",isbn:"978-1-80356-441-8",printIsbn:"978-1-80356-440-1",pdfIsbn:"978-1-80356-442-5",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,isSalesforceBook:!1,isNomenclature:!1,hash:"9117bd12dc904ced43404e3383b6591a",bookSignature:"Assistant Prof. Erik Froyen",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/11669.jpg",keywords:"Total Cholesterol, Triglycerides, Seizures, Epilepsy, Low-Fat Diet, High-Fat Diet, Cardiovascular Disease, Saturated Fatty Acids, Monounsaturated Fatty Acids, Polyunsaturated Fatty Acids, Fat Food Sources, Omega-3 Fatty Acids",numberOfDownloads:8,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"March 1st 2022",dateEndSecondStepPublish:"May 3rd 2022",dateEndThirdStepPublish:"July 2nd 2022",dateEndFourthStepPublish:"September 20th 2022",dateEndFifthStepPublish:"November 19th 2022",dateConfirmationOfParticipation:null,remainingDaysToSecondStep:"2 months",secondStepPassed:!0,areRegistrationsClosed:!1,currentStepOfPublishingProcess:3,editedByType:null,kuFlag:!1,biosketch:"An assistant professor in the Department of Nutrition and Food Science at California State Polytechnic University, Pomona, with multiple publications and presentations on the mechanisms by which fatty acids impact the risk factors for cardiovascular disease.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"415310",title:"Assistant Prof.",name:"Erik",middleName:null,surname:"Froyen",slug:"erik-froyen",fullName:"Erik Froyen",profilePictureURL:"https://mts.intechopen.com/storage/users/415310/images/system/415310.jpg",biography:"Erik Froyen is an assistant professor in the Department of Nutrition and Food Science at California State Polytechnic University, Pomona. 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\n
1. Introduction
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Energy conversion and storage become more and more important in the context of the increasing global energy demand because of the inadequacy of fossil fuels, climate change, and deteriorating environmental conditions. Currently, among the available energy conversion and storage technologies, lithium-ion battery (LIB) is the most versatile and successful technology that possess high-energy densities (2–3 times higher than conventional batteries), no memory effects, relatively slow self-discharge rates, and longer battery lifetimes, and therefore they have received intense attention from both the academic community and industry as the dominant power source in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and full electric vehicles (EVs) [1–4]. For further enhancing the performance of LIBs, many studies concentrated on changing either the chemical composition or macroscopic structure of the components [5, 6].
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As one of the most important components in LIBs, anode plays an important role in determining the overall performance of LIBs. At present, most commonly used anode materials for commercial LIBs are graphite powders that have limited theoretical capacity (372 mA h g−1) and long diffusion pathways for the lithium ions [7]. This may result in low energy and low power densities, which cannot meet the ever-expanding demands for next-generation LIBs. To resolve the problem, a variety of nanostructured carbonaceous materials have been investigated as anode materials for LIBs, such as carbon nanobeads [8], hollow carbon nanospheres [9, 10], carbon nanotubes [11–13], carbon nanofibers (CNFs) [14–16], graphenes [17–19], and their composites [20–22].
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Among various carbon nanostructures, CNFs and its morphological-controlled derivatives (such as porous or hollow CNFs) have attracted much attention because they could provide an enhanced surface-to-volume ratio for the electrode–electrolyte interface, short transport lengths for ionic transport, and efficient one-dimensional (1D) electron transport along the longitudinal direction when compared to the powder materials [23]. Moreover, these CNFs can be used to encapsulate various second phases to form functional composite, meeting the ever-growing demand for advanced batteries. Electrospinning has been widely used as a simple, versatile, and cost-effective industry-viable technology to prepare various CNFs and their composites in a continuous process, with controllable morphology and compositions [24–42]. The principle of electrospinning has been well introduced in several excellent reviews on electrospun materials for energy-related applications [43–46]. In this chapter, we have summarized some recent advances in the area of 1D CNF-based materials for LIB anodes, covering the structure evolution from electrospun solid CNFs into morphology-constructed porous CNFs, and their composites with various functional nanoparticles.
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2. Electrospun CNFs
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2.1. Solid CNFs
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Carbon materials including graphite, graphene, fullerenes, carbon nanotubes, and CNFs have attracted tremendous attention in both fundamental research and industrial applications, especially in the applications of energy storage and conversion devices such as LIBs [47, 48]. Among these various carbon materials, 1D electrospinning-derived CNFs are of high interest as potential anode materials due to their high-specific surface area, good conductivity, and structural stability, which are the key factors influencing the electrochemical properties of carbon electrodes [23, 49–52]. The 1D nature of the CNF anode not only facilitates the electron transport along the axial direction, but also reduces the lithium-ion diffusion distance through short radial direction, both of which are beneficial for the improved specific capacity and rate capability.
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The CNFs can be derived from many synthetic or natural polymeric precursors such as polyacrylonitrile (PAN), polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), lignin, or cellulose. It should be noted that the physical and chemical properties of CNFs highly depend on the chemical structure of the carbon precursors. Currently, the commonly used precursor for CNFs is PAN, which has good spinnability, and can yield a high amount of carbon residue after simple stabilization and carbonization processes [44]. Moreover, owing to the robust integrated network structure and good electrical conductivity, PAN-derived CNF webs can be directly used as the anode materials without adding any adhesive and conductive additives, which can reduce the weight of anode, and thus improving the energy density of a full cell [53]. Endo’s group [23] synthesized the PAN-derived CNF webs by the electrospinning technique combined with two-step heat-treatments and investigated their lithium-storage properties along the variation of carbonization temperature (from 700°C to 2800°C). The composition ratio of amorphous carbon and graphitic carbon in these CNFs was demonstrated to affect the reversible capacity, slope or plateau charge–discharge characteristic, and rate/cycling performance. The high-purity CNF web thermally treated at 1000°C shows the high-rate capability (350 mA h g−1 at a charge current of 100 mA g−1) owing to the interlinked nanofibers, a large accessible surface area, and relatively good electrical conductivity, which make it an ideal candidate for the anode material of high-power LIBs. Nevertheless, the large-scale applications of PAN-derived CNFs might be hampered by the following two reasons. First, PAN is a relatively expensive synthetic polymer, of which the price varies with that of the crude oil [54]. Second, PAN is hard to dissolve in many solvents, and its most commonly used solvent, dimethylformamide (DMF), is known to be harmful for human beings during the electrospinning process [55].
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Water or ethanol/polymer system is a better choice to avoid the aforementioned problems and lower the production cost. PVP is the type of water-soluble polymer, and has been widely used in industry due to its merits of low cost, nontoxicity, and good compatibility with metallic precursors. The preparation process of well-controlled PVP-derived CNFs has also been comprehensively investigated; however, the lithium-storage of this fiber-based electrode is temporarily lower than that of PAN-derived CNFs [54]. Other common water-soluble CNF precursors such as PVA [55, 56], lignin, and cellulose [57, 58] have been used to prepare fibrous electrode; nevertheless, all of them show low mechanical properties as compared with PAN-derived CNFs.
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Coaxial electrospinning or coelectrospinning, a breakthrough in the electrospinning method, has been used to prepare core–shell soft-hard CNFs, in which a spinneret consisting of two coaxial capillaries is used, with PAN/DMF as the external solution and mineral oil as the inner solution (Figure 1) [59]. After the stabilization and carbonization processes, the soft–hard core–shell CNFs were obtained with shell PAN converted to hard carbon and core mineral oil decomposed to soft carbon. The coaxial CNFs combine the advantages of both hard carbon (possess a high capacity of 400–500 mA h g−1, but poor capacity retention performance) and soft carbon (has a lower, but reversible capacity of 200–300 mA h g−1, however, it shows a very serious voltage hysteresis during the delithiation process), and therefore exhibits enhanced reversible capacity as an anode in LIBs (390 mA h g−1 at a charge current of 100 mA g−1) even though the kinetics of the charge process requires further improvement.
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Figure 1.
Schematic illustrations of (a) the coaxial electrospinning apparatus and (b) preparation of coaxial CNFs [59].
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2.2. Porous CNFs
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Recent research has showed that the introduction of various porous structures into CNFs could greatly enhance both the specific capacity/capacitance and the rate capability. This is because the incorporated pore can possibly create high-specific surface area that provides more charge transfer. Up to date, many strategies have been used to control the porous structure in CNFs for LIB application. Template-based processes are of great interest for the preparation of porous CNFs with high surface area. Kang’s group [60] synthesized porous CNFs by etching off the silica template in CNFs from pyrolysis of the electrospun polyamic acid/tetraethoxysilane (TEOS) nanofibers. The porous CNF electrode showed a high reversible capacity of 445 mA h g−1 after 50 cycles, which is higher than that of commercial graphite (372 mA h g−1). The nitrogen adsorption–desorption isotherms showed that the specific surface area can reach to 950 m2 g−1, which is contributed to the large amounts of micropores. Here, the micropores can serve as the active “reservoir” for absorbing more lithium during cycling, thus improving the lithium-storage capacity based on the bare CNFs. Lee et al. [61] have utilized coaxial electrospinning to fabricate hollow CNFs (HCNFs) as anode materials and studied the effect of carbonization temperature on the electrochemical performance. Styrene-co-acrylonitrile (SAN) and PAN in DMF solutions were served as the core and shell materials. The as-spun nanofibers were stabilized at 270–300°C for 1 h in air, and then carbonized at 800, 1000, 1200, and 1600°C for 1 h in nitrogen, respectively. During thermal treatment, the linear PAN molecules were transformed to the ladder structure and got carbonized in the following process; meanwhile, the core component burned out leading to the hollow structure (Figure 2). The large continuous hollow pore can facilitate the Li+-carrying electrolyte penetrate into the inner part of CNFs, thus highly reducing the Li+-diffusion distance, and making the full use of the active lithium-storage part at high charge–discharge rate. The capacities after 10 cycles at a current of 50 mA g−1 were 390, 334, 273, and 243 mA h g−1 in accordance to their carbonization temperature (800–1600°C), with a very high coulombic efficiency. The reversible discharge capacities are slightly reduced even though four times higher current density is supplied (Figure 3).
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Figure 2.
FE-SEM images of HCNFs carbonized at (a) 800°C, (b) 1000°C, (c) 1200°C, and (d) 1600°C [61].
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Figure 3.
Discharge capacity vs. discharge rate for the HCNFs carbonized at various temperatures [61].
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Recently, nitrogen-doped carbon materials are a researchers owing to the high capacity and rate capability [10, 62–65]. In a recent research, Liu et al. fabricated a new type of nitrogen-doped carbon tube by pyrolyzing polydopamine (PDA) using silica nanofibers as templates (Figure 4) [65]. The SiO2 NFs were first fabricated by an electrospinning technique and subsequent calcination in air, and then immersed in a dopamine aqueous solution (pH: ~8.5). Subsequently, the dopamine monomers were covalently joined via aryl–aryl linkages owing to the oxidization and cyclization reactions, forming a PDA coating layer on the surface of the SiO2 NFs. Then, the core–shell SiO2 NFs/PDA nanofibers were carbonized at 750°C for 3 h in a N2 atmosphere. Finally, N-CTs were obtained by etching off the silicate template with sodium hydroxide solution. The N-CTs show a fibrous morphology (diameter, 200–400 nm; length, several micrometers), a typical hollow feature (wall thickness, ~16 nm), and discontinuous and randomly constructed graphene-like layers (the d002 interlayer spacing, 0.354 nm) (Figure 5). The PDA-derived carbon tubes (N-CTs) as anode materials for LIBs show a remarkable self-improved capacity along cycling. This is contributed to the continuous interlamellar spacing expansion between the graphene-like carbon layers during cycling. (Figure 6) Moreover, owing to the unique hollow structure, ultrafine carbon-tube wall, and nitrogen doping, the N-CT electrode shows very high specific capacity, outstanding rate capability, and robust durability, giving a superior reversible capacity of 1635 mA h g−1 at 100 mA g−1 after 300 cycles and 1103 mA h g−1 at 500 mA g−1 after 500 cycles. The excellent electrochemical performance makes the N-CTs a potential anode material for the next-generation LIBs.
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Figure 4.
Schematic illustration of the synthesis of N-doped carbon tubes [65].
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Figure 5.
(a) SEM image of SiO2 NFs, (b and c) SEM images of N-CTs, and (d–f) HR-TEM images of N-CTs [65].
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Figure 6.
Illustration of lithium-ion storage/transport in N-CTs during the repeated lithiation and delithiation processes [65].
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Figure 7.
(a) Schematic illustration of the preparation of the HPCNF electrode. (b and c) Photographs of supported and flexible HPCNF film [68].
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Besides, some other additives such as ZnCl2 and H3PO4 usually act as the activating agents to produce porous structures in CNFs [66, 67]. These activating agents lead to large amounts of micropores in the surface of CNFs, thus providing more surface active sites for absorbing the Li+. Lately, a novel and simple method (air activation method) have attracted much attention as the method needs no template and activating agents. Yu’s group [68] prepared highly porous CNFs (HPCNFs) by two-step carbonization of electrospun PAN nanofibers. During carbonization process at 1000°C in Ar, a certain volume of air were mixed into the Ar flow, where the CNFs were partially burnt off and numerous micro/mesopores were formed simultaneously (Figure 7). The as-synthesized HPCNFs exhibit a paper-like external morphology and highly porous internal nanostructure. When used as a binder-free anode in LIBs, the HPCNFs deliver a very high capacity of 1780 mA h g−1 at 50 mA g−1 after 40 cycles, greatly improved rate capacity and ultralong cycle life (1550 mA h g−1 at 500 mA g−1 after 600 cycles) in comparison with CNFs. The outstanding electrochemical performance is contributed to the electrospinning-derived 3D porous interconnected networks and the air-activated mesoporous structure in the CNFs that can facilitate the electrolyte into the electrode, thus reducing the Li+ diffusion distance. Consideration of the low-cost and efficient preparation, this method is hoped to design highly porous materials in large-scale production used for advanced energy-storage devices.
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3. Composite anodes with CNFs
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The capacities of pure CNFs are insufficient for high-performance batteries. Therefore, various components such as silicon, tin and tin oxides, titanium oxides, and other metal oxide nanoparticles have been loaded into CNFs via an electrospinning process to enhance the performance.
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3.1. Si-loaded CNF composite anodes
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\nSilicon nanoparticles (with a theoretical specific capacity of 4200 mA h g−1) could be incorporated into the CNF matrix by electrospinning PAN–Si nanoparticles and the subsequence carbonization to improve the poor cycling performance resulted from large volume changes (~400%) and nanoparticle aggregation upon the alloying and dealloying reaction with Li+ [69, 70]. By optimizing the Si content, Si particles were dispersed homogeneously along the fibers, thus inhibiting the agglomeration of Si nanoparticles and suppressing mechanical failure during Li+ insertion and extraction [71]. Additionally, introduction of various porous structures into CNFs could greatly enhance the specific capacity and rate performance of Si/CNF composite electrodes. For example, porous Si/CNF composites used without binding and conductive additives showed high discharge capacity of 1100 mA h g−1 at a high current density of 200 mA g−1 [72].
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Another example, Si–CNF core–shell fibers with void space in the core section were fabricated by coaxial electrospinning, in which Si–PMMA was chosen as the core and PAN as the shell [73]. After carbonization process, PAN can still remain stable in the shell, while PMMA could be removed to form the void space in the core of the fibers, which can accommodate the volume expansion of Si (Figure 8). This unique Si–CNF core–shell structure shows a high capacity of 1384 mA h g−1 at a rate of C/10 and an outstanding cycle life of 300 cycles with 99% capacity retention. Another promising strategy to improve the performance of Si/CNFs is adding conductive component such as graphitized carbon [74] or TiO2 [75] into the electrospun Si–CNF composite. The electrical conduction of the surrounding material significantly improved the reversible capacity and cycling stability.
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Figure 8.
Schematic illustration of Si–CNF core–shell fibers [73].
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3.2. Tin-based composite anodes with CNFs
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Tin and its oxides have much higher theoretical capacities (Sn: 992 mA h g−1, SnO2: 780 mA h g−1) than the commercial graphite (372 mA h g−1), but they also suffer from large volume changes and nanoparticle aggregation during cycling, resulting in capacity and stability losses. Dispersing these metallic nanoparticles into CNFs via electrospinning is an efficient approach to overcome these drawbacks because CNFs can hinder particle aggregation, provide continuous long-distance electron transport pathway, support numerous active sites for charge-transfer reactions, and eliminate the need for binding or conducting additive [23]. Yu et al. [53] fabricated a reticular Sn/CNF webs used as anodes for rechargeable LIBs via electrospinning technique and carbonization treatment, and studied the carbonization temperature effect on electrochemical performance of the Sn/CNF webs. It is demonstrated that carbonization temperature will influence Sn grain size, surface area or fiber diameter, and the electrical conductivity of CNFs, which dominate the electrochemical performance of the electrode. The Sn/CNF webs carbonized at 850°C exhibited a reversible capacity of 450 mA h g−1 after 30 cycles at a current of 25 mA g−1. Herein, the overall capacity looks low because the direct electrospinning technique limits the loading amount of active materials (with ~22 wt% Sn particles), which could be improved by constructing novel nanostructures.
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Porous or hollow structure is introduced into Sn/CNF systems to enhance the cycling stabilities and rate capabilities. Sn nanoparticles have been encapsulated into porous multichannel carbon microtubes (SPMCTs) [76] and bamboo-like hollow CNFs (SBCNFs) [77] using a single-nozzle and a coaxial electrospinning technique, respectively. Such porous or hollow carbon shells could provide appropriate void volume to buffer the large volume change, prevent pulverization of the Sn nanoparticles, serve as an electron supplier, and allow more Li+ access. As a result, both of them showed good cycling stabilities and excellent rate capabilities. Specifically, the SBCNFs display a better cycling stability and a more excellent rate capability with a reversible discharge capacity as high as 480 mA h g−1 at 5 C after 100 cycles.
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SnOx/CNF composites have been synthesized by electrospinning and subsequent thermal treatment [78, 79]. For example, ultrauniform SnOx/carbon nanohybrid (denoted as U-SnOx/C) has been fabricated by solvent replacement and subsequent electrospinning homogeneous dispersion of SnO2 nanoparticles in PAN/DMF solution [79]. The strong interaction between SnOx and nitrogen-containing CNFs (Sn–N bonding) could effectively confine the uniformly embedded SnOx. This unique nanostructure can not only suppress the agglomeration of SnOx and tolerate the substantial volume change during cycling, but also enhance the transport of both electrons and ions due to shortened conducting and diffusion pathways. As a consequence, the U-SnOx/C nanohybrids exhibit a high reversible capacity of 608 mA h g−1 after 200 cycles, with excellent rate capability. However, the effect of homogeneous distribution is also limited. Sn- or SnO2/CNF composites have also been doped with various transition metals, such as Co, Cu and Ni, to improve the cycling stability and rate performance. Co–Sn alloy particles embedded in CNFs improved the cycling stability by increasing the conductivity of the CNF and also enhanced the specific anodic capacity because of different Co–Sn alloys in the structure, as controlled by the carbonization temperature [80]. Incorporation of amorphous Cu into Sn/CNF achieved the highest cycling stability of 490 mA h g−1 after 600 cycles at a current density of 156 mA g−1 [81]. Addition of Ni into SnO2 CNF suppressed the reduction of SnO2 to Sn during carbonization and the agglomeration of SnO2, thus enhancing the cycling stability [82].
\n
In recent literature, Yu et al. [83–86] have achieved the in-site addition of transition metallic (Ti and Cu) and nonmetallic elements (P and B) into SnOx/CNF composites for the enhancement of cycling stability and rate performance via the electrospinning technique and subsequent thermal treatments. It was demonstrated that the doped SnOx nanoparticles were all ultrafine and uniformly dispersed in the conductive CNF matrix, and the doping content should be kept to an optimal value. The incorporation of heteroatoms into SnOx/CNFs endowed them with the enhancement of cyclic capacity retention and rate performance compared with the pristine SnOx/CNFs (Table 1) due to the more complete reversible conversion reaction and the higher Li+-diffusion coefficient. Especially, the addition of Cu into SnOx/CNFs exists in the form of Cu2O, which can be transformed into Cu nanoparticles dispersed in a lithia matrix (Li2O), inhibiting the aggregation of Sn particles in the following alloying–dealloying cycling (Figure 9). Meanwhile, the existence of Cu nanoparticles not only improves the Li+-transport capability and the electronic conductivity of the overall electrode, but also enhances the chemical reacting activity of Sn back to SnOx during the Li+-extraction process; therefore, the addition of Cu+ can endow the SnOx/CNF electrode with greatly enhanced reversible capacity and rate capability [86].
\n
\n
\n
\n
\n
\n\n
\n
Materials
\n
Performance
\n
Rates
\n
References
\n
\n\n\n
\n
SnOx/CNFs
\n
640 mA h g−1 after 60 cycles
\n
200 mA g−1
\n
85
\n
\n
\n
230 mA h g−1 after 100 cycles
\n
2 A g−1
\n
\n
\n
\n
Ti-doped SnOx/CNFs
\n
670.7 mA h g−1 after 60 cycles
\n
200 mA g−1
\n
84
\n
\n
\n
302.1 mA h g−1 after 80 cycles
\n
2 A g−1
\n
\n
\n
\n
P-doped SnOx/CNFs
\n
676 mA h g−1 after 100 cycles
\n
200 mA g−1
\n
85
\n
\n
\n
288 mA h g−1 after 120 cycles
\n
2 A g−1
\n
\n
\n
\n
B-doped SnOx/CNFs
\n
670.2 mA h g−1 after 100 cycles
\n
200 mA g−1
\n
86
\n
\n
\n
300 mA h g−1 after 80 cycles
\n
2 A g−1
\n
\n
\n
\n
Cu-doped SnOx/CNFs
\n
743 mA h g−1 after 100 cycles 347 mA h g−1 after 1000 cycles
\n
200 mA g−1 5 A g−1
\n
87
\n
\n
\n
SnO2@PC/CTs
\n
1045 mA h g−1 after 300 cycles 499 mA h g−1 after 1000 cycles
\n
500 mA g−1 2A g−1
\n
88
\n
\n
\n
U-SnOx/CNFs
\n
608 mA h g−1 after 200 cycles 175 mA h g−1 after 40 cycles
\n
500 mA g−1 5 A g−1
\n
80
\n
\n\n
Table 1.
Electrochemical performance of Sn-based composites with CNFs.
\n
Figure 9.
(a and b) HRTEM images of SnOx/CNFs and (c) corresponding selected area electron diffraction (SAED) pattern; (d and e) HRTEM images of SnOx–20%Cu/CNFs and (f) corresponding SAED pattern after 1000-cycle performance test at a current density of 2 A g−1 [86].
\n
Highly enhanced performance of SnO2 could be achieved by designing a novel 1D nanostructure. Liu et al [87] have designed and synthesized a novel fiber-in-tube hierarchical nanostructure of SnO2@porous carbon in carbon tubes (denoted as SnO2 @PC/CTs), with 1D SnO2@PC as the fibrous core and PDA-derived carbon tubes as the tubular shell, through N-doped carbon coating on electrospun hybrid nanofiber template and a post-etching technique (Figure 10). The internal PC skeleton could link and support SnO2 nanoparticles for inhibiting the nanoparticle aggregation during cycling, while the external carbon protective shell could confine the volume expansion of SnO2 for preserving the integrity of the overall electrode and facilitate electron and ion transport to the internal active materials. As a result, compared with SnO2/CTs (without internal porous carbon skeleton), the SnO2@PC/CT nanohybrids exhibit a higher reversible capacity of 1045 mA h g−1 at 0.5 A g−1 after 300 cycles and a high-rate cycling stability after 1000 cycles (Table 1) compared with those of SnO2/CTs (without internal porous carbon skeleton). This unique 1D hierarchical nanostructure could be extended for improving other high-capacity metal oxides materials such as MnO/MnO2, Fe2O3, and Co3O4.
\n
Figure 10.
Schematic illustration on the preparation of SnO2@PC/CT and SnO2/CT nanohybrids: (A) preparing nanofiber web using electrospinning technique; (B) calcining electrospun nanofiber web (B1) at 500°C for 1 h in air to obtain SnO2/SiO2/C HNF web and (B2) at 600°C for 6 h in air to obtain SnO2/SiO2 HNF web (C) coating PDA on the surface of SnO2/SiO2/C HNFs or SnO2/SiO2 HNFs at room temperature; (D) carbonizing two types of PDA-coated HNFs at 600°C, and then etching SiO2 to obtain SnO2@PC/CTs with a fiber-in-tube hierarchical nanostructure or SnO2/CTs with a particle-in-tube nanostructure [87].
\n
\n
\n
3.3. Ti-based composite anodes with CNFs
\n
TiO2 has been regarded as a promising high-rate anode material due to its low cost, high working voltage, and structural stability during lithium insertion and extraction processes [88–93]. Bulk TiO2 particle has poor ion and electron conductivity, which has limited its practical capacity and high-rate capability. So much attention has been paid to produce nanostructured and open-channeled TiO2 materials, which can provide increased reaction active sites and short diffusion lengths for electron and lithium-ion transport [94–100].
\n
Figure 11.
Schematic representation of the preparation for the 3D porous TiO2 nanotube/carbon nanofiber architecture (ST–TiO2/C: electrospun TiO2/C nanofibers after calcination as a starting raw material; 3D-TiO2/C: 3D porous TiO2 nanotube/carbon nanofiber architecture prepared by a hydrothermal method) [106].
\n
Moreover, tailoring these TiO2 fires by coating or incorporation of carbon materials can greatly influence the capacity values and hence the battery performance [101, 102]. CNFs have also been used to load TiO2 particles or fibers for improving electrochemical performance [103–106]. The TiO2–CNF composite nanofibers were prepared by electrospinning technique and thermal treatment. Owing to the unique features of encapsulating TiO2 nanocrystals into porous conductive carbon matrix, the composite nanofibers demonstrated an excellent electrochemical performance [103, 104]. A coaxial electrospinning technique combined with subsequent calcination treatment was also used to develop porous TiO2–CNFs for LIB anodes [105]. In addition, a 3D porous architecture composed of TiO2 nanotubes connected with a CNF matrix was successfully prepared by a hydrothermal method using electrospun rutile TiO2/C nonwoven as the starting raw material (Figure 11) [106]. With its unique structure and connected conductive CNF network, the 3D architecture of the electrode resulted in superior rate performance: the reversible capacities were 214, 180, 138, and 112 mA h g−1 at the rate of 5, 10, 20, and 30 C, respectively. Additionally, the 3D structured electrode shows a very stable cycling performance, especially at a high rate of 30 C, without undergoing decay after 1000 cycles.
\n
Spinel Li4Ti5O12 has attracted particular attention for LIB application due to its nearly zero-strain characteristics [107] However, the practical application of Li4Ti5O12 in LIBs is hampered by its poor natural electronic conductivity. In order to improve the conductivity of Li4Ti5O12 materials, various approaches such as surface coating with conductive materials, e.g., Ag nanoparticles [108, 109], dispersion of Li4Ti5O12 nanoparticles into a carbon matrix [110–112], and preparation of submicron or nanosized Li4Ti5O12 [113, 114] aiming to significantly shorten the Li+-diffusion length, etc., have been developed.
\n
Li4Ti5O12/carbon hybrid nanowebs consisting of interconnected nanofibers were prepared by a combination of electrospinning and subsequent thermal treatments [115, 116]. The as-prepared Li4Ti5O12/carbon nanowebs exhibited high reversible charge stability and good cycling performance (166 mA h g−1 at 0.1 C). Highly porous Li4Ti5O12/C nanofibers are successfully designed and prepared through electrospinning combined with a post-two-step annealing process [117]. The Li4Ti5O12/C hybrid with a well-defined porous nanoarchitecture exhibits ultrahigh cycling rates and superior cycling stability. Mesoporous structures were also obtained by adding an amphiphilic triblock copolymer surfactant into a PVP solution, driving the self-assembly of a hydroxyl Li–Ti–O precursor to form mesopores after calcination [118]. Even better performances were obtained from combining dual-phase Li4Ti5O12–TiO2 with CNFs, prepared by immersing TiO2/CNF in a LiOH solution at high temperatures. This imparted a pseudocapacitive effect, with a 204 mA h g−1 discharge capacity after 200 cycles at 100 mA g−1 from an initial capacity of ~220 mA h g−1 [119].
\n
\n
\n
3.4. Other metal oxide/CNF composites
\n
Many other metal oxide nanoparticles have also been incorporated into the CNF matrix for the usage of LIB anode materials. For example, the MnOx particles, existed as MnO or Mn3O4, were incorporated into porous CNFs via electrospinning technique and subsequent heat treatment [120]. The porous MnOx/C nanofibers experienced limited volume change with Li+ insertion/extraction because the ductile and strong C matrices suppressed the disintegration and aggregation of MnOx. Compared with pure CNF anodes, the MnOx/C exhibited larger charge and discharge capacities (542 mA h g−1 for MnOx/C and 396 mA h g−1 for pure CNF at the 50th cycle) [121]. MnOx was also incorporated into fibrous structures by the electrochemical deposition of MnOx nanoparticles on PAN-based electrospun CNFs [122]. Similarly, Zhang et al. [123] prepared porous Co3O4–CNFs, which show an improved electrochemical performance compared to pure Co3O4 nanoparticles. C/Fe3O4 nanofibers with amorphous C structure and crystalline Fe3O4 particles were carbonized at a relatively low temperature (600°C), and showed high reversible capacity of 1007 mA h g−1 at the 80th cycle and excellent rate capability [124]. Recently, maghemite (γ-Fe2O3) nanoparticles were uniformly coated on CNFs by a hybrid synthesis procedure combining an electrospinning technique and hydrothermal method. Electrospun PAN nanofibers serve as a robust support for iron oxide precursors during the hydrothermal process and successfully limit the aggregation of nanoparticles at the following carbonization step (Figure 12) [125]. Such design not only increases the loading of Fe2O3 up to more than 60%, but also limits the aggregation of nanoparticles in the following carbonization step, which leads to a high reversible capacity of above 830 mA h g−1 after 40 cycles.
\n
Figure 12.
Schematic of the preparation of γ-Fe2O3@CNFs and its microstructure and performance [125].
\n
\n
\n
\n
4. Summary and perspective
\n
In this chapter, the progress in electrospun CNFs and the composites with CNFs, which are used as LIB anode materials, has been summarized. Silicon, tin-based materials, and transition metal oxides are the candidates for the next generation anodes due to their expected high theoretical capacity, but suffer from some issues such as the vast volume change and low electronic conductivity, which could result in lower cycling stability and rate performance. Fortunately, these issues might be solved via composing with electrospun CNF matrix due to their superior mechanical properties and electrical conductivity as well as unique 1D nanostructure. More importantly, these CNF-based composite anodes with an interfibrous web structure could be directly used as anodes without any conductive agent and binder or current collectors, which can greatly reduce the inactive weight and cost of the cells, and significantly improve the electrochemical performance of LIBs [126, 127]. Further enhancement of electrochemical performance could be achieved by constructing controllable 1D nanostructures and doping various materials with CNF-based hybrid nanofibers.
\n
In addition, sodium-ion batteries (SIBs) are new-emerged promising candidates for new battery systems especially for large-scale and long-term electric energy storage applications due to their cost advantages [5, 6, 128–133]. Currently, many researchers have paid more attention to electrospun materials for SIBs [134–142]. So far, research has mainly focused on the electrode materials based on electrospun 1D composite with CNFs. By constructing controllable 1D nanostructure to take full advantage of the electrospun materials including shorter diffusion pathways, high surface areas and porosities, good mechanical strengths, etc., one can find the wide use of the electrospun materials in commercial LIBs or SIBs, and even in flexible battery devices in the years ahead.
\n
\n\n',keywords:"electrospinning, carbon-based nanofibers, anode, lithium-ion batteries, nanomaterials",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/50608.pdf",chapterXML:"https://mts.intechopen.com/source/xml/50608.xml",downloadPdfUrl:"/chapter/pdf-download/50608",previewPdfUrl:"/chapter/pdf-preview/50608",totalDownloads:2568,totalViews:737,totalCrossrefCites:1,totalDimensionsCites:3,totalAltmetricsMentions:0,impactScore:1,impactScorePercentile:71,impactScoreQuartile:3,hasAltmetrics:0,dateSubmitted:"October 14th 2015",dateReviewed:"March 21st 2016",datePrePublished:null,datePublished:"June 1st 2016",dateFinished:"May 8th 2016",readingETA:"0",abstract:"Considerable efforts have been devoted to the research of high-performance and long-lifespan lithium-ion batteries (LIBs) for their applications in large-scale power units. As one of the most important components in LIBs, anode plays an important role in determining the overall performance of LIBs. Nowadays, graphite has been the most successfully commercialized anode material. However, its limited theoretical capacity (372 mA h g−1) and limited power density seems insufficient for the next-generation LIBs. To overcome these problems, new materials with fundamentally higher capacity and higher power density are urgently needed. Recently, there is an ever-increasing interest in developing novel carbonaceous nanomaterials to replace graphite as the anode materials for LIBs. Such materials have included carbon spheres, carbon nanotubes, carbon nanofibers (CNFs), porous monoliths, and graphene. Among these alternative forms of carbon, CNFs and its morphological-controlled derivatives (such as porous or hollow CNFs) have attracted much attention due to their unique and interesting properties such as one-dimensional (1D) nanostructure, good electronic conductivity, and large surface areas. Moreover, these CNFs can be used to encapsulate various second phases to form some functional composite, meeting further requirements including higher energy density, higher power density or flexible requirements, for the advanced LIB operation.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/50608",risUrl:"/chapter/ris/50608",book:{id:"5168",slug:"alkali-ion-batteries"},signatures:"Yunhua Yu, Yuan Liu and Xiaoping Yang",authors:[{id:"46392",title:"Prof.",name:"Xiaoping",middleName:null,surname:"Yang",fullName:"Xiaoping Yang",slug:"xiaoping-yang",email:"yangxp@mail.buct.edu.cn",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null},{id:"179242",title:"Prof.",name:"Yunhua",middleName:null,surname:"Yu",fullName:"Yunhua Yu",slug:"yunhua-yu",email:"yuyh@mail.buct.edu.cn",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:{name:"Beijing University of Chemical Technology",institutionURL:null,country:{name:"China"}}},{id:"185629",title:"Dr.",name:"Yuan",middleName:null,surname:"Liu",fullName:"Yuan Liu",slug:"yuan-liu",email:"827575630@qq.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Electrospun CNFs",level:"1"},{id:"sec_2_2",title:"2.1. Solid CNFs",level:"2"},{id:"sec_3_2",title:"2.2. Porous CNFs",level:"2"},{id:"sec_5",title:"3. Composite anodes with CNFs",level:"1"},{id:"sec_5_2",title:"3.1. Si-loaded CNF composite anodes",level:"2"},{id:"sec_6_2",title:"3.2. Tin-based composite anodes with CNFs",level:"2"},{id:"sec_7_2",title:"3.3. Ti-based composite anodes with CNFs",level:"2"},{id:"sec_8_2",title:"3.4. Other metal oxide/CNF composites",level:"2"},{id:"sec_10",title:"4. Summary and perspective",level:"1"}],chapterReferences:[{id:"B1",body:'\nD. Linden, T. B. Reddy. Handbook of Batteries, McGraw-Hill: Unite States, 2002.\n'},{id:"B2",body:'\nB. Scrosati, J. Garche. Lithium batteries: status, prospects and future. J. Power Sources 195 (2010) 2419.\n'},{id:"B3",body:'\nJ. M. Tarascon, M. Armand. Issues and challenges facing rechargeable lithium batteries. Nature 414 (2001) 359.\n'},{id:"B4",body:'\nP. Poizot, S. 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Nanoscale 6 (2014) 693.\n'},{id:"B142",body:'\nY. J. Zhu, X. G. Han, Y. H. Xu, Y. H. Liu, S. Y. Zheng, K. Xu, L. B. Hu, C. S. Wang. Electrospun Sb/C Fibers for a Stable and Fast Sodium-Ion Battery Anode. ACS Nano 7 (2013) 6378.\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Yunhua Yu",address:"yuyh@mail.buct.edu.cn",affiliation:'
State Key Laboratory of Organic–Inorganic Composites, Beijing University of Chemical Technology, P. R. China
State Key Laboratory of Organic–Inorganic Composites, Beijing University of Chemical Technology, P. R. China
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1. Introduction
Hydrogels are three-dimensional polymeric networks that are utilized in various medical applications due to their unique properties: hydrophilicity, biodegradability, non-toxicity, and their controllable mechanical properties to mimic the mechanics of biological tissues [1, 2]. Furthermore, their structural properties exhibit similarities with biological extracellular matrix components which makes them ideal for cell culture and growth [3].
From the mechanical perspective, the concentration of the polymer network in hydrogels controls, to large extent, their mechanical strength allowing them to mimic the mechanics of physiologically loaded tissues [4]. Consequently, due to their availability and relatively low cost, hydrogels have become an attractive option when developing quantitative techniques that measure the mechanics of biological tissues [5, 6, 7, 8].
On structural level, hydrogels can be produced by chemical or physical cross-linking. In chemical (permanent) hydrogels, the network is crosslinked with strong covalent bonds that connect the molecular chains [9]. In physical (reversable) hydrogels, the gel’s molecular chains are connected with weaker forces such as hydrogen-bonding and ionic forces, thus, they can be easily dissolved by altering their environmental conditions (e.g., temperature, ionic strength, or pH of the gels [10]). These crosslinking methods allow the synthesis of multi-network hydrogels. For instance, hydrogels can be fabricated to have highly crosslinked rigid chains that are entangled with weakly crosslinked chains to provide a functional network system used in synthesizing biomaterials for several medical applications [11, 12].
One of the medical applications the hydrogels used in is contact lenses, mainly due to their unique physical properties and ease of processing; for example, Bauman et al. [13] developed Silicone Hydrogel lenses with nano-textured surface that mimics the surface of human cornea. Hydrogel lenses are also known for their wettability, a property necessary to avoid tear deposits [10], thanks to plasma treatment during the synthesis process [14]. Gas permeability is also a key characteristic of contact lenses to provide the cornea with efficient supply of oxygen at sufficient rates. Hydrogel lenses can be designed to meet this requirement thanks to their hydrated polymer matrix [10]. Hydrogels are also commonly used in wound dressing; they have been used in combination with other materials to form composite products efficient for different dressing applications; for example, a gauze impregnated with thermoplastic hydrogels allows for absorbing wound exudate while maintaining relative slimy consistency, as a result, it prevents adherence to the wound that normally results in pain during gauze changes [15]. Moreover, flexibility and transparency of hydrogels also made them an attractive option in wound dressing. While flexibility facilitates easy removal of the dressing products, transparency allows for continuous observation of the wound healing process [16].
Nowadays, delivery and release of drug molecules is receiving significant attention in many fields of medicine in which therapeutic drugs are loaded in polymer-based-carriers. These carriers transport the drugs to the targeted location [17, 18]. The efficacy of gels as drug-carriers relies in their adjustable porosity through controlling the crosslinking density of their matrix. Their porous structure allows for drug loading and releasing with high efficiency [19, 20]. Numerous studies have been published on the potential applications of hydrogels in drug delivery focusing on their mechanism, shape of the gel-carriers, and types of transported drugs. Therefore, this chapter, will discuss different drug loading and releasing mechanisms with respect to their corresponding medical application. Furthermore, the drug dosage is dependent on the design of the hydrogel systems, which in turn depend on the route of the drug administration (e.g., rectal, ocular, peroral, etc.), thus, this chapter will shed the light on the types of hydrogel-based carriers applied via different routes of drug administration. Lastly, this chapter will cover different classifications of the delivered drugs using gel-based delivery systems including small molecular weight drugs; therapeutic proteins and peptides; and vaccines.
2. Drug loading, targeting and releasing
2.1 Drug loading
Drug loading is an important property of a drug delivery system, and it is defined as the process of incorporating a drug into a carrier. The therapeutic agents can be introduced into gel-carriers by ionic interaction, dipole interaction, hydrogen bonding, physical encapsulation, covalent bonding, precipitation, or surface absorption. It’s common that more than a loading mechanism is used in drug delivery systems, and the ideal loading strategies are determined based on the compatibility between the physicochemical properties of the drug and the carrier.
The drug-loading process can take place during the formation of the carriers, or by incubating carriers into a concentrated drug solution to allow the loading through adsorption on their surface area [21]. However, this method has limited loading capacity, and the incubation time can influence the drug loading efficacy [22, 23]. In general, the entrapment and loading of drug molecules into polymer carriers depend on several characteristics: polymer and crosslinker concentrations, molecular weight of the polymer, and drug-polymer interactions [24, 25, 26]. The higher the polymer concentration the more efficient the drug entrapment is; at a high concentration, the polymer viscosity is increased, which delays the drug diffusion within the polymer particles [27]. Similarly, the high concentration of the crosslinker yields tangible increase in the loading efficiency [28]. Conversely, Fu et al., 2004 reported that the encapsulation efficiency decreases when the molecular weight of the polymer increases [29]. In protein based drugs, the interaction between the polymer and the drug molecules contribute to the entrapment efficiency; it increases if the protein molecules are entrapped into hydrophobic polymers, moreover, ionic interaction between the molecules and the polymer particles increase the efficiency of encapsulation, specifically, in polymers that belongs to carboxylic end groups [30].
2.2 Targeting
The delivery of therapeutics by nanocarriers can be passive: transport of drug-carrying nanoparticles through permeable vessels due to the enhanced permeability and retention (EPR) effect; or active: based on molecular recognition in which peripherally targeting moieties that interact with specific cell receptors [31].
In localized cancer therapy, the mechanism of passive targeting relies heavily on the tumor characteristics; tumor hypoxia causes rapid growth of leaky vessels, which increases the permeation of nano-delivery systems into the tumor, the lack of lymphatic filtration allows for the retention of these systems on the tumor’s interstitial space [32]. Moreover, this targeting strategy also depends on the carriers’ size; delivery systems larger than 50 kDa permeate through leaky vessels and retained in the tumor, smaller molecules are washed out quickly (very short circulation time) from the tumor [33]. The charge and the surface chemistry affect the circulation time of carriers; mononuclear phagocyte system (MPS) cells tend to opsonize largely hydrophobic and charged systems. Thus, water-soluble and neutral (or slightly anionic) compounds (e.g., Polyethylene Glycol) are used to coat the nanocarriers surface [31, 32, 34]. Active targeting also depends on the EPR effect to accumulate the delivery nanocarriers in the tumor region, however, the efficacy of this strategy capitalize on equipping the nanocarriers’ surface with ligands that bind to specific receptors of cancer cells, thus, enhancing the penetration and efficiency of the chemical therapeutics. Figure 1 illustrates passive and active targeting strategies.
Figure 1.
Schematic illustration of active and passive delivery of drug molecules.
2.3 Drug releasing
Biodegradation of the nanocarriers is essential for the release of the drug molecules over extended periods of time (days or weeks). It is also crucial for the removal of delivery systems from the body [35]. The carrier size has an effect on the efficacy of the releasing process; drug molecules loaded at or in proximity to the surface of small particles are released at a fast rate due to the large surface-to-volume ratio. On the other hand, slower release rates are associated with larger particles, nevertheless, more drug molecules can be loaded. Modulation of the drug release can also be controlled by the molecular weight of the gel composition; higher molecular weight tends to exhibit slower release rates [36, 37]. In general, the mechanism of releasing drugs is dependent on three main parameters: drug diffusion and dissolution, gel matrix design, and interaction between the drug and the gel matrix.
The transport of the therapeutic molecules out of the gel matrix is a complex process that depends on the dissolution and diffusion of the drug [38]. Several studies have been conducted to develop mathematical models that describe this process [39, 40, 41]. The basic equation of the dissolution rate as a function of diffusion can be described as [42].
dMdt=DAhCs−CE1
Where dM/dt is the rate of dissolution, A is the surface area of solid in contact with the dissolution milieu, D is the diffusion coefficient, Cs is the drug solubility, and C is the drug concentration at time t, and h is the diffusion boundary layer thickness at the solid’s surface. This equation shows that the dissolution rate is directly dependent on the surface area of the particle and the solubility of the drug. Conversely, larger thickness of the diffusion boundary layer reduces the dissolution rate. When the size of the nanocarriers is reduced from the micro-domain to nano-domain, the surface area increases resulting in a higher rate of dissolution as reported in [43].
There are several mechanisms to release the drug, most common strategies are diffusion and swelling controlled. In diffusion-controlled delivery systems, drug molecules diffuse from a region of high drug concentration (reservoir) through the gel matrix or membrane. The design of these systems is commonly available as spheres, cylinders, slabs, or capsules. These systems can have a constant rate of release as described by Eq. (1), or their release rate can be proportional to the square root of time. In the latter case, the drug is usually dispersed or dissolved uniformly through the matrix of the hydrogel [10]. In swelling controlled systems, the drug is dispersed within carriers made of a glassy gel, and upon contact with biofluids, they swell beyond their boundary which results in the diffusion of the drug during the relaxation of the gel chains, this process is known as anomalous transport [10, 44]. Illustrations of the two releasing mechanisms provided in Figure 2. The structure of the nanocarriers’ controls the release of the drugs; using hydrogels alone in synthesizing the nanocarriers can result into fast premature release of drugs and poor tunability [45]. Therefore, using additives can enhance the control of the drug delivery process; using Polydopamine (PDA) as an additive to the hydrogel materials in making the nanocarriers provides an on-demand capability to release the drug. In high glutathione (GSH) and acidic condition, the bond between the drugs and PDA experience weakening. This is a useful property to release the drugs in inflammatory areas or tumor cites where pH levels are low. While at neutral pH levels such as in normal tissues, the bond between the PDA and the therapeutic dugs is not affected [46, 47, 48, 49, 50]. Furthermore, PDA generates heat upon exposure to near infrared (NIR) laser, which makes it ideal for NIR triggered drug delivery [51].
Figure 2.
Schemes of drug release systems: (a) from a reservoir system; (b) from a matrix system.
3. Hydrogel administration
Besides long-term stability and release properties, passing the toxicity screening is essential for hydrogel formulations to be used in drug delivery. This is mainly due to the rise of inflammatory reactions that occur as a result of the degradation of synthetic polymers [52]. Therefore, achieving biocompatibility is necessary to use hydrogels in an environment of living organisms. Most in-vivo tests are conducted on animal models to provide reliable biomedical mimicry. As a result, several hydrogel-based drug delivery systems have been developed and approved for clinical use through different administration routes. Currently, the common accessible routes of these systems are Oral [53], rectal [54], subcutaneous [55], transdermal [56], ocular [57], and intraperitoneal [58]. These administration routes are illustrated in Figure 3. Table 1 provides examples of gel-based products used in drug delivery through different administration routes.
Figure 3.
In-vivo hydrogel-based drug delivery in most common routes of administration. The schematic illustration is reproduced from [59].
Route of administration
Shape
Typical dimensions
References
Oral
Spherical beads; Discs; Nanoparticles
1 μm–1 mm Diameters of 8 mm and thickness of 1 mm 10–1000 nm
Types of hydrogel-based products applied via different routes of drug administration [10, 59].
3.1 Oral route
Oral administration currently is the most common and convenient for hydrogel drug delivery systems, thanks to their bioavailability and nontoxicity they provide [67, 68]. However, such systems have limitations due to the metabolic effect these systems have on the living organism including but not limited to denaturation and reduction of epithelial membrane permeability [52]. Delivery systems in this strategy are usually made from caprolactone, MPEG, itaconic acid pH-sensitive hydrogels as they were reported to have no signs of toxicity [68].
3.2 Rectal route
This route provides an alternative to intravenous and subcutaneous medication delivery. It has faster absorption of the medication through rectum’s blood vessels, which makes it ideal for therapeutics that have high bioavailability and shorter duration [69, 70]. Moreover, it provides a stable environment in which the drugs are released since this administration strategy bypasses the gastrointestinal tract. As a result, minimal alterations occur to the drug concentration when it reaches the circulation system [71]. Hydrogel-based delivery systems such as catechol-chitosan gels have shown excellent biocompatibility and were reported to have no toxicity in-vitro and in-vivo [54, 72].
3.3 Subcutaneous route
This route is very common in studies that involve animal models when developing gel-based injectable biomaterials such as alginate [73], gelatin [74], poly-acrylamide [75], ellagic acid [76], and pectin [77]. While these biomaterials have shown no toxic response when deployed in-vivo into the animal model, the majority of the studies have reported inflammatory effect due to the vascularized nature of the subcutaneous region that is associated with reactions against foreign moieties [78].
3.4 Transdermal route
In topical delivery, the therapeutics reach the circulation system through penetrating the skin layers; the drug passes through the startum corneum to deeper epidermis and dermis until it is absorbed by the dermal microcirculation [79, 80]. The hydrophilic nature of hydrogels allows them to hold considerable amounts of fluid content that ranges between 10% to 1000 times gels’ dry weight [81], which makes them ideal for carrying drugs such as insulin, theophylline, sodium fluoride, and progesterone and heparin. Transdermal hydrogel patches can provide a controlled rate of drug delivery in addition to providing a cooling effect at the location where they are applied [81]. Hydrogels can also be combined with bio-adhesives to prolong the therapeutic effect of the delivered drug when applied topically [82].
3.5 Intraperitoneal route
Intraperitoneal injections of hydrogel systems are considered a successful delivery strategy for various therapeutic agents. The injected hydrogels compounds can achieve efficient drug delivery while exhibiting anti-adhesiveness properties on the peritoneum [83]. Although intraperitoneal hydrogels were reported to be non-toxic [84], their hydrophilicity can compromise the concentration of the delivered pharmaceutical agents [58].
4. Types of therapeutics delivered using hydrogels-based delivery systems
4.1 Small molecular weight drugs
Budhian et al. [85] categorized the release of this class of drugs into three stages; (i) initial burst, during which the drugs immediately released into the medium; (ii) induction, in which the release of drugs is gradual; and (iii) slow release, in which the release reaches a steady slow rate [85]. These stages are controlled by three unique properties of the gel in use to synthesize the delivery systems: hydrophobicity, surface coating, and particle size [35]. The lower the hydrophobicity the higher the release of drugs during the burst stage; for example, the percentage of released drugs after 1 day is 45% for 220 nm strongly hydrophobic PLA particles, on the other hand, the release percentage is 70% for the same size of the moderately hydrophobic PLGA particles. The release stages are also affected by the surface coating of the nanoparticles; coating PLGA particles reduces the number of drugs released by 40%. The rate of release and the initial burst are affected by the size of the particles; increasing the size decreases the total surface area which reduces the burst period, furthermore, the larger the size, the longer the pathways the drug molecules take during the diffusion which increases the induction period [85].
4.2 Therapeutic peptides and proteins
Among several peptides- and proteins-based therapeutics that are used in drug delivery, enzymes are the most studied class of drugs [86]; examples of such enzymes include L-asparaginase, cysteine desulfatase, cysteine oxidase, arginase, and arginine decarboxylase [87]. Currently, only a few protein- and peptide-based drugs have been used in medicinal setting. The clinical use of this class of drugs is hindered by several factors: enzymatic degradation, renal filtration, inefficient cell entry, accumulation in nontargeted organs, immune system response that causes allergic reaction, and protein inactivation due to intrinsic properties such as low stability in an environment of physiological pH and temperature [88].
A simple approach to overcome the elimination of this class of drugs is introducing it via injection to the targeted organ. However, this strategy has its own limitations such as difficulty or delocation of the targeted site, drug toxicity, and long-term hospital setting administration [88]. Other delivery strategies were proposed such as microfabricated chips and implantable devices [89, 90]. While these strategies have shown promising results, their deployment and extraction require surgical intervention. To overcome these challenges and to stabilize the therapeutic proteins and peptides in the physiological environment, they are encapsulated into nanocarriers. This technique protects the enzymes from the degradation parameters imposed by the physiological environment while delivering different types of protein-based drugs [88].
Shimizu et al. [91] developed nanocarriers that efficiently encapsulates bone morphogenic proteins (BMPs), which have significant capability to convince bone formation. When BMPs are encapsulated by the developed nanocarriers, they provided sustained delivery of the BMPs over a time period of 14 days. In cancer therapy, polymersomes are used to deliver therapeutics; Danafar et al., 2016 investigated the delivery of drug molecules encapsulated into mPEG-PCL hydrogel nanocarriers in treating breast cancer. Their mPEG-PCL carriers provided suitable pH-dependent delivery of therapeutics to breast cancer cells [92].
4.3 Vaccines
Establishing an immunological memory and provoking sufficient immune response are the two primary factors that determine the efficacy of a vaccine delivery system [93, 94]. The main administration routes of vaccine delivery systems are parenteral and non-parenteral. The first is administered using hypodermic needles inserted through subcutaneous, intramuscular, and intradermal routes [95, 96]. On the other hand, non-parenteral delivery systems capitalize on needle-free devices such as jet injectors, liquid, powder, and polymeric (including hydrogel) systems [97]. In hydrogel-based systems, gel particles encapsulate the vaccine molecules and deliver it through intramuscular, oral, and transcutaneous routes [98, 99]. In recent years, different hydrogel delivery systems were developed to increase the efficiency of the vaccine delivery, Table 2 summarizes these systems and their applications.
Hydrogel based system
Applications
References
Thermo-sensitive
H5N1 Influenza vaccination; Ebolavirus glycoprotein antigen; prevention of ovine brucellosis
Hydrogel-based delivery systems and their applications.
5. Conclusion
Drug carriers are revolutionary delivery systems in the field of medicine. While there have been several studies that reported different types of polymers that has been used to synthesize the carriers, hydrogel-based systems seem to be very promising due to their affordability, production simplicity, and their unique ability to load different types of drugs. Although several gel-based systems have been investigated, designed and IP-protected, it seems only limited number of these product has actually reached the market, which indicates the need for further investigations on improving the performance of current products and develop new ones. This chapter addressed different hydrogel-based drug delivery systems from different perspectives including mechanisms (loading, releasing, and targeting), design (shape and route of administration), and the classes of delivery drugs. These elements are essential when designing and investigating state-of-the-art hydrogel-based delivery systems.
Acknowledgments
The author acknowledges the support of BK21 FOUR Program through the National Research Foundation of Korea (NRF), the Ministry of Education.
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Thus, several drug targeting, loading, and releasing mechanisms have been devised and reported in the literature. This chapter discusses these mechanisms and their efficacy with respect to different drug delivery applications. Furthermore, the drug dosage is dependent on the design and shape of the hydrogel systems, which in turn depend on the route of the drug administration. This chapter covers the types of hydrogel-based products applied via different routes of drug administration. Lastly, this chapter addresses different classifications of delivered drugs including small molecular weight drugs; therapeutic proteins and peptides; and vaccines.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/80823",risUrl:"/chapter/ris/80823",signatures:"Wanis Nafo",book:{id:"11130",type:"book",title:"Hydrogels - From Tradition to Innovative Platforms With Multiple Applications",subtitle:null,fullTitle:"Hydrogels - From Tradition to Innovative Platforms With Multiple Applications",slug:null,publishedDate:null,bookSignature:"Prof. Lacramioara Popa, Dr. Mihaela Violeta Ghica and Prof. Cristina Dinu-Pirvu",coverURL:"https://cdn.intechopen.com/books/images_new/11130.jpg",licenceType:"CC BY 3.0",editedByType:null,isbn:"978-1-80355-583-6",printIsbn:"978-1-80355-582-9",pdfIsbn:"978-1-80355-584-3",isAvailableForWebshopOrdering:!0,editors:[{id:"228211",title:"Prof.",name:"Lacramioara",middleName:null,surname:"Popa",slug:"lacramioara-popa",fullName:"Lacramioara Popa"}],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. Drug loading, targeting and releasing",level:"1"},{id:"sec_2_2",title:"2.1 Drug loading",level:"2"},{id:"sec_3_2",title:"2.2 Targeting",level:"2"},{id:"sec_4_2",title:"2.3 Drug releasing",level:"2"},{id:"sec_6",title:"3. Hydrogel administration",level:"1"},{id:"sec_6_2",title:"3.1 Oral route",level:"2"},{id:"sec_7_2",title:"3.2 Rectal route",level:"2"},{id:"sec_8_2",title:"3.3 Subcutaneous route",level:"2"},{id:"sec_9_2",title:"3.4 Transdermal route",level:"2"},{id:"sec_10_2",title:"3.5 Intraperitoneal route",level:"2"},{id:"sec_12",title:"4. Types of therapeutics delivered using hydrogels-based delivery systems",level:"1"},{id:"sec_12_2",title:"4.1 Small molecular weight drugs",level:"2"},{id:"sec_13_2",title:"4.2 Therapeutic peptides and proteins",level:"2"},{id:"sec_14_2",title:"4.3 Vaccines",level:"2"},{id:"sec_16",title:"5. 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UK Research and Innovation (former Research Councils UK (RCUK) - including AHRC, BBSRC, ESRC, EPSRC, MRC, NERC, STFC.) Processing charges for books/book chapters can be covered through RCUK block grants which are allocated to most universities in the UK, which then handle the OA publication funding requests. It is at the discretion of the university whether it will approve the request.)
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Travieso-González received his MSc degree in Telecommunication Engineering at Polytechnic University of Catalonia (UPC), Spain in 1997, and his Ph.D. degree in 2002 at the University of Las Palmas de Gran Canaria (ULPGC-Spain). He is a full professor of signal processing and pattern recognition and is head of the Signals and Communications Department at ULPGC, teaching from 2001 on subjects on signal processing and learning theory. His research lines are biometrics, biomedical signals and images, data mining, classification system, signal and image processing, machine learning, and environmental intelligence. He has researched in 52 international and Spanish research projects, some of them as head researcher. He is co-author of 4 books, co-editor of 27 proceedings books, guest editor for 8 JCR-ISI international journals, and up to 24 book chapters. He has over 450 papers published in international journals and conferences (81 of them indexed on JCR – ISI - Web of Science). He has published seven patents in the Spanish Patent and Trademark Office. He has been a supervisor on 8 Ph.D. theses (11 more are under supervision), and 130 master theses. He is the founder of The IEEE IWOBI conference series and the president of its Steering Committee, as well as the founder of both the InnoEducaTIC and APPIS conference series. He is an evaluator of project proposals for the European Union (H2020), Medical Research Council (MRC, UK), Spanish Government (ANECA, Spain), Research National Agency (ANR, France), DAAD (Germany), Argentinian Government, and the Colombian Institutions. He has been a reviewer in different indexed international journals (<70) and conferences (<250) since 2001. 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He won the “Catedra Telefonica” Awards in Modality of Knowledge Transfer, 2017, 2018, and 2019 editions, and awards in Modality of COVID Research in 2020.\n\nPublic References:\nResearcher ID http://www.researcherid.com/rid/N-5967-2014\nORCID https://orcid.org/0000-0002-4621-2768 \nScopus Author ID https://www.scopus.com/authid/detail.uri?authorId=6602376272\nScholar Google https://scholar.google.es/citations?user=G1ks9nIAAAAJ&hl=en \nResearchGate https://www.researchgate.net/profile/Carlos_Travieso",institutionString:null,institution:{name:"University of Las Palmas de Gran Canaria",institutionURL:null,country:{name:"Spain"}}},editorTwo:null,editorThree:null},{id:"23",title:"Computational Neuroscience",coverUrl:"https://cdn.intechopen.com/series_topics/covers/23.jpg",isOpenForSubmission:!0,annualVolume:11419,editor:{id:"14004",title:"Dr.",name:"Magnus",middleName:null,surname:"Johnsson",slug:"magnus-johnsson",fullName:"Magnus Johnsson",profilePictureURL:"https://mts.intechopen.com/storage/users/14004/images/system/14004.png",biography:"Dr Magnus Johnsson is a cross-disciplinary scientist, lecturer, scientific editor and AI/machine learning consultant from Sweden. \n\nHe is currently at Malmö University in Sweden, but also held positions at Lund University in Sweden and at Moscow Engineering Physics Institute. \nHe holds editorial positions at several international scientific journals and has served as a scientific editor for books and special journal issues. \nHis research interests are wide and include, but are not limited to, autonomous systems, computer modeling, artificial neural networks, artificial intelligence, cognitive neuroscience, cognitive robotics, cognitive architectures, cognitive aids and the philosophy of mind. \n\nDr. Johnsson has experience from working in the industry and he has a keen interest in the application of neural networks and artificial intelligence to fields like industry, finance, and medicine. \n\nWeb page: www.magnusjohnsson.se",institutionString:null,institution:{name:"Malmö University",institutionURL:null,country:{name:"Sweden"}}},editorTwo:null,editorThree:null},{id:"24",title:"Computer Vision",coverUrl:"https://cdn.intechopen.com/series_topics/covers/24.jpg",isOpenForSubmission:!0,annualVolume:11420,editor:{id:"294154",title:"Prof.",name:"George",middleName:null,surname:"Papakostas",slug:"george-papakostas",fullName:"George Papakostas",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002hYaGbQAK/Profile_Picture_1624519712088",biography:"George A. 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His research interests include computer/machine vision, machine learning, pattern recognition, computational intelligence. \nDr. Papakostas served as a reviewer in numerous journals, as a program\ncommittee member in international conferences and he is a member of the IAENG, MIR Labs, EUCogIII, INSTICC and the Technical Chamber of Greece (TEE).",institutionString:null,institution:{name:"International Hellenic University",institutionURL:null,country:{name:"Greece"}}},editorTwo:null,editorThree:null},{id:"25",title:"Evolutionary Computation",coverUrl:"https://cdn.intechopen.com/series_topics/covers/25.jpg",isOpenForSubmission:!0,annualVolume:11421,editor:{id:"136112",title:"Dr.",name:"Sebastian",middleName:null,surname:"Ventura Soto",slug:"sebastian-ventura-soto",fullName:"Sebastian Ventura Soto",profilePictureURL:"https://mts.intechopen.com/storage/users/136112/images/system/136112.png",biography:"Sebastian Ventura is a Spanish researcher, a full professor with the Department of Computer Science and Numerical Analysis, University of Córdoba. 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He obtained both his M.Sc. and Ph.D. from the University of Liverpool, England, in the field of Intelligent Systems. He is a full professor at the Universidad Autonoma de Queretaro, Mexico, and a member of the National System of Researchers (SNI) since 2009. Dr. Aceves Fernandez has published more than 80 research papers as well as a number of book chapters and congress papers. He has contributed in more than 20 funded research projects, both academic and industrial, in the area of artificial intelligence, ranging from environmental, biomedical, automotive, aviation, consumer, and robotics to other applications. He is also a honorary president at the National Association of Embedded Systems (AMESE), a senior member of the IEEE, and a board member of many institutions. 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