studies like colon transit time (CTT), anorectal manometry with balloon expulsion test, and colonic manometry should be performed to rule out organic causes before labelling constipation as refractory [20].
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6.2.4. Slow transient constipation
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In radiographic CTT study, after oral administration of radio-opaque markers, radiograph of abdomen is taken sequentially on the fourth and seventh day; X-ray markers are counted in right colon; and if retention of contrast occurs after 62 h, it is called as slow transient constipation. Clinical features of slow transit constipation in these children include history of delayed passage of meconium, onset of symptoms early of symptoms early in first year and/or failure to toilet training, feces soft rather than rock hard, high fiber diets worsen the symptoms, and delay in colonic transit on transit study [21]. The management of slow transit constipation is challenging as they do not respond to conventional laxative therapy and the main concern is soiling. Fiber therapy is contraindicated. The only effective therapy for this subset of patients is antegrade continence enema. Malone antegrade continence enema (MACE) helps in refractory slow transit constipation cases [22]. Appendix is exteriorized as small opening on to the skin. Colonic manometry results should be optimal before contemplating MACE.
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Internal anal sphincter achalasia (IAS) is a rare but important cause of refractory constipation. In a study of 332 patients with severe constipation, De Caluwe et al. [23] have reported this as a cause in just 4.5% of cases. This is associated with severe constipation and incontinence. It is diagnosed by the absence of anorectal inhibitory reflex (ARIR) on anorectal manometry along with the presence of ganglion cell on rectal. Sphincter myectomy is more rewarding than intrasphincteric botulinum toxin injection.
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7. Conclusions
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Functional constipation is quite common in both developed and not developed nations and is benign. Parent education, toilet training, dietary changes, initial moral or rectal disimpaction and use of appropriate laxative and follow-up of the responses to the treatment are keystone of successful management. Meticulous history and proper physical examination, including digital rectal examination, can differentiate functional from organic constipation. Treatment in functional constipation can be started before any investigation. Disimpaction either with oral polyethylene glycol or rectal enemas is the first step in the management of constipation. Polyethylene glycol is more effective but costlier than lactulose. At times, prolonged maintenance of laxative therapy (months to years) may be required and noncompliance leads to recurrence. Radiological colon transit time is useful in the management of refractory constipation. Slow transit constipation is a different entity, and Malone continence enema helps in this subset of patients. Some pathological and surgical causes need to be ruled out if warning signs or symptoms are present, which may require contrast enema, anorectal manometry, and rectal biopsy.
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\n\n',keywords:"functional constipation, laxatives, children",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/65371.pdf",chapterXML:"https://mts.intechopen.com/source/xml/65371.xml",downloadPdfUrl:"/chapter/pdf-download/65371",previewPdfUrl:"/chapter/pdf-preview/65371",totalDownloads:411,totalViews:0,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,dateSubmitted:"September 28th 2018",dateReviewed:"December 3rd 2018",datePrePublished:null,datePublished:"October 2nd 2019",dateFinished:"January 28th 2019",readingETA:"0",abstract:"Constipation is a common problem in children. It accounts for 20–30% of pediatric outdoor office. It is common in both rich and poor countries despite the belief that developing countries consume food rich in fiber. Normal bowel movement in breastfed babies may range from several times a day to once in every 10 days. Constipation can be both functional and pathological. Functional constipation has no underlying cause and is the most common type of constipation found in children. My main focus will be on this common type of constipation. In functional constipation routine, digital rectal examination is not recommended unless impaction is suspected. Abdominal radiography is recommended only in equivocal clinical examination or if impaction is suspected and examination not conclusive. Dietary and behavior modifications, toilet training, and parent education are important in the management of functional constipation. Initial management of functional constipation includes disimpaction of stools. Lactulose is safe in all age groups. Polyethylene glycol is more effective than lactulose but is costly. Maintenance therapy may take some time till constipation improves. Some rare situations such as refractory and slow transient constipation are also discussed in this chapter.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/65371",risUrl:"/chapter/ris/65371",book:{slug:"constipation"},signatures:"Raashid Hamid and Shazada Shahid Banday",authors:[{id:"213319",title:"Dr.",name:"Raashid",middleName:null,surname:"Hamid",fullName:"Raashid Hamid",slug:"raashid-hamid",email:"drraashidhamid@gmail.com",position:null,institution:{name:"University of Kashmir",institutionURL:null,country:{name:"India"}}},{id:"286547",title:"Dr.",name:"Shahid",middleName:null,surname:"Banday",fullName:"Shahid Banday",slug:"shahid-banday",email:"bandaysajid89@gmail.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Definition of constipation",level:"1"},{id:"sec_3",title:"3. Etiology and pathogenesis of constipation",level:"1"},{id:"sec_4",title:"4. Sequelae of constipation",level:"1"},{id:"sec_5",title:"5. Evaluation of constipation",level:"1"},{id:"sec_6",title:"6. Treatment",level:"1"},{id:"sec_6_2",title:"6.1. Education and behavior modification/dietary changes",level:"2"},{id:"sec_7_2",title:"6.2. Management of children with functional constipation",level:"2"},{id:"sec_7_3",title:"6.2.1. Initial treatment with disimpaction",level:"3"},{id:"sec_8_3",title:"Table 5.",level:"3"},{id:"sec_9_3",title:"6.2.3. Refractory constipation",level:"3"},{id:"sec_10_3",title:"6.2.4. Slow transient constipation",level:"3"},{id:"sec_13",title:"7. Conclusions",level:"1"}],chapterReferences:[{id:"B1",body:'Benninga M, Candy DC, Catto-Smith AG, et al. The Paris Consensus on Childhood Constipation Terminology (PACCT) Group. Journal of Pediatric Gastroenterology and Nutrition. 2005;40:273-275\n'},{id:"B2",body:'Weaver LT, Steiner H. The bowel habits of young children. Archives of Disease in Childhood. 1983;59:649-652\n'},{id:"B3",body:'Poddar U. Approach to constipation in children. Indian Pediatrics. 2016;53:319-327\n'},{id:"B4",body:'Southwell BR, Clarke MC, Sutcliffe J, et al. Colonic transit studies: Normal values for adults and children with comparison of radiological and scintigraphic methods. Pediatric Surgery International. 2009;25:559-572\n'},{id:"B5",body:'Hyman PE, Milla PJ, Benninga MA, Davidson GP, Fleisher DF, Taminiau J. Childhood functional gastrointestinal disorders: Neonate/toddler. Gastroenterology. 2006;130:1519-1526\n'},{id:"B6",body:'Baucke VL. Prevalence, symptoms and outcome of constipation in infants and toddlers. The Journal of Pediatrics. 2005;146:359-363\n'},{id:"B7",body:'Loening-Baucke V. Chronic constipation in children. Gastroenterology. 1993;105:1557-1564\n'},{id:"B8",body:'Loening-Baucke V. Constipation in early childhood: Patient characteristics, treatment and long-term followup. Gut. 1993;34:1400-1404\n'},{id:"B9",body:'Kehar M, Yadav SP, Sachdeva A. Constipation in children. JIMSA. 2012;25:31-33\n'},{id:"B10",body:'Khanna V, Poddar U, Yachha SK. Constipation in Indian children: Need for knowledge not the knife. Indian Pediatrics. 2010;47:1025-1030\n'},{id:"B11",body:'Loening-Baucke V. Polyethylene glycol without electrolytes for children with constipation and encopresis. Journal of Pediatric Gastroenterology and Nutrition. 2002;34:372-377\n'},{id:"B12",body:'Benninga MA, Buller HA, Staalman CR, Gubler FM, Bossuyt PM, van der Plas RN, et al. Defecation disorders in children, colonic transit times versus the Barr-score. European Journal of Pediatrics. 1995;154:277-284\n'},{id:"B13",body:'Tabbers MM, Di Lorenzo C, Berger MY, Faure C, Langendam MW, Nurko S, et al. Evaluation and treatment of functional constipation in infants and children: Evidence-based recommendations from ESPGHAN and NASPGHAN. Journal of Pediatric Gastroenterology and Nutrition. 2014;58:25874\n'},{id:"B14",body:'Taitz LS, Water JKH, Urwin OM, Molnar D. Factors associated with outcome in management of defecation disorders. Archives of Disease in Childhood. 1986;61:472-477\n'},{id:"B15",body:'Partin JC, Hamill SK, Fischel JE, Partin JS. Painful defecation and fecal soiling in children. Pediatrics. 1992;89:1007-1009\n'},{id:"B16",body:'Metaj M, Laroia N, Lawrence RA, Ryan RM. Comparison of breast- and formula-fed normal new born in time to first stool and urine. Journal of Perinatology. 2003;23:624-628\n'},{id:"B17",body:'Jung PM. Hirschsprung’s disease: One surgeon’s experience in one institution. Journal of Pediatric Surgery. 1995;30:646-651\n'},{id:"B18",body:'Candy D, Belsey J. Macrogol (polyethylene glycol) laxatives in children with functional constipation and fecal impaction: A systematic review. Archives of Disease in Childhood. 2009;94:156-160\n'},{id:"B19",body:'Southwell BR, King SK, Hutson JM. Chronic constipation in children: Organic disorders are a major cause. Journal of Paediatrics and Child Health. 2005;41:1-15\n'},{id:"B20",body:'Kwshtgar A, Ward HC, Clayden GS. Diagnosis and management of children with intractable constipation. Seminars in Pediatric Surgery. 2004;13:300-309\n'},{id:"B21",body:'Hutson JM, McNamara J, Gibb S, Shin YM. Slow transit constipation in children. Journal of Paediatrics and Child Health. 2001;37:426-430\n'},{id:"B22",body:'Malone PS, Ransley PG, Kiely EM. Preliminary report: The antegrade continence enema. Lancet. 1990;336:1217-1218\n'},{id:"B23",body:'De Caluwe D, Yoneda A, Akl U, Puri P. Internal anal sphincter achalasia: Outcome after internal sphincter myectomy. Journal of Pediatric Surgery. 2001;36:736-738\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Raashid Hamid",address:"drraashidhamid@gmail.com",affiliation:'
Department of Pediatric and Neonatal Surgery, Sheri-I-Kashmir Institute of Medical Sciences, Soura, Srinagar, Jammu and Kashmir, India
Department of Pediatric and Neonatal Surgery, Sheri-I-Kashmir Institute of Medical Sciences, Soura, Srinagar, Jammu and Kashmir, India
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1. Introduction
Lithium and its compounds are widely used in manufactured glass, ceramics, greases, batteries, refrigerants, chemical reagents and other industries. World lithium reserves are about 14 million tons, mostly 70–80% is stored in salt lake brine, geothermal water and solid lithium contained in lithium ore. Currently, many researchers are turning their attention to 2600 billion tons of lithium-containing seawater, which is about 15,000 times more than solid lithium ores [1].
Figures for lithium resources and reserves differ considerably accordingly to the source, although there is a unanimous agreement that lithium resources in brine are much larger than those in hard rock [2, 3, 4, 5, 6]. The most recent figures from the US Geological Survey indicate total lithium resources (brine + hard rock) to be 54.1 million tons [5]. Approximate minimum and maximum hard rock lithium resources were reported at 12.8 and 30.7 million tons, respectively; while brine field data were reported as 21.3 and 65.3 million tons, respectively, for minimum and maximum estimates [3].
Lithium has various uses, but its abundance in nature is only 0.0018% [7]. The use of lithium on ceramics enriched with Li6 is up to 15% for use in the production of tritium [8, 9]. In addition, enriched Li6 is very expensive, what is commensurate with the value of gold. Consequently, it is necessary to extract and recycle lithium from the waste of solid breeding materials. Hence widespread use of lithium in various spheres, many studies have been conducted to extract lithium from various sources.
Lithium demand is expected to grow continuously and dramatically in the coming years as different types of lithium batteries are the most promising candidates for powering electric or hybrid vehicles [10, 11]. Lithium batteries include both current technologies such as lithium-ion and growing battery technologies such as lithium-sulfur or lithium-air [12, 13, 14, 15].
Lithium demand is projected to increase by ~60% from 102,000 to 162,000 tonnes of lithium carbonate equivalent in the next 5 years, with battery applications taking a huge percentage of this growth [16, 17]. It was reported that the present lithium resource in continental and Salar brines is roughly 52.3 million tons of lithium equivalent, mainly in Argentina, Chile and Bolivia, from which 23.2 million tons can be extracted [18]. From the other side, lithium from mineral resources is 8.8 million tons, where there are huge deposits in the United States, Russia and China. Evans estimated lithium reserves and recoverable resources at 29.79 million tons [19].
Meanwhile, the general public mainly associates lithium batteries with portable electronics and electric and hybrid vehicles, large storage capacity lithium batteries are also a lead candidate for a possible energy storage solution for the electric grid, intelligent network, etc. Batteries with large capacity are needed to store green energy, wind, that is, sun and waves, all this by their nature intermittent sources of energy [20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30]. Nowadays battling to achieve a greater percentage of green energy, high-capacity batteries or energy banks are mandatory. Basically, if in the near future we want our energy matrix to be highly dependent on renewable energy, energy banks will be needed to provide continuous energy to the grid, during the time these intermittent energy sources are either off or not working completely (no wind, no waves, at night) [20, 21, 22]. After all, on its own of the energy source, high-capacity batteries are also an alternative for storing energy during periods of low demand, allowing this excess energy to be re-injected into the grid at high demand peaks [24].
Currently, lithium is relatively not expensive (a ton of Li2CO3 is about 15,000 USD), the market shows that, its price is rising with increasing demand [25].
In China, lithium prices have risen about 300% since 2016, and contract prices for existing manufacturers have risen to more than 16,000 USD per tonne.
Because of the exhaustion of lithium ores, recent studies have shown recovery of lithium from seawater, brine and geothermal water. Production of lithium from water resources has become more important due to its wide availability, ease of process and cost-effectiveness compared with its production from various resources [26].
Many methods for extracting lithium from seawater, brines and geothermal water have been reported [27]: solvent extraction, including precipitation, liquid-liquid extraction, selective membrane separation, electrodialysis, ion exchange adsorption, etc. [28, 29, 30, 31, 32, 33, 34]. Of these methods, the most attention was paid to ion exchange adsorption methods based on lithium-ion sieves because of their good lithium-ion selectivity and high adsorption properties [35, 36, 37]. From the point of view of cost and efficiency, extraction of lithium ions from solutions by ion exchange adsorption is an important method [38].
Various methods of removing lithium from water have been proposed in recent years. In their midst, adsorption has been proven to be a perfect way to extract lithium, offering significant benefits, such as availability, lower cost, profitability, efficiency and easy operation. For lithium removal, various Li adsorbent materials have previously been reported, including metal oxides, clay minerals, silicotitanates and zirconium phosphate. The main attention of the researchers was focused on the adsorbents of titanium-lithium ion sieves [39, 40, 41, 42, 43] manganese-lithium ion sieves [44, 45, 46, 47, 48, 49, 50] and aluminum salts [51, 52]. Adsorbents of aluminum salts [52] showed stable and high selectivity for Li+ with lithium absorption of only 2–3 mg g−1. By Chitrakar et al. [53] nanoscale H2TiO3 was synthesized by solid-phase reaction and its adsorption capacity with lithium reached 32 mg g−1 [41]. Tang et al. and Zhang et al. were synthesized H2TiO3 using different raw materials [41, 42]. Wang et al. synthesized lithium-enriched β-Li2TiO3 with a maximum lithium absorption of 76.7 mg g−1 in LiOH alkali solution [43]. Despite the fact the maximum absorption of Li+ adsorbent H2TiO3 from the lithium-enriched solution has reached 76.7 mg g−1, the high cost of synthesis and loss of dissolution of the titanium ion is still an obstacle. Chitrakar et al. by hydrothermal reaction synthesized Li1.6Mn1.6O4 and with 52 mg g−1 Li+ adsorption capacity [48]. By Xiao et al. synthesized spinel-structured hydrogen oxides of manganese, the saturated adsorption capacity of which was up to 42 mg g−1 [54]. 1-D MnO2 was synthesized with a maximum adsorption capacity reaching 46.34 mg g−1 in LiOH solution (C0 = 35 mg L−1) [50]. In this case, the dismutation reaction during etching can lead to distortion of the lattice and dissolution of manganese, which will violate its cyclicality.
In addition to lithium and magnesium, the treated salt lake brines may contain significant concentrations of potassium, sodium and boron. Zhou et al. compared the competitive sequences for several cations using TBP/FeCl3 in MIBK as the extractant [55, 56, 57]. However, quantitative correlations for competing for ion extractions, which are crucial in industrial design, were not reported.
The review is devoted to the extraction of lithium from brines, marine and geothermal waters, the collection of different methods of lithium extraction from water resources, which makes it possible to compare different methods that determine the optimal path for further research. Moreover, scientists around the world are challenged to find a way to extract lithium from water resources that are environmentally friendly, highly selective, economical, time-efficient and easy to process.
2. Lithium extraction
Lithium is comparatively abundant on the earth’s crust, being the affluent 25th more element [58]. More than 150 minerals contain lithium, in solid sediments, in geothermal waters, in many continental brines and in seawater. The concentration of lithium in seawater is very low, with an average of 0.17 ppm [3, 59]. The change in concentration from 1 to 100 ppm shows geothermal waters around the world [2, 4]. Although lithium deposits in all of the above forms are widespread throughout the world, only a very few are large enough and/or concentrated to potentially allow their exploitation. Several high-grade lithium minerals and brines are the only ones currently manufacturing at lithium extraction [2, 3, 4].
Interest in the recycling of lithium batteries has grown in recent years. However, recycling is still not economically attractive if compared with the mining of the raw materials [60]. Facilities for recycling are now available in the USA, Canada, Belgium, Germany and Japan. However, lithium availability from recycling is insignificant as compared with mined raw materials [61].
Figures for lithium resources and reserves differ considerably accordingly to the source, although there is unanimously agreement that lithium resources in brine are much larger than those in hard rock [2, 3, 4, 6]. The latest data from the U.S. Geological Survey show that total lithium resources (brine + hard rock) are 54.1 million tons. It was reported that the minimum and maximum reserves of lithium in hard rocks were 12.8 and 30.7 million tons, respectively; while the brine field data were reported as 21.3 and 65.3 million tons, respectively, for the minimum and maximum evaluation [3].
3. Lithium resources
In contradistinction to the uses of lithium, it is necessary to discuss the question of responsibility for Li from a variety of sources. The economic efficiency of lithium is found in minerals, clays and brines. High-grade lithium ores and brines are the current sources for all commercial lithium manufacture. Figure 1(a) demonstrates the distribution of lithium over different resources. The figure shows that continental brine is the largest resource (59%) for lithium, followed by solid rock (25%). Figure 1(b) demonstrates the spread of lithium across countries. The largest of the studied lithium deposits are in Bolivia and Chile. Figure 1(c) demonstrates the distribution of lithium production across countries. The main producers and exporters of lithium ores are Chile and Australia. Chile and China have huge resources of lithium ore. Canada, Russia, Serbia and Congo (Kinshasa) have lithium ores of about 1 million tons each, and equal reserve for Brazil is total 180,000 tons [62].
Figure 1.
The distribution of lithium (a) different natural resources, (b) worldwide distribution, (c) the number of producers around the world.
It is estimated that the earth’s crust contains an average of about 0.007% lithium. In nature, lithium does not occur freely, but it occurs in small quantities in almost all magmatic breeds and the ocean, in seawater, in the waters of many mineral springs. Of the approximately 20 known minerals containing lithium, only 4, that is, Lepidolite (KLi1.5Al1.5[Si3O10][F,OH]2), Spodumene (LiO2·Al2O3·4SiO2), Petalite (LiO2·Al2O3·8SiO2) and Amblygonite (LiAl[PO4][OH,F]) are known to occur in quantities sufficient for commercial interest as well industrial importance [63, 64, 65, 66]. The spodumen (LiAlSi2O6) mineral is the most significant industrial lithium ore mineral. Minerals of lithium also exist as cookeite as (LiAl4(Si3Al)O10(OH)8) in fine hydrothermal veins of quartz. Taeniolite (KLiMg2 Si4O10F2) is present in veins of smoky quartz in recrystallized novaculite, in manganese deposits the appearance of Lithiophorite ((Al, Li) Mn4+O2(OH)) is noted. Pegmatites, Taeniolite, Lithiophorite and Cookeite are considered to be economically inefficient sources of lithium [67, 68, 69]. A large part of the lithium is extracted from brine or seawater has a high concentration of lithium carbonate. In the earth’s crust, there are brines called continental brines/subsurface brines are the main source for the production of lithium (lithium carbonate). The literature reports that lithium is also present in seawater at about 0.17 mg L−1. Lithium is found in significant quantities in oil well brines and geothermal waters. These sources of brine and seawater are considered less expensive than mining from rocks such as spodumene, lepidolite, amblygonite and petalite containing lithium.
4. Lithium extraction from various resources
4.1 Lithium extraction from brine
Extracting lithium from brine is an important potential resource. When considered from an economic and scientific perspective, the following points are important to consider lithium recovery from brine: (1) suitability of pond soil and admissibility of the area for solar evaporation; (2) the concentration of lithium in brine; (3) the ratio of alkali metals and alkaline earth elements to lithium and (4) the complexity of the phase chemistry. The resources of brines containing lithium can be divided into three types: evaporative, geothermal and oilfield brines. In the process of evaporation of the brine about 50% of the original natural brine, lithium remains in the residual brine. This expression has been ascribed to the retention of lithium by precipitated salts. Residual brine is highly loaded with Mg2+ as compared with K+ and Na+, this makes it difficult to extract lithium from this residual brine [70].
The extraction of lithium from brine does not correspond to any general regularity since each process is specific depending on the composition of the brine field. Typical lithium production technology used for lithium extraction by Outotec®, where different methods such as precipitation, solvent extraction and flotation were used (Figure 2). Lithium extraction by Outotec® uses a lithium carbocation process to produce lithium [71]. Various lithium separation and purification methods have been reported in the literature, which is discussed below. By Chagnes and Swiatowska the general technological scheme of lithium production from brine and seawater is proposed [72]. In this method, liquid-liquid extraction, ion exchange, electrodialysis and adsorption are important hydrometallurgical processes necessary to concentrate lithium before production [72]. Table 1 discusses and summarizes the extraction of lithium from both brine and synthetic brine in various ways.
Figure 2.
Outotec lithium production technology from brine. Reproduced with permission from Outotec.
1-Alkyl-3-methylimidazolium-based ionic liquids (ILs), in which the alkyl chain lengths were 4-butyl (C4), 5-pentyl (C5), 6-hexyl (C6), 7-heptyl (C7), 8-octyl (C8) or 9-nonyl (C9)
Recovery of lithium from brines by various processes.
4.2 Recovery of lithium from brine by precipitation
Pelly et al., Epstein et al. and Kalpan et al. it has been reported that lithium recovery as precipitation of lithium aluminate from Dead sea brine and final brine [73, 74, 75]. Pelly et al. have reported, it is necessary to control the pH of the brine through dilution to achieve 90% extraction efficiency end brine and Dead sea brine [73]. As indicated, the optimal pH should be in the range of 6.6–7.2 For Dead sea brine and 6.8–7.0 for end brine. The optimum reaction time should be 3 hours at room temperature. AlCl3·6H2O (30–40 g L−1) was added to the brine. The negative effect was given by higher temperature, but better yields were obtained at room temperature and the yield decreased with increasing temperature [73]. The importance of extracting lithium from the Dead sea by precipitation as lithium aluminate followed by liquid-liquid extraction to separate lithium from aluminum with economic evaluation was reported [74]. Kaplan et al. reported on the process of extracting lithium by lithium aluminate from Dead sea brine by precipitation [75]. A small amount of lithium, which is mainly present as LiCl, was precipitated as a lithium aluminate precipitate using ammonia and aluminum salt at room temperature. Although subsequent reduction processes both by dissolving lithium in sulfuric acid and followed by precipitation with calcium chloride lithium were reduced as alum [75]. An et al. reported on the process of extracting lithium from brine collected in Salar de Uyuni, Bolivia. Mg and Ca were extracted from the brine as Mg(OH)2 and gypsum (CaSO4·2H2O) using sulfate and lime. Both CAO and MgO were extracted using oxalic acid followed by firing using residual Ca and Mg. In the end, by heating at 80–90°C lithium was recovered in the form of Li2CO3. As a result of precipitation processes with a high content of pure (99.55%) and crystalline Li2CO3 were reduced [93].
4.3 Ion-exchange method of lithium recovery from brine
Through the use of a specially made resin/aluminates composite/inorganic ion exchanger, from brine lithium can be recovered productively. Bukowski et al. reported through a process of carbocation and ion exchange an extract of pure LiCl from brines containing higher levels of CaCl2 and MgCl2 [77]. Three different ion exchange resins Y80-N Chemie AG (Chemie AG Bitterfeld-Wolfen)), TP207 resin (Bayer AG), (MC50 resin, (Chemie AG Bitterfeld-Wolfen) for lithium extraction from synthetic brine were investigated. As a result of the conducted researches, it is established that it is possible to clean LiCl solutions with Y 80 resin at room temperature and with TP 207 resin at 50°C [77]. Hui et al. synthesis of H2TiO3 ion exchanger and extraction of lithium from the brine of natural gas wells have been reported [76]. Ion exchanger H2TiO3 was synthesized from Li2CO3 and TiO2 or precipitation of LiOH and TiO2 followed by calcination at 400–800°C. Ion exchanger H2TiO3 provided high selectivity for Li+ at an exchange capacity of Li+ 25.34 mg g−1 in mixtures of alkaline earth metal and an alkali metal. From brine ion exchanger H2TiO3 showed 97% exchange rate and 98% elution rate for Li+ [76]. Chitrakar et al. reported with the same H2TiO3 ion exchanger extract lithium from Salt lake brine. Adsorption of lithium ions by H2TiO3 ion exchanger according to Langmuir model having exchange capacity for Li+ 25.34, 32.6 mg g−1 at pH 6.5 from brine was reported [53].
4.4 Liquid-liquid method of lithium recovery from brine
Many studies have provided my traditional liquid-liquid extraction and liquid-liquid extraction by ionic liquids (ILs) have been reported for lithium extraction from brine. Gabra et al. using synthetic solutions of nbutanol containing different amounts of lithium, potassium, calcium and sodium chloride, a laboratory-scale of LiCl extraction process were developed. A method for lithium reduction for separation and LiCl reduction is proposed, derived from distribution coefficients, separation coefficients and the presentation of McCabe-Thiel results. According to this method, 99.6% purity of LiCl can be restored [78]. Liquid-liquid extraction of lithium from brines by alcohol such as isoamyl alcohol and n-butanol, combined with precipitation of the lithium-aluminum complex reported by Bukowski et al. The amount of LiCl extraction from brine at pH 5.4 with different alcohol follow the order: 2-ethyl-1,3-hexanediol > isoamyl alcohol > di-isopropyl ether > diethyl ether and can extract 32.8, 25.2, 11.4, 9.1% lithium, respectively, along with Na, Mg and Ca. Lithium extraction was also studied using a binary mixture of the above compounds in a 1:1 ratio at a pH of 5.4. 2-ethyl-1,3-hexanediol mixed with isoamyl alcohol is suitable for 90% LiCl reduction as well as suppression of metal co-extraction [79]. Zhou et al. reported the extraction of lithium from brine sources using tributyl phosphate (TBP) in three different diluents [55]. Three salt solutions (ZnCl2, FeCl3 and CrCl3) were selected as co-extractors to investigate the possibility of extracting lithium metal from brine sources. The method of liquid-liquid extraction equilibrium of lithium with tributyl phosphate (TBP) in methylisobutyl ketone (MIBC), TBP in kerosene and TBP in 2-octanol was analyzed. In liquid–liquid extraction, lithium equilibrium is investigated by FeCl3 solution as a co-extractor. The results showed that the extraction efficiency followed the sequence: TBP/2-octanol < TBP/kerosene < TBP/MIBK. It was significantly larger than the TBP/2-octanol system than the TBP/MIBK and TBP/kerosene systems for lithium recovery [55]. A method for extracting lithium from neutral brines using beta-diketone and trioctyl phosphine oxide in benzene was patented by Baldwin and Seeley [80]. The mechanism of extraction was discussed in more detail with scientists [81].
4.5 Liquid-liquid extraction using ionic liquid method to extract lithium from brine
Unlike traditional liquid-liquid extraction, ionic liquid extraction is considered not only as a solvent but also as a co-extraction reagent. Gao et al. reported the extraction of lithium from salt lake brine using tri-isobutyl phosphate in ionic liquid and kerosene [82]. Three ionic liquids (ILs) have been reported, that is, 1-ethyl-3-methyl-imidazolium-bis[(trifluoromethyl)-sulfonyl]-imide, 1-butyl-3-methylimidazolium-bis[(trifluoromethyl)-sulfonyl]-imide and 1-butyl-3-methylimidazolium-hexafluorophosphate with triisobutyl phosphate (TIBP) and kerosene for ion recovery lithium from salt lake brine. The results show that the best selective lithium extraction was obtained using IL 1-ethyl-3-methylimidazole bis[(trifluoromethyl)-sulfonyl] imide. Under optimal extraction conditions, the one-stage efficiency of lithium ion extraction was 83.71% and the one-stage distillation efficiency was 85.61% at 1.0 mol L−1 HCl in 1.0 mol L−1 NaCl as a stripping agent at (O/A) = 2 [82]. Also, lithium extraction from brine is performed using imidazolium-containing ionic liquids with varying alkyl chain lengths in a series of ionic liquids based on 1-alkyl-3-methylimidazolium (ILs), in which the alkyl chain lengths are 4-butyl (C4), 5-pentyl (C5), 6-hexyl (C6), 7-heptyl (C7), 8-octyl (C8) or 9-nonyl (C9), in the presence of tri-isobutyl phosphate (TIBP) and kerosene systems presented by Gao et al. [83]. Studies have shown that the shorter the alkyl chain length of imidazolibased ILs, the higher the lithium recovery efficiency. Optimal lithium extraction can be achieved using ionic liquids based on n-butyl (C4) based on 1-alkyl-3-methylimidazoline (ILs). With a single contact of extraction and distillation, the efficiency of lithium extraction under optimal conditions was 74.14 and 86.37%, respectively. And the optimal condition was ionic liquids based on N-butyl-3-methylimidazole: TIBP: kerosene = 1:8:1 (vol/vol), pH = 5.0, O/A = 2.0 at the extraction stage using 1 mol L−1 HCl at O/A = 3 at the distillation stage [83]. Separation of lithium and magnesium from Salt lake brine by liquid-liquid extraction using ILs containing tributyl phosphate, reported Chenglong et al. [84, 85]. Tributyl phosphate (TBP), ILs and 1-octyl-3-methylimidazolium hexafluorophosphate, respectively, were used as the extraction medium and extractant for lithium extraction from Salt lake brine. The most suitable conditions for the extraction of this system were the ratio of TBP/ILs at 9/1(vol), O/A at 2:1. The pH of the brines of salt lakes is maintained constant. The obtained data show that the efficiency of single-stage extraction of lithium and magnesium was 80.64 and 5.30%, respectively. The total extraction efficiency of 99.42% was achieved by three-stage countercurrent extraction. With a one-stage method of removing lithium and magnesium, the efficiency was at A/O phase ratio of 298.78 and 99.15%, respectively, at 80°C. Provisional result showed that ILs has the potential to replace volatile organic solvents in liquid-liquid recovery of lithium cations [84]. At room temperature, ionic liquid solvent extraction of lithium cations using TBP was reported by Chenglong et al. The authors used TBP against the widely used ILs bis(trifluoromethylsulfonyl) imide and quantitative reduction of lithium [85].
4.6 Membrane process of extraction of lithium from brine
The extraction of lithium from brine by membrane method is a relatively modern and novel technology reported by various authors, which are discussed below. Through electroelectrodialysis with bipolar membranes, the production of lithium hydroxide from brines has been reported by Jiang et al. [86]. In a laboratory-scale process, a sequentially configured electro-electrodialysis with a bipolar membrane was installed with a permutation of the conventional electrodialysis stack. Standard electrodialysis stacks were reconfigured using five cation exchange membranes and four anion exchange membranes. With conventional electrodialysis and Na2CO3, through preconcentrating and precipitating brine, respectively, 98% pure Li2CO3 powder can be recovered. The authors investigated the influence of current density and raw material concentration on the production of lithium hydroxide (LiOH). Cost-effective was electro-electrodialysis with bipolar membranes at a current density of 30 mA/cm2 and a feed concentration of 0.18 MPa. Jiang et al. argued that the process is environmentally friendly and cost-effective [86]. The extraction of lithium from salt lake brine by membrane electrolysis was reported by Liu et al. [87]. Different technological parameters are optimized: the distance between the anode and the cathode, the initial concentration of lithium in the analyte, the electrolyte temperature, the electrolysis time and the surface density of the active substrate. The electrode demonstrates a remarkable Li+ 38.9 mg g−1 exchange capacity and an analyte pH value below 8.00 at optimal conditions [87]. Extraction of lithium from Dead sea brine by membrane separation using an ion-exchange hybrid process reported by Jagur-Grodzinski and Schori [88]. Lithium cations can be selectively permeated by solvent-polymer membranes. Better selectivity of Li+ transport by Mg2+ and Ca2+ gave membranes with (2-ethylhexyl)-diphenyl phosphate. No significant changes in membrane permeability and selectivity were observed during the 6 months of operation. Preliminary concentration of lithium and subsequent selective separation of lithium by membrane and ion exchange fusion were described by Jagur-Grodzinski and Schori. The expediency of lithium separation by combination of ion exchange process and membrane is substantiated [88]. The processes of concentration and separation of lithium from brine by reverse osmosis, nanofiltration was used. Sun et al. reported the isolation of lithium and magnesium from brine using a desalination nanofiltration membrane [89]. Magnesium lithium rejection rate was estimated by optimizing various operational parameters such as pressure, supply water temperature, pH and Mg2+ to Li+ ratio. Lithium extractions from salt lake brine using RO and NF processes have also been investigated. Studies show that the separation of magnesium and lithium was strongly dependent on the operating pressure, Mg2+/Li+ ratio and pH [89]. Lithium recovery from salt lake brine has been reported using NF and a low-pressure RO membrane by Somrani et al. [90]. Lithium selective membrane NF90 compared with XLE with low-pressure reverse osmosis membrane. For Li+ extraction, the NF90 membrane is more efficient than the XLE on the low pressure RO membrane due to its higher permeability to clean water and 0.1 m NaCl solution. A lower critical pressure (Pc = 0) and higher selectivity were obtained at a low operating transmembrane pressure (<15 bar) between monovalent cations (40%). Nf90 membrane showed 100% magnesium rejection in the initial step separation from dilute brine (15% for Li+, 10 times dilution). An 85% separation between Mg2+/Li+ was achieved in the final. Lithium can easily be separated by dialysis from the solution [90].
5. Lithium extraction from seawater
In the near future, to meet the needs of the world community in lithium, the ocean is considered the most important and promising resource for lithium [66]. It is reported that the total amount of lithium reserves in the oceans is approximately 2.6 × 1011 t [91]. Lithium extraction from hydromineral sources is carried out on a semi-industrial and industrial scale in the USA from salt lakes [66, 92, 94, 95], in Japan from thermal waters [96, 97], in Israel from the Dead sea [66, 73]. The extraction of lithium metal from geothermal and brine has also been studied in Russia, Germany, Bulgaria and Korea [98]. Typically, lithium is extracted from seawater by these two processes: (1) co-precipitation and extraction process and (2) ion exchange and sorption process.
Various methods have emerged with the development of technology, such as liquid-liquid extraction, a membrane process is used to extract lithium from seawater Table 2. The process of lithium extraction from both brine and synthetic brine has been considered and generalized through various processes such as liquid–liquid extraction, ion exchange and sorption, co-deposition and membrane processes.
Recovery of lithium from seawater by various processes.
5.1 Co-precipitation method for extracting lithium from seawater
Like other methods, it has not received wide application the extraction process of lithium recovery and extraction by co-precipitation. For lithium recovery, an important problem is the presence of higher concentrations of alkali and alkali metals in seawater. The alkali metal group has a very similar parameter, which creates problems for lithium recovery. The problems associated with lithium recovery from seawater and terrestrial hydromineral resources are very similar [66]. To extract lithium from seawater, various reagents such as potassium, iron sulfates and aluminum hydroxides, are successfully used to co-precipitate lithium [66, 96]. To obtain lithium concentrate, the dissolution of the co-precipitate after an ion exchange process is used. A hydrometallurgical process for extracting lithium from seawater using an adsorption process with a manganese oxide adsorbent followed by a deposition process reported by Um and Hirato [99]. By this method, at a temperature of (25–90°C), MgCl2 and CaCl2 from seawater were precipitated as Mg(OH)2 and Ca(OH)2. Using the NaOH, pH was managed between 7 and 14 with an initial concentration of CaCl2, MgCl2 and MnCl2 (10 and 100 mmol/dm3). Followed by the second stage Li2CO3 was recovered through carbonation using Na2CO3 by neutralization using HCl [99].
5.2 Ion exchange and sorption method for extracting lithium from seawater
Although various mega-industries are interested in extracting lithium from seawater in the present decade, extracting lithium from seawater has become increasingly attractive to researchers over several years through ion exchange and sorption. Several alternative methods of lithium extraction from seawater using ion-exchange after solar evaporation and fractional crystallization of NaCl, KCl and CaSO4 are also proposed. According to this method, organic and inorganic sorbents are similar to the compounds used to extract lithium. Reports explaining this method are discussed below. Obtained by treating a Dowex-1 type microporous anion exchanger with a lithium-selective aluminum-containing resin with a saturated solution of ammonia, AlCl3, and finally a solution of lithium halide before heating to produce a composite matrix of the microcrystalline resin LiX·2Al(OH)3 is an example of such products that have been patented in the United States [66, 116, 117]. High selectivity for lithium extraction was synthesized with sorbents based on antimony, tin, dioxides based on titanium and zirconium [118], mixed oxides of titanium and iron, titanium and chromium, titanium arsenate and magnesium and thorium [66]. To extract lithium from seawater, only manganese oxide-based cation exchange yields effective results in a wide range of lithium-selective ion exchange materials. Russian scientists use manganese oxide and mixed oxides of manganese and aluminum, known as ISM-1 and ISMA-1, respectively, to reduce lithium [66, 119]. For Li+ in mixtures of alkali metal and alkali metal ions, the H2TiO3 ion exchanger resulted in high selectivity. Achieving the exchange capacity of Li+ was 25–34 mg g−1. High selectivity for lithium cations by synthetic inorganic materials of titanium (IV) antimonate cation exchanger (TiSbA) ion exchange has been reported by Abe et al. Recovery of lithium cations from hydrothermal water as well as seawater can be successfully applied. Using the periodic method, the effect of K+, Mg2+ and Ca2+ cations on the adsorption of lithium cations on TiSbA has been reported by Abe et al. They showed that lithium adsorption decreases significantly with increasing concentrations of K+, Mg2+ and Ca2+ cations. Lithium from the sea and hydrothermal water is enriched through TiSbA columns. To separate lithium cations from seawater and hydrothermal water TiSbA exchanger potentially be reused. With HNO3 solution as the eluent, the adsorbed lithium can be eluted [120].
Selective extraction of lithium from seawater using two sequential ion exchange processes has been reported by Nishihama et al. [100]. By bench chromatographic operation with adsorbent k-MnO2, lithium was concentrated from seawater, which has a 33% lithium recovery efficiency. A combination of ion exchange using resin and solvent impregnated resin is carried out lithium purification from the concentrated liquor of the reference unit. The cleaning process consists of the removal of divalent metal ions with a strong acid cation exchange resin accompanied by the removal of Na+ and K+ with b-diketone/TOPO impregnated resin; finally, the reduction of Li+ as Li2CO3 precipitates using a saturated solution (NH4)2−CO3. According to the method, the concede was 56%, and the cleanness was 99.9% [100]. Takeuchi reported on a new method of extracting lithium from seawater, also supported [101]. At a temperature of 50°C, almost 70% for lithium ion recovery is achieved in a periodic mode with a high selectivity of the Al(OH)3 layer [101].
Several authors have reported that the extraction of lithium from seawater by sorption/desorption is a fairly common process, which is discussed below [108]. Many studies based on manganese oxide sorbate are used for the sorption/desorption of lithium from seawater. Japanese scientists have developed a sorbet based on hydrated c-oxides of manganese and mixed oxide of manganese and magnesium [102, 103]. By Ooi et al. lithium extraction from seawater using manganese oxide ion sieve (HMnO) was investigated. Maximum (7.8 mg g−1) absorption of lithium HMnO from seawater was achieved [102]. A study using ISMA-1 sorbents to extract lithium from seawater shows the following information: (1) The Li+ cation distribution ratio is 4 × 104. (2) Sorbents are easily regenerated by nitric acid. (3) They exhibit a high capacity for lithium cations of about 20 mg/m. (4) Lithium concentrates containing up to 1 g L−1 of lithium can be achieved under optimal conditions. A two stage scheme for obtaining Li2CO3 from seawater using this information of a pilot plant with a capacity of 3 m3 of seawater per hour has been developed and presented [66]. ISMA-1 sorbents provide higher chemical stability, but manganese oxide degradation associated with ion exchange remains the most serious drawback for their large-scale application in the lithium reduction process. A Japanese researcher developed a composite material by introducing a fine powder k-MnO2 with spinel structure into polyvinyl chloride to improve the kinetic properties of manganese oxide sorbents [121]. Sorbents ISM and ISM-1, synthesized in Russia, are also a composite material obtained using a polymer binder [66, 119]. In Korea, it has also been reported to recover lithium from seawater using an ion exchange type of manganese oxide adsorbent. To recover dissolved lithium in seawater a highly efficient ion exchange adsorbent was prepared according to their method. A highly efficient ion exchange type adsorbate was synthesized as a result of the solid state reaction of Li2CO3 and MgCO3. The ion sieve is formed after treatment of seawater with adsorbate, which is reduced by acid treatment. The lithium-ion sieve was produced by 3 cycles of 0.5 m HCl treatment with 24 h/cycle stringing, which shows 25.7 mg L−1 lithium absorption from artificial seawater [98]. Extraction of lithium from seawater by manganese oxide ion-sieve reported by Liu et al. The most promising method of industrial application was considered to be the extraction of lithium from seawater by adsorption using manganese oxide-ion sieves [104]. The sorption properties of HMnO in seawater and wastewater have been studied by Park et al. [105]. Lithium recovery from lake Urmia by the MnO2 ion sieve, where more than 90% lithium recovery can be achieved, was reported by Zandevakili et al. [122]. Wajima et al. studied the adsorption behavior of lithium from seawater using the adsorbent manganese oxide [106]. In studies using a pseudo-second-order kinetic model, a higher adsorption Kinetics of lithium cations in seawater was observed [106]. Reduction of lithium from seawater using manganese oxide adsorbent synthesized from Li1.6Mn1.6O4 precursor studied by Chitrakar et al. Manganese oxide adsorbent LiMnO2 was synthesized from H1.6Mn1.6O4 at 400°C by hydrothermal and reflux method. H1.6Mn1.6O4 was synthesized from precursor Li1.6Mn1.6O4. The sufficiently effective adsorbent can absorb lithium up to 40 mg g−1 from seawater [48].
5.3 Liquid-liquid extraction method of recovery of lithium from seawater
Scientists reported that liquid-liquid lithium extraction from seawater and liquid-liquid extraction are considered a potential process for extracting lithium from seawater. The use of liquid-liquid extraction to extract lithium from seawater is very limited, but the separation, purification and extraction of lithium by liquid-liquid extraction have been considered by several authors [81]. On the basis of the reference liquid-liquid extraction of lithium from seawater discussed below.
Scientists have used several extractants, such as primary alcohol C3-C5 and aliphatic alcohol C6-C8, to extract lithium from seawater, but the most effective and promising is Isobutanol. Japanese scientists have developed the most interesting method of extraction and in fact the most modern technology [107, 115]. In these methods, lithium is first extracted with cyclohexane and trioctyloxyphosphine, then the lithium reacts with hydrochloric acid and potassium phosphate, followed by lithium precipitation. The product obtained by this method has a purity of more than 95%. Synergistic extraction of lithium from seawater using a TTA-TOPO mixture has been reported by Harvianto et al. [123]. About 93% of the lithium can be recovered by TTA-TOPO. With acidic solutions, the lithium ion can be easily removed, but the removal efficiency decreases with increasing pH of acidic solutions. The type of acid does not affect the stripping efficiency. Similarly, by liquid-liquid extraction, 65% of lithium can be extracted from seawater, in the liquid-liquid extraction process, a magnesium ion is precipitated in advance. The recovery efficiency of lithium ions is negated by other metal ions in seawater [123].
5.4 Membrane process recovery of lithium from seawater
In recent years a number of authors have studied lithium recovery using different types of membranes. The membrane process of lithium reduction is a fairly advanced process that is gaining the attention of various researchers around the world.
Polysulfone (PSf)-based mixed matrix nanofiber dispersed with particulate lithium ion sieves as a flow-through membrane Li+ absorber has developed by Park et al. A mixed matrix of electro-spinning nanofibers was prepared by thermal annealing, where lithium-ion sieves were activated by acid pickling as Li0.67H0.96Mn1.58O4 or MO. PSF based mixed matrix nanofiber effectively improved Li+ selectivity. At minimal trans-membrane pressure, the mixed matrix nanofiber membranes were very permeable to water. By supporting the dynamic adsorption capacity of Li+ mixed matrix nanofibers, the shorter adsorption–desorption cycle time (24 h) was successfully controlled by continuous streaming operations. In a small volume of acid solution, Li+ enrichment was successfully achieved by repeated desorption of Li+ [115]. Recovery of lithium from seawater using an inorganic adsorbent containing a polymer membrane reservoir system, reported Chung et al. To extract lithium from seawater, Chung et al. used three different membranes: a PSf nonwoven membrane, a PSF nonwoven composite membrane and a Kimtex® composite membrane.
The proposed system has the advantage of direct application in the seawater eliminates the use of a pressurized flow system [124]. The proposed system can have a direct application in seawater using a pressure flow system. In addition, lithium extraction from seawater using an inorganic adsorbent containing a polymer membrane has been reported by Umeno et al. Lithium recovery from seawater desalination retentate using composite poly(acrylonitrile) nanofibers with H1.6Mn1.6O4 (HMO) lithium ion sieves was reported by Park et al. [110]. To obtain nanofibers, HMO/PAN dope solutions in N,N-dimethylformamide (DMF) with different HMO loads were used, and nanofibers were obtained by electrospinning. For efficient lithium extraction from seawater desalination retentate the material may be a potential membrane (Park et al.) [110]. The use of poly(vinyl chloride) (PVC) membrane adsorbent spinel-type manganese oxide by solvent exchange reported by Umeno et al. Poly(vinyl chloride) was dissolved in DMF solution, then lithium manganese oxide (spinel type) was mixed with DMF to obtain a suspension. The cured PVC film was prepared by applying a suspension to a thin film and immersed in water. To extract lithium obtained as a membrane type adsorbent the membrane was treated with HCl solution. Lithium extraction has been reported to be highly dependent on the method of preparation [109]. Hoshino reported on the recovery of lithium by dialysis and electrodialysis of seawater [111, 112, 113]. Selective extraction of lithium from seawater under laboratory conditions was investigated by electrodialysis using an ionic liquid (PP13-TFSI) impregnated with a membrane. The lithium recovery process was developed using a membrane process [112, 113]. Lithium extraction from seawater was selectively achieved by dialysis using a lithium ion superconducting membrane. For appropriate industrial lithium mass production applications, the dialysis process can be energy efficient and easily scalable [111]. Recovery of lithium by membrane desalination followed by crystallization was reported by Quist-Jensen et al. [114]. Extraction of lithium chloride and comparison of membrane crystallization in direct contact, vacuum and osmotic configuration were carried out. In their environment, the necessary supersaturation for crystallization was achieved for the simultaneous production of pure water and lithium by vacuum-membrane distillation [114].
6. Lithium ion-sieve effect
In 1971, ion-sieve oxides were first prepared by Volkhin et al. [125] since ion-sieve oxides have received increasing attention in the last few decades due to the special properties and performance as metal ions [126, 127, 128, 129, 130]. To extract specific metal ions with effective ion-sieve characteristics, ion-sieve oxides are fine adsorbents. Ion-sieve oxide adsorbents are obtained from corresponding precursors containing ions of the target metal. Characteristically, precursors are stable molecular structures, even if target ions are removed from their crystal sites, free crystal sites can still be retained. Thus, the resulting free crystal regions can only contain ions whose ionic radii are less than or equal to the radii of the target ions. In fact, only lithium ions can re-enter the free spaces of lithium ion sieves because lithium has the smallest ionic radius among all metal ions.
The study shows that only lithium ions can be adsorbed when LISs are placed in aqueous solutions containing different kinds of metal ions. Figure 3 shows how LIS works. The main stage is the formation of LIS with hydrogen filled state [LIS (H)] by removing lithium ions from the lithium filled state [LIS (Li)], principally through Li-H ion exchange, then the adsorption isolation of lithium ions LIS from Li+-containing solutions based on the steric effect. The spent LIS (H) is then regenerated to form LIS (Li) by adsorption of lithium ions. In General, the process can be called “LIS effect” [131, 132, 133, 134, 135].
Figure 3.
Schematic representation of LIS process.
7. Lithium ion-sieve
In fact, two types of chemical elements can be used, such as LISs, lithium manganese oxide type (LMO type) and lithium titanium oxide type (LTO type). LMO-type LISs are the most popular selective lithium adsorbents at present because of superior lithium absorption abilities, magnificent regeneration performance and high lithium selectivity. In addition, the extraction of lithium from aqueous solutions has recently improved significantly through the use of electrochemical methods. However, the LISs type suffers from the dissolution of manganese in aqueous solutions, which in industrial conditions can lead to serious water contamination. In this regard, LISs type LTO can overcome this problem, can be easily removed from the aqueous solution, and titanium compounds are not harmful to the aquatic environment [136, 137, 138]. In addition, LTO-type LISs has much more stable molecular structures due to the high energy of the titanium-oxygen bond compared with LMO-type LISs. But when an electrical potential is applied LISs of type LTO have limited use in extracting lithium from an aqueous solution. This restriction may prevent future industrial use of LISs type LTO. Thus, LMO-type and LTO-type LISs have their own unique benefits and problems. Therefore future research to meet large scale industrial applications may focus on minimizing their respective disadvantages.
7.1 Lithium recovery by LMO type lithium-ion sieves
7.1.1 Study of ternary phase diagram of Li-Mn-O
With research [44], several LMO-type LISs have been well developed by many scientists [48]. As a rule, their precursors demonstrate a spinel structure. Because of multiple valence states of manganese, several lithium manganese oxides with different crystal structures can be formed. At 25°C, the phase diagram Li-Mn-O shows the isothermal cross-section Figure 4 [139, 140, 141, 142, 143].
Figure 4.
(a) An isothermal cross section of the Li-Mn-O phase diagram at 25°C and (b) an expanded region of the Li-Mn-O phase diagram.
In the blue area in Figure 4a, the stoichiometric spinel phase defect is defined by the triangle Mn3O4·Li4Mn5O12·λ-MnO2. Using the general formula LixMn3−xO4 (0 ≤ x ≤ 1.33), one can imagine the stoichiometric spinel phases lying on the bond between Mn3O4 and Li4Mn5O12. According to the general formula Mn3−xO4 (0 ≤ x ≤ 1) defective spinels of manganese oxides located between Mn3O4 and λ-MnO2 are presented. In accordance with the general formula Li2O·yMnO2 (y > 2.5), the defect of lithium-manganese-oxide spinel is expressed and the communication line lies between Li4Mn5O12 and λ-MnO2. At this point, in LiMn2O4·Li2Mn4O9·Li4Mn5O12 the blue triangle in Figure 4b is the active area for preparing the precursors of LMO-type LISs. Therefore, it is possible to obtain high Li-Mn precursors such as Li5Mn4O9 and Li7Mn5O12 in principle, implying that high Li+ capacity LISs may be obtained in the future.
Currently, only a few LMO-type LIS precursors with high Li+ adsorption capacities such as λ-MnO2, MnO2·0.31H2O and MnO2·0.5H2O, which are derived from LiMn2O4, Li4Mn5O12 and Li1.6Mn1.6O4, respectively, were prepared. As shown in Figure 5, a phase diagram consisting of additional proton-type manganese oxides depending on the valence state of manganese, molar Li/Mn and H/Mn ratios constructed by Chitrakar et al. [47].
Figure 5.
Phase diagram of LMO and their delithiated products [47]. Reproduced from Ref. [47].
As shown in the figure, LIS precursors of the LMO-type can be classified into two types of reactions and are represented in two perpendicular planes: the vertical plane represents the redox reaction region, and the horizontal plane represents the ion exchange region. Table 3 mainly summarizes their main properties for the absorption of lithium from aqueous solutions.
400 times higher conc. of Li+ could be achieved while most of Na+ remains in artificial seawater that contains 10 ppm of Li+ and 10,000 ppm of Na+ by chromatographic separation
7.1.2 The spinel structure of the precursors of LMO
Inevitably, the chemical properties depend on the chemical structures to be determined, so the extraction of lithium by LMO precursors is explained by their peculiar chemical structure. Actually, all synthesized precursors of LMOs have spinel structures [144, 145, 146, 147, 148, 149, 150, 151, 152]. Among these, the LiMn2O4 structure is the most representative one, as shown in Figure 6.
Figure 6.
Promising type (a) cubic core in spinel unit cell LiMn2O4, (b) LiMn2O4 of extended three-dimensional frame structure and (c) λ-MnO2 with voids after Li ions removal. Green, pink and red represent Li, Mn and O atoms, respectively [146].
Spinel LiMn2O4 has a cubic crystal structure that belongs to the spatial group Fd3m. The structure shows that the tetrahedron’s 8a sites occupy lithium ions. At a molar ratio of 1:1, Mn3+ and Mn4+ ions are randomly distributed over 16d sites of octahedra, and oxygen anions occupy 32e sites of the face-centered cubes. Accordingly, the formula (Li)8a[Mn(III)Mn(IV)]16dO4 can be represented by spinels LiMn2O4, which can be described by the general spinel formula (AB2O4). From other side, the LiMn2O4 unit cell can be viewed as a complex cubic structure: oxygen atoms are 32 and 16 manganese atoms occupy half of the octahedral pore (16d), while the other half of the sections (16c) are free. Here are 8 of the lithium atoms occupy 1/8 of tetrahedral interstices plot (8a). Li+ can intercalate/deintercalate in three-dimensional networks of free octahedral and octahedral gaps along the 8a-16c-8a-16c channel, what is the structural basis of Li+ intercalation/deintercalation in LiMn2O4 spinel [145].
The 1:2 ratio shows a spinel LiMn2O4 of the two metal cations Li and Mn; although the stoichiometric proportion may be somewhat weakened in some circumstances. For example, in Figure 7 it is shown that manganese ions in 16d sites can be replaced by lithium ions without changing the entire crystal framework.
Figure 7.
(a) Cubic spinel lithium manganese oxide quadrants were comparison and (b) recorded under the 8.6 GPa. C, cubic spinel phase (spatial group Fd3m); W, tungsten strip model of polyhedral structure and structure refinement by Rietveld X-ray diffraction powder sample for Li1.33Mn1.67O4 (or Li4Mn5O12).
Since more lithium ions can be extracted or inserted, the corresponding LIS of the substituted precursor Li1.33Mn1.67O4 (or Li4Mn5O12) is theoretically a higher lithium capacity than λ-MnO2. Ammundsen et al. [148] the results of neutron diffraction studies of the lithium reinsertion process are given only for tetrahedral sites and not for octahedral sites, which indicates that the lithium extraction/insertion reaction can be expressed by the equation below:
LiLi0:33Mn1:67O4+H+↔HLi0:33Mn1:67O4+Li+E1
Another typical lithium-rich precursor to LMO is Li1.6Mn1.6O4 (or Li2Mn2O5), which are relevant LIS is MnO2·0.5H2O. Among all available manganese, LISs MnO2·0.5H2O has the highest theoretical lithium capacity (ca. 72.3 mg g−1). With this composition, the ratio of cations and anions (4:5) differs from that of typical spinel compounds (3:4), meaning that additional lithium ions are likely to be found in interstitial regions of the spinel structure with a single-digit arrangement [143]. Chitrakar et al. [47] proposed three hypothetical models through a preliminary Rietveld analysis, since there is still no published structural model for Li1.6Mn1.6O4: (1) (Li)8a[Li0.2]16c[Li0.4-Mn1.6]16dO4 site at the of 16c model with excess Li; (2) a (Li)8a[Li0.5Mn1.5]16dO3.75 model with oxygen deficiency and (3) a hexagonal lattice model with cation deficiency (Li0.8□0.2)3b(Mn0.8□0.2)3aO2 (the “□” are the free areas in the spinels). The modulation results showed that all models traced the X-ray peaks of the heat-treated sample, but the third model (a hexagonal lattice with a deficit of cations) accurately traced the relative intensity of the X-ray peaks. By Ariza et al. [147] showed that X-ray absorption spectroscopy of Li1.6Mn1.6O4 samples does not result in the complete displacement of the manganese absorption edge after lithium extraction/reintroduction. In addition, the structural arrangement and oxidation state of manganese remained unchanged during lithium extraction and re-administration, confirming the ion exchange mechanism for lithium extraction and re-administration. Thus, there is still some disagreement on the crystal structure of Li1.6Mn1.6O4. Possible future research by scientists should focus on this issue to link the development of LIS to the excellent absorption properties of lithium.
7.1.3 The doping modification
Because of the specific configuration of the 3d electron orbit,
Mn3+ can cause the Jahn-teller effect, which can cause severe distortions in the octahedral structure of MnO6. This distortion will be accompanied by a decrease in LMO stability and a decrease in the efficiency of the intercalation/deintercalation process of Li+ [153, 154, 155, 156, 157]. Much more seriously in industrial operations dissolving large amounts of manganese in water can lead to water contamination. Consequently, some alloying modifications have been proposed to replace Mn3+ with other metal ions, which is more efficient.
In the field of lithium-ion batteries, a wide variety of cation substitution (including Co2+, Ni2+, Cr3+, Mg2+, Al3+, Fe3+ and ions of rare earth element) has been applied to inhibit capacity fading and improve electrochemical performance [158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183]. Analogously, modifications of LIS by doping with metal ions to improve the absorption properties of lithium in aqueous solutions are proposed. The effect of LimMgxMn(III)yMn(IV)zO4 (0 ≤ x ≤ 0.5) on the dissolution of manganese within acid treatment, the results showed that the adsorption capacity of lithium and the chemical stability of protonated samples increased with the mg/MN ratio studied by Chitrakar et al. [181]. Mild chemical method of Mg2+ doped lithium-manganese spinel synthesized by Tian et al. [36]. During the periodic experiment, it was found that the sorption of Li+ showed a high pH and a dependence profile of the initial concentration. In addition, kinetic experiments have shown that the adsorption process followed by a pseudo-second-order model. Li+ extraction process in both compound LiMg0.5Mn1.5O4 spinel and LiZn0.5Mn1.5O4 spinel studied by Feng et al. [182, 183]. Discovered that the extraction and insertion of Li+ are topotaxically through ion exchange mechanisms. In addition, with LiAlMnO4 and LiFeMnO4 spinel Li+ extraction/insertion reactions in the aqueous phase, also follow the ion exchange mechanisms tested by Liu et al. [184]. LiMxMn2-xO4 spinel series (M = Ni, Al, Ti; 0 ≤ x ≤ 1) and comparison of their lithium reduction properties in aqueous solutions prepared by Ma et al. [185]. Studies have shown that LiAl0.5Mn1.5O4 spinels exhibit relatively high Li extraction coefficient and relatively low Mn and Al extraction coefficients when treated with acid, and LiNi0.5Mn1.5O4 and LiTi0.5Mn1.5O4 spinels do not exhibit satisfactory Li+ extraction and adsorption properties because of substantial cell contraction or expansion. By Chitrakar et al. Sb-doped LMO spinel was synthesized for the first time [186]. Samples received Li1.16Sb(V)0.29Mn(III)0.77Mn(IV)0.77O4 was a well-crystallized spinel-type structure, in the following order of affinity K < Na ≪ Li and exchange capacity reaching 5.6 mmol g−1 for Li+. In a subsequent study, a series of Li-Sb-Mn composite oxides with various Sb/Mn molar ratios by solid-state reactions obtained by Ma et al. [187]. Studies have shown that the molar ratio Sb/Mn of composite oxides Li-Sb-Mn is a decisive factor in the identification of their structure and extraction-adsorption properties Li+. Hereinafter, the acid-treated composite spinel oxide Li-Sb-Mn with a molar ratio Sb/Mn of 0.05 showed in lithium solution a high adsorption capacity of Li+ 33.23 mg g−1. By Chitrakar et al. the ion-exchange property of iron-doped lithium manganese oxides Li1.33FexMn1.67-xO4 (x = 0.15, 0.30 and 0.40) in Bolivian brine was studied [38]. Studies have shown that the adsorbent with a Fe/Mn ratio of 0.1, obtained by calcining the precursor at 450°C, has the highest extractability of lithium with HCl solution. Finally, from crude brine at a final pH of 2.0, the adsorbent showed lithium absorption of 18.1 mg g−1 with an increase in absorption to 28 mg g−1 at a final pH of 7.2 after adding 1 mol L−1 NaOH l-1 solution to the crude brine.
Study of the description of the LMO-doped spinels, it is obvious that doping modifications can effectively improve the adsorption properties of lithium. Nevertheless, little attention has been paid to refining LIS compared with the great progress of ion-doped manganese oxide spinels in the field of electrochemistry. At present, just several studies of LISs doped with a single metal have been studied. Lithium adsorption property of multicharged ions doped LISs, including several cation-doped, several anion-doped and cation-anion-doped LISs in aqueous solution, still an untouched area for research. Early research of numerous ion-doped LiMn2O4 showed high capacity retention, high discharge capacity, and lithium ion batteries good cycling performance. This is due to the fact that multiple ions doped LiMn2O4, have increased structural stability [188, 189, 190, 191, 192, 193, 194, 195, 196, 197]. Besides, as cathodes, co-doping has a synergistic effect on increasing the cyclic durability of materials, which can for single ion-doped LiMn2O4 discourage all factors responsible for capacity loss [198, 199, 200, 201]. Similarly, it has been convincingly shown that multiple ion doping has a beneficial effect on improving the regeneration efficiency and absorption capacity of lithium LISs in aqueous solutions. Prospective studies should focus on the synergistic effects of different ions on the reductive properties of lithium.
7.2 About LTO-type LISs
There are currently two categories of LTO-type LISs: layered structure H2TiO3 and spinel structure H4Ti5O12. Albeit the amount of LTO-type LISs is confined, there is great potential to develop these green lithium adsorbents for application in the industry, avoiding water pollution.
7.2.1 Study of layered H2TiO3 LISs
The chemical structure of layered H2TiO3 is shown in Figure 8. From the layered precursor Li2TiO3 a layered H2TiO3 is obtained. One can better describe as Li[Li1/3Ti2/3]O2 the crystal structure of this precursor; precisely, when metal atoms are placed in octahedral voids the structure can be represented as cubic close packed oxygen atoms. In the structure of Li2TiO3 two types of layers form Li and Ti. The first layer (Li) is inhabited only by lithium atoms, while the other layer (LiTi2) occupies Li 1/3 and Ti 2/3. In fact, in the structure of Li2TiO3, lithium ions in the layers make up 75% of the total amount of lithium, while the surviving 25% are in layers (LiTi2) [53].
Figure 8.
Crystal structure of Li4Ti5O12 (yellow tetrahedra represent lithium, and green octahedra represent disordered lithium and titanium) [39]. Reproduced from Ref. [39].
Accordingly, whole lithium ions are changed by protons in the layered structure of H2TiO3. Accordingly, in early studies, some researchers believed that the structure of H2TiO3 was converted from layered Li2TiO3 by topotactic substitution of lithium ions by protons. The authors explore the composition of H2TiO3 by reviewing the variation among Li2TiO3 and H2TiO3 and modeling the XRD patterns of HxLi2−xTiO3 (0 ≤ x ≤ 2), they pointed out that a structure with a layered double hydroxide type with a sequence of 3R1 oxygen layers is more acceptable for H2TiO3, and H2TiO3 can be described as laying charge-neutral metal oxyhydroxide plates [(OH)2OTi2O(OH)2] [202]. In advanced research, requires additional experimental testing to confirm the well-honed structure.
In 1988, Onodera et al. first obtained Li2TiO3 [203], many kinds of research have been conducted on its electrochemical application [204, 205, 206, 207, 208] and in the degradation of pollutants the photocatalytic applications [209, 210, 211]. Chitrakar et al. investigated the behavior of ion exchange in salt lake brines [53]. While the rate of adsorption of lithium was relatively slow (it took 1day to reach equilibrium at room temperature), at pH 6.5 the capacity of the Li+ can reach up to 32.6 mg g−1, that is among the adsorbents of lithium the greatest value is studied in an acidic solution. Besides, H2TiO3 has been found to be able to efficiently absorb lithium ions from Na+, K+, Mg2+ and Ca2+ containing competitive cations in brine. With ionic radii exceeding Li+ (0.074 nm), it is not possible to introduce sites into the LTO adsorbent, since exchange sites have radii sizes Na+ (0.102 nm), K+ (0.138 nm) and Ca2+ (0.100 nm), which do not allow adsorption due to the large size of the ionic radii. Although the ionic radius of Mg2+ (0.072 nm) is close to the ionic radii of Li+, dehydration of magnesium ions requires high energy to enter the exchange nodes, since the free hydration energy for Mg (∆G0h = −1980 kJ mol−1) is four times greater than for Li (∆G0h = −475 kJ mol−1) [212]. In addition, the Li-Mg separation ratio reached 102.4 on the 8th adsorption cycle, that in salt lake brines represents the excellent separation of Li+ and Mg2+ found by Shi et al. [40]. In designing the orthogonal test, the maximum absorption of lithium by H2TiO3 reached 57.8 mg g−1 at the optimal state studied by He et al. [213].
7.2.2 Study of spinel titanium oxides
The LTO-type LISs represent the different types of spinel titanium oxides that are derived from spinel precursors Li4Ti5O12. In the field of lithium-ion batteries, spinel Li4Ti5O12 is seen as one of the most promising future anode candidates for large-scale lithium-ion batteries used for hybrid electric vehicles or power electric vehicles. Through high efficient due to high potential during charge and discharge of about 1.55 V (vs. Li/Li+), good cycle property and good heat resistance and security [214, 215, 216]. There is great potential for the development of spinel Li4Ti5O12 in the extraction of lithium from aqueous solutions. High capacity lithium has on LIS (H4Ti5O12) and due to stronger Ti–O bond cycling performance is better than that of manganese-type LISs. Withal, Li4Ti5O12 has an identical chemical structure like Li4Mn5O12 (Figure 9).
Figure 9.
Schematic representation in spinel manganese oxides by the composite mechanism (a) Li+ extraction reactions and (b) Li+ insertion reactions.
Nevertheless, as far as we know, there are currently very limited reports on the property of extracting lithium from H4Ti5O12. A three-dimensionally ordered precursor to nano Li4Ti5O12 using colloidal PMMA crystal matrices developed by Dong et al. [217]. High selectivity for Li+, 56.81 mg g−1 showed corresponding ion sieve and good stability to acid. LISs H4Ti5O12 with nanotube morphology synthesized by an ordinary two-stage hydrothermal process presented a lithium capacity of 39.43 mg g−1 in a 120 mg L−1 in lithium solution reported by Moazeni et al. [39].
8. Conclusions
Lithium is one of the rarest metals with various applications and the demand for lithium will increase with the ever-increasing use of electric and electronic devices and hybrid electric vehicles.
Therefore, the search for ways to obtain lithium from water sources suitable for the production of lithium compounds is a serious and very important problem.
Various methods have been given in the literature for lithium recovery from brines, seawater and geothermal water: including precipitation, solvent extraction, selective membrane separation, liquid-liquid extraction, ion exchange adsorption, electro dialysis and so on.
The recovery of lithium by the absorption method shows promising results for future production. Because of the adsorption method, evaporation, crystallization process can be avoided. That is why it is necessary to develop and recommend a technically and economically feasible, environmentally friendly and sustainable process.
Scientists and manufacturers are faced with the task to solve several problems: the ion sieve has a relatively low ion exchange capacity and weak stability; lithium absorption reaches from 16 to 26–28 mg g−1, the theoretical adsorption capacity is 54 mg g−1; dissolution of sorbents. Weight loss was observed in almost all compositions; low stability during cycling; the appearance of secondary waste in the regeneration of acids; the process takes a long time.
To solve this problem, scientists of the world have carried out many scientific works to improve the stability of sorbents, increase the absorption capacity, selectivity, acceleration of sorption time, for this purpose, many methods were used, including organic chemicals, synergies, binders, various composites. But none of them makes it possible to industrialize the method of lithium adsorption. That is why there is still a goal to find ways to improve the method of lithium adsorption. Lithium adsorption extraction may be an alternative option to meet future demand, energy sustainability, environment and circular economy.
Acknowledgments
The authors gratefully acknowledge partial financial supports from the National Natural Science Foundation of China (U1607123 and 21773170), the Key Projects of Natural Science Foundation of Tianjin (18JCZDJC10040), the Major Special Projects of Tibet Autonomous Region (XZ201801-GB-01) and the Yangtze Scholars and Innovative Research Team of the Chinese University (IRT_17R81).
\n',keywords:"thermodynamics, lithium energy, lithium recovery, adsorption, precipitation, membrane process",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/70887.pdf",chapterXML:"https://mts.intechopen.com/source/xml/70887.xml",downloadPdfUrl:"/chapter/pdf-download/70887",previewPdfUrl:"/chapter/pdf-preview/70887",totalDownloads:1250,totalViews:0,totalCrossrefCites:1,dateSubmitted:"September 2nd 2019",dateReviewed:"November 4th 2019",datePrePublished:"January 21st 2020",datePublished:"July 29th 2020",dateFinished:"January 21st 2020",readingETA:"0",abstract:"Demand to lithium rising swiftly as increasing due to its diverse applications such as rechargeable batteries, light aircraft alloys, air purification, medicine and nuclear fusion. Lithium demand is expected to triple by 2025 through the use of batteries, particularly electric vehicles. The lithium market is expected to grow from 184,000 TPA of lithium carbonate to 534,000 TPA by 2025. To ensure the growing consumption of lithium, it is necessary to increase the production of lithium from different resources. Natural lithium resources mainly associate within granite pegmatite type deposit (spodumene and petalite ores), salt lake brines, seawater and geothermal water. Among them, the reserves of lithium resource in salt lake brine, seawater and geothermal water are in 70–80% of the total, which are excellent raw materials for lithium extraction. Compared with the minerals, the extraction of lithium from water resources is promising because this aqueous lithium recovery is more abundant, more environmentally friendly and cost-effective.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/70887",risUrl:"/chapter/ris/70887",signatures:"Samadiy Murodjon, Xiaoping Yu, Mingli Li, Ji Duo and Tianlong Deng",book:{id:"8572",title:"Thermodynamics and Energy Engineering",subtitle:null,fullTitle:"Thermodynamics and Energy Engineering",slug:"thermodynamics-and-energy-engineering",publishedDate:"July 29th 2020",bookSignature:"Petrică Vizureanu",coverURL:"https://cdn.intechopen.com/books/images_new/8572.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",isbn:"978-1-83880-569-2",printIsbn:"978-1-83880-568-5",pdfIsbn:"978-1-83880-570-8",editors:[{id:"12354",title:"Prof.",name:"Petrică",middleName:null,surname:"Vizureanu",slug:"petrica-vizureanu",fullName:"Petrică Vizureanu"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Lithium extraction",level:"1"},{id:"sec_3",title:"3. Lithium resources",level:"1"},{id:"sec_4",title:"4. Lithium extraction from various resources",level:"1"},{id:"sec_4_2",title:"4.1 Lithium extraction from brine",level:"2"},{id:"sec_5_2",title:"4.2 Recovery of lithium from brine by precipitation",level:"2"},{id:"sec_6_2",title:"4.3 Ion-exchange method of lithium recovery from brine",level:"2"},{id:"sec_7_2",title:"4.4 Liquid-liquid method of lithium recovery from brine",level:"2"},{id:"sec_8_2",title:"4.5 Liquid-liquid extraction using ionic liquid method to extract lithium from brine",level:"2"},{id:"sec_9_2",title:"4.6 Membrane process of extraction of lithium from brine",level:"2"},{id:"sec_11",title:"5. Lithium extraction from seawater",level:"1"},{id:"sec_11_2",title:"5.1 Co-precipitation method for extracting lithium from seawater",level:"2"},{id:"sec_12_2",title:"5.2 Ion exchange and sorption method for extracting lithium from seawater",level:"2"},{id:"sec_13_2",title:"5.3 Liquid-liquid extraction method of recovery of lithium from seawater",level:"2"},{id:"sec_14_2",title:"5.4 Membrane process recovery of lithium from seawater",level:"2"},{id:"sec_16",title:"6. Lithium ion-sieve effect",level:"1"},{id:"sec_17",title:"7. Lithium ion-sieve",level:"1"},{id:"sec_17_2",title:"7.1 Lithium recovery by LMO type lithium-ion sieves",level:"2"},{id:"sec_17_3",title:"Table 3.",level:"3"},{id:"sec_18_3",title:"7.1.2 The spinel structure of the precursors of LMO",level:"3"},{id:"sec_19_3",title:"7.1.3 The doping modification",level:"3"},{id:"sec_21_2",title:"7.2 About LTO-type LISs",level:"2"},{id:"sec_21_3",title:"7.2.1 Study of layered H2TiO3 LISs",level:"3"},{id:"sec_22_3",title:"7.2.2 Study of spinel titanium oxides",level:"3"},{id:"sec_25",title:"8. Conclusions",level:"1"},{id:"sec_26",title:"Acknowledgments",level:"1"}],chapterReferences:[{id:"B1",body:'Ji Z-Y, Yang F-J, Zhao Y-Y, Liu J, Wang N, Yuan J-S. Preparation of titanium-base lithium ionic sieve with sodium persulfate as eluent and its performance. Chemical Engineering Journal. 2017;328:768-775'},{id:"B2",body:'Kesler SE, Gruber PW, Medina PA, Keoleian GA, Everson MP, Wallington TJ. 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Journal of Power Sources. 2010;195:3293-3299'},{id:"B179",body:'Singh P, Sil A, Nath M, Ray S. Synthesis and characterization of Li[Mn2-xMgx]O4 (x = 0.0-0.3) prepared by sol-gel synthesis. Ceramics-Silikáty. 2010;54:38-46'},{id:"B180",body:'Liu Q , Wang S, Tan H, Yang Z, Zeng J. Preparation and doping mode of doped LiMn2O4 for Li-ion batteries. Energies. 2013;6:1718-1730'},{id:"B181",body:'Chitrakar R, Yoji M, Kenta O, Akinari S. Magnesium-doped manganese oxide with lithium ion-sieve property: Lithium adsorption from salt lake brine. Bulletin of the Chemical Society of Japan. 2013;86:850-855'},{id:"B182",body:'Feng Q , Kanoh H, Miyai Y, Ooi K. Li+ extraction/insertion reactions with LiZn0.5Mn1.5O4 spinel in the aqueous phase. Chemistry of Materials. 1995;7:379-384'},{id:"B183",body:'Feng Q , Miyai Y, Kanoh H, Ooi K. Lithium(1+) and magnesium(2+) extraction and lithium(1+) insertion reactions with lithium magnesium manganese oxide (LiMg0.5Mn1.5O4) spinel in the aqueous phase. 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Preparation and characterization of spinel LiNi0.5-xMgxMn1.5O4 cathode materials via spray pyrolysis method. Journal of Power Sources. 2013;244:35-42'},{id:"B189",body:'Yang MC, Xu B, Cheng JH, Pan CJ, Hwang BJ, Meng YS. Electronic, structural, and electrochemical properties of LiNixCuyMn2−x−yO4 (0 < x < 0.5, 0 < y < 0.5) high-voltage spinel materials. Chemistry of Materials. 2011;23:2832-2841'},{id:"B190",body:'Verrelli R, Scrosati B, Sun YK, Hassoun J. Stable, high voltage Li0.85Ni0.46Cu0.1Mn1.49O4 spinel cathode in a lithium-ion battery using a conversion-type CuO anode. ACS Applied Materials & Interfaces. 2014;6:5206-5211'},{id:"B191",body:'Kim W-K, Han D-W, Ryu W-H, Lim S-J, Eom J-Y, Kwon H-S. Effects of Cl doping on the structural and electrochemical properties of high voltage LiMn1.5Ni0.5O4 cathode materials for Li-ion batteries. Journal of Alloys and Compounds. 2014;592:48-52'},{id:"B192",body:'Ebin B, Gürmen S, Lindbergh G. Preparation and electrochemical properties of spinel LiFexCuyMn1.2O4 by ultrasonic spray pyrolysis. Ceramics International. 2014;40:1019-1027'},{id:"B193",body:'Li R, Gong F, Wang W. Co-precipitation synthesis and performance of multi-doped LiCrxNixMn2−2xO4−2F2 cathode materials for lithium ion batteries. Ionics. 2006;12:353-363'},{id:"B194",body:'Sang HP, Park KS, Yang KS, Nahm KS. Synthesis and characterization of a new spinel, Li1.02Al0.25Mn1.75O3.97S0.03, operating at potentials between 4.3 and 2.4 V. Journal of the Electrochemical Society. 2000;147:2116-2121'},{id:"B195",body:'Sun YK, Park GS, Lee YS, Yoashio M, Nahm KS. Structural changes (degradation) of oxysulfide LiAl0.24Mn1.76O3.98S0.02 spinel on high-temperature cycling. Journal of the Electrochemical Society. 2001;148:A994-A998'},{id:"B196",body:'Xiao J, Zhu H-L, Chen Z-Y, Peng Z-D, Hu G-R. Preparation and property of spinel LiMn2O4 material by co-doping anti-electricity ions. 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Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries. Ionics. 2008;15:233-239'},{id:"B202",body:'Yu C-L, Wang F, Cao S-Y, Gao D-P, Hui H-B, Guo Y-Y, et al. The structure of H2TiO3-a short discussion on “lithium recovery from salt lake brine by H2TiO3”. Dalton Transactions. 2015;44:15721-15724'},{id:"B203",body:'Onodera Y, Iwasaki T, Hayashi H, Torii K. A new inorganic material with high selective adsorbability for lithium ions. Chemistry and Industry (London). 1988(24):786'},{id:"B204",body:'Aceves JM, West AR. Electrochemical decomposition of Li4SiO4 and Li2TiO3 in solid-state thermal cells. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 1982;78:2599-2608'},{id:"B205",body:'Johnson CS, Kim J-S, Kropf AJ, Kahaian AJ, Vaughey JT, Thackeray MM. Structural and electrochemical evaluation of (1-x)Li2TiO3·(x)LiMn0.5Ni0.5O2 electrodes for lithium batteries. Journal of Power Sources. 2003;119-121:139-144'},{id:"B206",body:'Zhao E, Liu X, Hu Z, Sun L, Xiao X. Facile synthesis and enhanced electrochemical performances of Li2TiO3-coated lithium-rich layered Li1.13Ni0.30Mn0.57O2 cathode materials for lithium-ion batteries. Journal of Power Sources. 2015;294:141-149'},{id:"B207",body:'You NK, Yun CK, Park SB. Preparation and electrochemical properties of nanometer-sized Li2TiO3-LiCrO2 nanocomposite cathode powders by spray pyrolysis. International Journal of Electrochemical Science. 2013;8:2504-2514'},{id:"B208",body:'Chauvaut V, Cassir M. Behaviour of titanium species in molten Li2CO3 + Na2CO3 and Li2CO3 + K2CO3 in the anodic conditions used in molten carbonate fuel cells: II. Electrochemical intercalation of Li+ in Li2TiO3 at 600 and 650 °C. Journal of Electroanalytical Chemistry. 1999;474:9-15'},{id:"B209",body:'Grzechulska J, Hamerski M, Morawski AW. Incorporation of lithium into TiO2 host and its application in photocatalysis. Molecular Crystals and Liquid Crystals. 2000;341:243-248'},{id:"B210",body:'Song H, Jiang H, Liu T, Liu X, Meng G. Preparation and photocatalytic activity of alkali titanate nano materials A2TinO2n+1 (A = Li, Na and K). Materials Research Bulletin. 2007;42:334-344'},{id:"B211",body:'Yao H, Fan M, Wang Y, Luo G, Fei W. Magnetic titanium dioxide based nanomaterials: Synthesis, characteristics, and photocatalytic application in pollutant degradation. Journal of Materials Chemistry A. 2015;3:17511-17524'},{id:"B212",body:'Marcus Y. Thermodynamics of solvation of ions. Part 5. Gibbs free energy of hydration at 298.15 K. Journal of the Chemical Society, Faraday Transactions. 1991;87:2995-2999'},{id:"B213",body:'He G, Zhang L, Zhou D, Zou Y, Wang F. The optimal condition for H2TiO3–lithium adsorbent preparation and Li+ adsorption confirmed by an orthogonal test design. Ionics. 2015;21:2219-2226'},{id:"B214",body:'Park JH, Lee S, Kim SS, Kim JH, Park JH. Effect of conductive additives on the structural and electrochemical properties of Li4Ti5O12 spinel. Bulletin of the Korean Chemical Society. 2012;33:188-192'},{id:"B215",body:'Yi TF, Jiang LJ, Shu J, Yue CB, Zhu RS, Qiao HB. Recent development and application of Li4Ti5O12 as anode material of lithium ion battery. Journal of Physics and Chemistry of Solids. 2010;71:1236-1242'},{id:"B216",body:'Yi TF, Yang SY, Xie Y. Recent advances of Li4Ti5O12 as a promising next generation anode material for high power lithium-ion batteries. Journal of Materials Chemistry A. 2015;3:5750-5777'},{id:"B217",body:'Dong DQ , Wang WX, Wang ML. Preparation of 3DON Li4Ti5O12 and behavior of Li+ ion exchange. Applied Mechanics and Materials. 2014;618:175-179'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"Samadiy Murodjon",address:null,affiliation:'
College of Marine and Environmental Science, Tianjin University of Science and Technology, TEDA, P.R. China
College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, TEDA, P.R. China
College of Marine and Environmental Science, Tianjin University of Science and Technology, TEDA, P.R. China
College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, TEDA, P.R. China
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They feature unique properties stemming from their surface chemistry, their crystallinity, and their three-dimensional structure. CNCs have been exploited in a number of applications such as optically active coatings, nanocomposite materials, or aerogels. CNC size and shape determination is an important challenge and transmission electron microscopy (TEM) is one of the most powerful tools to achieve this goal. Because of the specifics of TEM imaging, CNCs require special attention. They have a low density, are highly susceptible to electron beam damage, and easily aggregate. Specific techniques for both imaging and sampling have been developed over the past decades. In this review, we describe the CNCs, their properties, their applications, and the need for a precise characterization of their morphology and size distribution. We also describe in detail the techniques used to record quality images of CNCs. 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He joined Ciba-Geigy Japan in 1987, where he was engaged in research on crystallography and electrophotography of organic substances. Since joining Nagoya University, Nagoya, Japan, in 1990, he has been engaged in research on crystallography and physical properties of metallic nano particles and ultrathin films. Since 1997, he has been an Associate Professor at the Graduate School of Engineering as well as the Graduate School of Information Science and Technology, Hokkaido University, Sapporo, Japan. His major subject at present is in-situ electron microscopy of electronic devices.",institutionString:"Hokkaido University",institution:{name:"Hokkaido University",institutionURL:null,country:{name:"Japan"}}},{id:"174365",title:"M.Sc.",name:"Łukasz",surname:"Mielańczyk",slug:"lukasz-mielanczyk",fullName:"Łukasz Mielańczyk",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Medical University of Silesia",institutionURL:null,country:{name:"Poland"}}},{id:"174440",title:"Dr.",name:"Kouichi",surname:"Hamada",slug:"kouichi-hamada",fullName:"Kouichi Hamada",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"174441",title:"Prof.",name:"Yasuo",surname:"Takahashi",slug:"yasuo-takahashi",fullName:"Yasuo Takahashi",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"174473",title:"Dr.",name:"Kelvii Wei",surname:"Guo",slug:"kelvii-wei-guo",fullName:"Kelvii Wei Guo",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"City University of Hong Kong",institutionURL:null,country:{name:"China"}}},{id:"175845",title:"Prof.",name:"Kazuhisa",surname:"Sueoka",slug:"kazuhisa-sueoka",fullName:"Kazuhisa Sueoka",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"175977",title:"Dr.",name:"Natalia",surname:"Matysiak",slug:"natalia-matysiak",fullName:"Natalia Matysiak",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"175978",title:"Dr.",name:"Olesya",surname:"Klymenko",slug:"olesya-klymenko",fullName:"Olesya Klymenko",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"175979",title:"Prof.",name:"Romuald",surname:"Wojnicz",slug:"romuald-wojnicz",fullName:"Romuald Wojnicz",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null}]},generic:{page:{slug:"OA-publishing-fees",title:"Open Access Publishing Fees",intro:"
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As a gold Open Access publisher, an Open Access Publishing Fee is payable on acceptance following peer review of the manuscript. In return, we provide high quality publishing services and exclusive benefits for all contributors. IntechOpen is the trusted publishing partner of over 128,000 international scientists and researchers.
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The Open Access Publishing Fee (OAPF) is payable only after your full chapter, monograph or Compacts monograph is accepted for publication.
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*These prices do not include Value-Added Tax (VAT). Residents of European Union countries need to add VAT based on the specific rate in their country of residence. Institutions and companies registered as VAT taxable entities in their own EU member state will not pay VAT as long as provision of the VAT registration number is made during the application process. This is made possible by the EU reverse charge method.
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Discoverability - electronic citation and linking via DOI
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Permanent and unrestricted online access to your work
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Exceeds 20 pages (for chapters in Edited Volumes), an additional fee of 40 GBP per page will be required
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Open Access Funding
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To explore funding opportunities and learn more about how you can finance your IntechOpen publication, go to our Open Access Funding page. IntechOpen offers expert assistance to all of its Authors. We can support you in approaching funding bodies and institutions in relation to publishing fees by providing information about compliance with the Open Access policies of your funder or institution. We can also assist with communicating the benefits of Open Access in order to support and strengthen your funding request and provide personal guidance through your application process. You can contact us at oapf@intechopen.com for further details or assistance.
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For Authors who are still unable to obtain funding from their institutions or research funding bodies for individual projects, IntechOpen does offer the possibility of applying for a Waiver to offset some or all processing feed. Details regarding our Waiver Policy can be found here.
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Added Value of Publishing with IntechOpen
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Choosing to publish with IntechOpen ensures the following benefits:
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Indexing and listing across major repositories, see details ...
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Long-term archiving
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Visibility on the world's strongest OA platform
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Live Performance Metrics to track readership and the impact of your chapter
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Dissemination and Promotion
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Benefits of Publishing with IntechOpen
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Proven world leader in Open Access book publishing with over 10 years experience
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+5,200 OA books published
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Most competitive prices in the market
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Fully compliant with OA funding requirements
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Optimized processes, enabling publication between 8 and 12 months
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Personal support during every step of the publication process
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+146,150 citations in Web of Science databases
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Currently strongest OA platform with over 150 million downloads
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