Nomenclature of graphene based on the structure.
\r\n\tIn this book, the different factors of liquefaction, the field methods and laboratory tests to identify a potentially liquefiable soil aim to be reviewed; in addition with history cases (ground behavior during the occurrence of an earthquake, state of stress, deformation, shear strength, flow, etc.).
\r\n\tA very important aspect of this topic is the presentation of the different constructive techniques used to ground improvement (vibrocompaction, dynamic compaction, jet grouting, chemical injection, replacement, etc.), placing special emphasis on those constructive methods used to solve problems on structures already located in areas of low relative density with liquefaction potential, where the installation of monitoring and control equipment is also required (tiltmeters, piezometers, topographic points, seismographs, pressure cells, etc.).
Due to lower consumption of vegetables by lizards, often the groups are overlooked in studies that discuss herbivory. However, it is important to discuss this matter in order to obtain a better understanding with regard to lizards/plant interaction, inasmuch as there are determinants physiological characteristics for the occurrence or absence of such interaction. Considering that the plants compose the diet of lizards, it is worth emphasizing the ecological importance of this relationship, which composes the trophic chain.
\nA few species of living lizards currently present are essentially herbivores, especially when compared with the extensive fauna of herbivorous reptiles of the Mesozoic [1]. Regarding diet, most lizards consume small animals and rarely plant material. On the other hand, there are omnivores species and some exclusively herbivores [2]. Accordingly, many factors can influence the consumption of plants, such as seasonal availability of food items, digestibility, and components from the consumed plants [3].
\nThe nutrient assimilation capacity in herbivores is less than in omnivores, while such capacity is lesser in omnivores than in carnivores [1]. The low nutrient assimilation capacity in lizards reduces growth rates and reproductive capability, causing a reduction in egg production by females [2, 4]. Thus, the consumption of plants can make them more susceptible to predation, influencing in the adaptive radiation of the species.
\nAn herbivorous diet requires adaptations, physiological or behavioral, for the digestion of cellulose. Such adaptations may be: specialized dentition, elongated intestines, colic valves, intestinal flora, and thermoregulation to maintain high body temperature [5], inasmuch as gut fermentation, which is necessary for plant digestion, requires prolonged periods of high body temperature [6]. Every part that makes up a plant requires different adaptations for digestion because the parts vary significantly in their structure and composition. Leaves and stems are more difficult to digest than nectar, pollen, flowers, and fruits, due to the greater amount of cellulose present.
\nThe consumption of plant material by lizards is less frequent than in other groups, such as mammals and birds. Many species consume vegetables, but they are considered omnivorous (capable of metabolizing different food items) and the majority of their diet is composed of small animals, consisting essentially of arthropods. Less than 3% of lizard species are considered essentially herbivorous [1, 2, 4, 7]. Lizards are considered strictly herbivorous only if more than 90% of its diet is composed of plant materials [3]. The ectothermy[1] - is one of the reasons for the lower consumption of vegetables by the lizards, compared to mammals and birds, insofar as the temperature variations according to the environment difficult digestion of these materials. For the occurrence of the digestion of plant material, a long time of thermoregulation is necessary, because at low temperatures the absorption of nutrients is compromised, reducing the energetic efficiency. On the other hand, a long exposure time for thermoregulation increases the risk of predation. As an example, it can be cited that the lizard Dipsosaurus dorsalis (Baird and Girard, 1852), a herbivorous lizard from the desert, maintains higher temperatures than other iguanids insectivorous lizards and is active for a long period of the day [8].
\nRegarding this issue, for some species, to increase the body temperature is not the main mechanism used for digestion of plant material. The lizard Cnemidophorus murinus (Laurenti, 1768) keeps the body temperature similar to other teiids lizards but it remains active much longer to facilitate the digestion of plant [9], in that way the body temperature is maintained constant at about 37°C, predominantly during the day [6].
\nSince plant tissues are more difficult to digest than animal tissue, lizards require mechanisms that facilitate the digestion. Moreover, birds and mammals that are exclusively herbivores have high energy efficiency due to temperature maintenance and digestive symbiotic associations [4].
\nThen, it raises the following question: what are the factors that allow some species of lizards feed on plants and not others? The first studies that have sought to elucidate this query, consider the size of the animal as decisive in choosing the type of diet. Theoretically, harder items need greater strength and efficiency in chewing, and to have a larger and more robust head, allowing a stronger bite [10]. Campos, in a work about the lizards of Microlophus genus, found differences in cranial morphology associated with their diet: species that consume plant material have larger and wider skulls than the insectivorous ones. In this sense, large lizards could employ greater strength in their jaws, producing a better grinding of the food. For a time, it was assumed that only large lizards would be able to reduce plant material into digestible portions [7]. Several recent studies have shown that smaller species are able to consume plant material. Nevertheless, the adaptations which allow these species consume plants are lesser known [5].
\nBesides the initial process of tissues breaking by chewing, for digestion of more resistant materials, it is necessary a more elongated digestive tract and, the presence of symbiotic relationships. More elongated intestines, as well as chewing ability, are related to the body size of the animal. It is known that most herbivorous lizards belong to Iguanidae family. This is one of the few groups of lizards known which have expertise to digest plant material. The iguana intestine contains colic valves in order to increase the area of absorption and residence time of food in the intestines as well as intestinal flora suitable for cellulose degradation [3].
\nIn a manner contrary to the trend related to body size, Liolaemus lutzae (Mertens, 1938), a species of small size, consumes large amounts of plant material, presenting evidence of capacity to cut leaves to consume them [11]. The same author concluded that the consumption of leaves by the species does not occur indiscriminately, inasmuch as the most common plant species in the stomach contents are less frequent in the studied area, suggesting that there is selection of the items to be consumed by their qualitative properties: amount of cellulose, sugars, fibers, tannins, and other components of the plant.
\nOmnivores Lizards, which include plant materials in their diets, tend to consume the softer parts of the plant, such as flowers and fruits containing large amounts of lipids, carbohydrates, sugar, and protein [12].
\nThe selection of certain plant parts is also observed in other species, such as Tropidurus torquatus (Wied‐Neuwied, 1820), species of omnivorous diet which also consumes plant material, tends to consume fruits, since they have a good digestibility [13]. Similarly, Tupinambis teguixin (Linnaeus, 1758) in a population of eastern Chaco, Argentina, presented plant material as its main diet composition (over 60%), in which most were fruits [14], even though it is a species of large size. Therefore, there is not an only factor, but a set of factors that influence the herbivory in the lizards.
\nLeiocephalus carinatus (Gray, 1827), another omnivorous species, has on your diet 47% of plant material. Kircher et al. [15] reported the use of Ipomoea pes‐caprae flowers by adults of the species, in the Cayman Islands, Cuba.
\nOmnivorous species, as well as the herbivorous ones, can select parts of plants rich in nutrients and low cellulose content to consume, according to their physiological demand or digestive adaptations. Lizards that consume plant material in small quantities, or that do it occasionally, choose parts easier to digest or that which do not require specific adaptations to digestion. Lizards of omnivorous diet consume fruits and flowers intentionally when their preys are scarce. Conversely, the consumption of fragments of plant material by carnivorous animals occurs accidentally [3].
\nSome lizard species have food preferences according to the presence or absence of certain components. Dicrodon guttulatum (Duméril and Bibron, 1839), from Teiidae family, prefers the Prosopis pallida tree. Velásquez et al. [16], examining the D. guttulatum diet, in the P. pallida absence, found predominantly leaves of Acacia sp. and fruits from Scutia spicata and Capparis sp. In a study carried out by Leeuwen et al. [5] about the diet of the same lizard species in an environment with P. pallida, it was detected mainly this plant species in stomach contents and rarely other plants, even if they were available in the environment.
\nThe presence of water in the fruit is also an important factor for consumption. Figueira et al. [17], investigating the interaction between T. torquatus with Melocactus violaceus (Cactaceae) reported the consumption of fruits always that they were available. These fruits have elevated water content and low sugar levels, indicating that the plant can be important to supply the need for water.
\nAlthough less frequent, some studies have looked for to understand how the lizards detect or choose vegetables to be consumed. Vasconcellos‐Neto et al. [18], using models of artificial fruit, concluded that T. torquatus consume fruits that have higher color contrast in relation to the substrate or plant where they are, as well as they prefer conic fruits to other forms. It should be noted that the species has accurate visual perception, used for catching prey. As previously mentioned, T. torquatus consumes fruits of M. violaceus, which is a cactus whose fruits are conical, colorful, and close to the ground. That fact supports the hypothesis that lizards can to use visual perception to the fruit location and for identification of the ideal shape for the extrusion process [17].
\nThe chemical perception ability for plant identification is correlated with the evolution of herbivory in Scleroglossa [3]. For Iguania lineage there are records of using of chemical samples collected by language in D. dorsalis [19]. In iguanas, the chemical discrimination of food has a strong correlation with the evolution of herbivory [20]. The use of chemical perception is important in the consumption of plant material, as these food items are motionless, making difficult the visual identification. Similarly, if different parts of the plant and different species have distinct compositions, the act of identifying the food before eating increases energy efficiency and also may avoid the consumption of species with toxins [3].
\nAlthough small fruits tend to be more easily handled and eaten by frugivorous, studies with lizards have not confirmed this trend. Rodríguez‐Pérez and Traveset [21] studied the interaction between Daphne rodriguezii, an endemic shrub from Menorca Island (in Spain), with the lizard Podarcis lilfordi (Günther, 1874), which is its disperser. In such study the seeds size was not an important factor for the selection of fruits, because seeds are not predictors of the amount of pulp mass.
\nThe chameleon Furcifer oustaleti (Mocquard, 1894) consume plant parts using different mechanism of collection if compared with animal prey. The capture of arthropods occurs through the projection of his tongue, while the consumption of fruit, for example, takes place by direct collection of the jaws. The mechanism indicates that the individuals identify the food item before consuming them and, since there is no need to capture vegetables items, the chameleons opt for direct collection, saving energy spent on the tongue projection [22].
\nBenítez‐Malvido et al. [23] in an investigation about seed dispersal by Iguana iguana (Linnaeus, 1758), have observed that individuals of the species select the items from their diet, consuming fleshy fruits. The reason is that fleshy fruits have higher amount of water, sugars and less material of hard digestion. In the same study it was observed that puppies of I. iguana have difficulty eating large fruits or coriaceous ones because of the reduced body size.
\nIt is worth mentioning that the presence of flowers and fruits in the diet of lizards is strongly influenced by the period in which the study was developed, due to seasonal availability of these items [24]. For that reason, the relative importance of consumption of plant material is dependent on the period of the sample, which limits discussions about the subject.
\nSome lizards choose to consume nectar or pollen in order to have a higher concentration of nutrients. That enables individuals pollinate plants, since they visit different flowers. The consumption of nectar for lizards is rarer, but there are some records. Although not common, such interaction is important, as it allows for pollination events. And, since the consumption occurs mainly on islands [25], environments that often lack pollinators, the lizards are fundamental in the maintenance of communities.
\nGeckos of the Hoplodactylus genus, in New Zealand, consume pollen from native plant species [26]. Geckos increase the consumption of flowers as enhance the viscous nectar (53% sugar). P. lilfordi are also potential pollinators of flowers belonging to the Euphorbia dendroides species, at island environments [27]. Furthermore, there are records of pollen consumption for the lacertid lizards Gallotia simonyi (Steindachner, 1889), P. lilfordi, and Podarcis pityusensis (Bosca, 1883) and the gecko Rhacodactylus auriculatus (Bavay, 1869) [3, 27].
\nFactors related to the habitat of species may have direct influence on the consumption of vegetables by lizards, such as the availability of prey, aridity [3] and island environments [15].
\nThe evolution of plant consumption may be favored by habitat factors that reduce the availability of prey [3]. It is observed on islands with low predation rates [4]. Another factor that likely influences in vegetable consumption is the intraspecific competition. When the density of the population increases, reducing the availability of prey, the feeding of alternative items favors the maintenance of the species.
\nHerbivorous in lizards evolves more commonly in species that occur in small islands, and appears to result from a lower abundance of arthropod preys available in these habitats [15]. An evidence is that when the diets of two populations of T. torquatus were compared, one continental and another insular, they were the same. This is likely because the availability of arthropods in both environments was similar [28].
\nIn addition, as in islands, the species diversity is smaller, the occurrence of predators is reduced; therefore, the risk of exposure to the sun for thermoregulation is also reduced. Considering that, in that case, the lizards are able to maintain higher body temperatures, the energy efficiency rises, becoming advantageous the consumption of vegetables.
\nFossil records of Gallotia clade, a group of lacertid lizards that inhabit the Canary Islands, shows that island environments are crucial in the development of herbivory, since even the individuals which are primitively of large body, the herbivory just has developed after the colonization of the islands [29]. Before the colonization they were carnivores. This study highlights the effect of abiotic factors on the ecology of the species.
\nHowever, all the evidence that island environments favor the development of herbivory are hypothesis, they have not been tested [3].
\nThere are evidences that an arid environment favors the development of herbivory because of seasonal and unpredictable scarcity of prey. On the other hand, it is not possible to assess the effect of this factor on diet in an isolated way, since many islands are arid, becoming impossible to isolate the factors.
\nAnyway, the main factor directly related to the consumption of plants, predominantly in omnivorous species, is the availability of prey. About 80% of species respond to that factor.
\nThe availability of prey is so decisive for the establishment of populations of insectivorous species that lizards of Liolaemidae family have a tendency to herbivory, related with the climate, which is contrary to the other groups. Espinoza et al. [30], in an article concerning the evolution of herbivory in individuals belonging to that family, concluded that vegetable consumption is directly correlated with cold climates while most herbivores live in habitats with hot and dry climate. Herbivorous tropical lizards (Iguana, Ctenosaura, and Amblyrhynchus) live in environments where the temperature remains high in most of the day.
\nLiving lizards are divided into two large lineages: the Iguania (e.g., iguanas and chameleons) and Scleroglossa (all other lizards). These groups have pronounced differences in foraging behavior: Iguania presents ambush foraging, consuming mainly insects, with some herbivores and omnivores individuals, which is a behavior derived from ambush forage. On the other hand, Scleroglossa includes mostly individuals with active foraging, a few ambush foragers, and a small amount of herbivores and omnivores [20].
\nThe consumption of plant material occurs in the families of both lineages: Iguania and Scleroglossa. In Iguania it is present in almost every family with known data. Except in Chamaeleontidae and Crotaphytidae, the vegetable diet is of universal occurrence in Iguanidae (occurs in all species) and frequent in the species of the Tropiduridae family. In Scleroglossa the herbivory is absent in Pygopodidae, Eublepharidae, Gymnophthalmidae, Cordylidae, and most families of Anguimorpha [3].
\nDespite the lack of known robust phylogenetic relationship in the lizards, which makes difficult to trace the exact epoch that occurred the vegetable consumption evolution in these reptiles, the discovered patterns allow to infer that such evolution happened in several periods of their evolutionary tree.
\nIn the following, some comments about the main families are presented, for which studies have been carried out concerning herbivory.
\nMost herbivorous lizards belong to the Iguanidae family. The majority of species are strictly herbivorous. Others present ontogenetic changes, consuming plant material when they are adults. This family also has folivorous feeders. It is worth remembering that some species have their adaptations proper to the consumption of plant material, as previously mentioned. Another fact is that the herbivory is present in the common ancestor of Iguanidae [3].
\nIn Tropiduridae family, the consumption of plant material is well known. Most genera are omnivores. And the degree of consumption varies considerably between genera and species. Many studies have shown data about the Tropidurus genus, stating that its diet has ontogenetic, seasonal and geographical variations [13, 31], as well as it reflects to local availability of foods [28]. Liolaemus lutzae also presents ontogenetic change in its diet [11].
\nThe Agamidae family, which comprises lizards known as Australian Water Dragon, has some omnivores genera and only two herbivores genera while Hydrosaurus pustulosus is an exclusively folivorous species [3]. The other species that include plant material in their diet tend to consume the parts easier to digest, such as fruit and leaves.
\nMany species of the Gekkonidae family consume small amounts of plant material. Some geckos from New Zealand have omnivorous diet with consumption of different parts of the plant. Wotton [24] described the diet of Mokopirirakau granulatus (Gray, 1985), while for Naultinus grayii (Bell, 1843) it was reported by Whitaker [26].
\nThe diet of lizards presents variations in response to different factors. Some species show changes between the sexes, possibly because of morphological differences, as in many species the males have larger body size than females. Other studies have indicated the seasonal variation in the diet. The species with such variation, in general, live in environments where there is rainfall variation over the year. However, a large part of the diet variation in lizards is explained by the availability of food in their living area. Considering that the main plant components in the diet of lizards are fruits and flowers, it is expected a seasonal influence on the diet [24].
\nThere is still, in a long term, ontogenetic changes in the diet of lizards, when young individuals have a different diet in comparison to the adults from the same species. This fact occurs due to the difference in energetic demands during the growth of individuals. Most lizards which are omnivorous and also consumes vegetables, as young they feed basically on insects. Only I. iguana has an exclusively herbivorous diet, both in adults and young ones [25].
\nThe evidences of ontogenetic change in the consumption of vegetables can be observed if it is considered the quantity of vegetables consumed or in relation to the plant parts that make up the diet such as leaves, fruits, flowers, or nectar. Since each component has a different proportion of protein, water, fiber, glycides, and cellulose (the most difficult component to digest). During the period, the demand for protein is higher thus, a diet plant‐based would not supply the energy needs. Therefore, puppies tend to look for food items with higher amounts of protein [3].
\nAs adults, certain species begin to add larger amount of plant material in the diet. There are several reasons for that. It may be the greater availability of these items, since in certain environments, such as islands, the availability of arthropod is reduced; presence of water in the fruits (in arid environments is an essential feature for maintaining the species metabolism); more facility of handling when compared to prey, inasmuch as in order to capturing small invertebrates it is necessary a higher energetic spent than the consumption employed only in collecting fruits. For example: reduced competition, as youth and adults consume different food items, they will not compete for the same niche, and nutritional content.
\nThe ontogenetic change in alimentation is well marked in omnivorous species despite being also observed in essentially herbivorous species. Microlophus thoracicus (Tschudi, 1845), an omnivorous species, presents ontogenetic change in its diet, consuming insects as juvenile, adding vegetables when adult [10].
\nRocha [11] carried out a study about ontogenetic changes in L. lutzae diet in Barra do Baricá, coast of Rio de Janeiro (Brazil). Despite its small size during adulthood (60–80 mm), nearly half of the diet of the species was composed by vegetables material, and the presence of these items increased according to increase of age and body size of the individuals. This is reinforced by the fact that lizards with snout‐vent‐length (SVL) smaller than 38 mm consumed only arthropods. Such trend was present in both sexes. However, males tend to consume more plant material than females. The low availability of arthropods in beach environments and abundant presence of shrubs make the ontogenetic change an advantage in terms of digestive efficiency. Then, the species begin to explore new niche, limiting the consumption of arthropods by adults in order to not competing intraspecifically with juveniles.
\nPopulations of T. torquatus, which inhabiting the same environment previously mentioned, have showed behavior similar to the L. lutzae, increasing gradually their diet with plant material during growth, and when adult they have almost half of the diet consisting of plant material [13]. The two papers, Rocha and Fialho et al., highlight the importance of environmental factors in the composition of the lizard\'s diet, leading the species to consume items that theoretically would be disadvantageous due to the difficulty of digestion, but that are more accessible.
\nIn environments with seasonality marked by precipitation difference, as well as in tropical environments with dry and rainy seasons (Barra de Maricá), the volume of rain is decisive for the availability of arthropods and also for the plants cycle. Since the more rain the more availability of arthropods. Thus, the diet will vary according to the availability of food in each station. It should be noted also that both species (L. lutzae and T. torquatus) are omnivorous, opportunistic predators and their diets reflect the availability of food items in the habitat.
\nIn order to consider an animal that consumes fruits as a disperser, it is necessary to validate quantitative and qualitative factors. Quantitative factors depend on the number of seeds consumed, while the qualitative ones depend on the location in which the seed is deposited and the effect of the passage through the digestive tract on seed germination [33–35]. The treatment that the seeds receive when they are consumed directly influences the capacity and the speed of germination [21]. In the same way that the distribution pattern of seeds on the microhabitats is a crucial aspect of the dispersion quality [36]. Inasmuch as different microhabitats provide different conditions (illumination, humidity, substrate characteristics, etc.), causing alterations in the rates of germination and seedling survival.
\nSimilarly to the studies of herbivores, research about dispersion syndrome also focuses mainly on birds and mammals. Studies concerning that syndrome in reptiles are less common [23]. However, this group plays an important role, especially species which inhabit arid environments and islands.
\nInformation on seed dispersal by lizards are known for: geckos in New Zealand islands [24, 26]; lizards in various environments in Brazil [31, 37], in the Mexico (Benítez‐Malvido et al.), in island of the Western Mediterranean [21, 38] and iguanas in the Galapagos Islands [39] and dry forests of Costa Rica [40].
\nMany studies have shown a positive effect of the passage through the digestive tract of lizards on the ingested seeds. However, this effect varies with the species consumed.
\nThe environment analyzed by Wotton [24], an island in New Zealand where the gecko Woodworthia maculatus lives (Gray, 1845), has reduced populations of birds and mammals that may disperse the seeds, and compete by the consumption of the fruits. In this sense, the gecko has fundamental importance for the maintenance of the local communities, due to its dispersal potential.
\nThe seed dispersal by lizards is peculiar because, even though being characterized by local events or short distances, it has fundamental importance due to the tendency to eat fallen fruit, inaccessible to other vertebrates like birds [24].
\nIn a paper about seed dispersal by T. torquatus, Pietczak et al. [37] have found that the seeds deposition of Chomelia obtusa (species consumed by the lizard at the studied site) usually occurs in a short distance from the mother plant, around five meters. But, despite the fact that the average dispersal distance is not too long, the species is benefited. The reason for this is that, according to Chapman and Chapman [41], seeds dispersed even in short distances germinate better than ones under the parent plant. The dispersion of seed in locations similar to that of natural occurrence of the species indicates favorable conditions for the germination. In this sense, Pietczak et al. verified that the population of T. torquatus studied merely remained in the areas around a rocky outcrop, depositing the seeds on the edges and clefts of the rocks. Therefore, the places where the lizard deposited the seeds favored the seed germination and seedling development.
\nRodríguez‐Pérez and Traveset [21], in a paper about the interaction of the bush D. rodriguezii and its disperser, namely, the lizard P. lilfordi, stated that the passage through the digestive tract neither increased nor decreased the germination capacity. Nevertheless, the passage through the digestive tract appeared to have caused a reduction in size of the seed, with an action on the coating thickness. Traveset [33] indicates that the reduction of the coating serves as a scarifying process, increasing the permeability of the seed and thus favoring the germination. However, such permeability was not evaluated in detail by Rodríguez‐Pérez and Traveset.
\nOnce again, regarding the work of Rodríguez‐Pérez and Traveset [21], it was observed that seedlings of seeds deposited under the mother plant had lower survival rates compared to the seeds dispersed. Accordingly, even though the passage through the digestive tract of lizards does not significantly increase the germination rate, the deposition pattern of seeds increases the viability of seedlings survival. Thus, the action of lizards is characterized as a disperser. Another paper, studying the same disperser, has obtained similar conclusions, in which the effect of ingestion had neutral results on germination rates, but the seed deposition favored the development of seedling [38]. In this case in particular, since P. lilfordi é is the only disperser of D. rodriguezii, such interaction is essential for the maintenance of the species.
\nThere are some studies that explain the consumption of vegetables by lizards. For a while it was considered the body size as a decisive factor for herbivory. It was thought that only large lizards were able to consume plant material. More recent publications, with small‐ and medium‐sized species, have shown that there are various reasons for some species consume vegetables and others do not.
\nIn relation to the anatomy, physiology and behavior of the species, it is necessary certain adaptations to consume vegetables, such as: specialized dentition, elongated intestines, colic valves, intestinal flora, and thermoregulation to maintain high body temperature. The Iguanas are the lizards with the most elaborate adaptations to herbivory.
\nMany lizards which have omnivorous diet consume plant material. For such a species of lizards, changes in their diet are strongly related to environmental factors. Vegetable consumption by lizards is more likely to occur in insular and arid environments, as well as in areas with reduced predators. But the deciding factor associated with the addition of vegetable items is the availability of prey. Insular and arid environments have lower availability of arthropods, which is the main food item of most lizards. Nevertheless, more studies are needed to isolate each of the following factors: insularity, aridity and availability of prey.
\nEnvironments with prey scarcity also favor the ontogenetic changes in the diet. If there are not enough arthropods for population maintenance, it is more beneficial that youth individuals maintain a diet richer in protein (arthropods) and adults change their diets for items with higher availability (vegetables). Since many species of omnivorous diet do not present physiological or anatomical adaptations to the digestion of plant tissue, they choose the parts of the plants easier for the digestibility, like fruits, flowers, and nectar.
\nDuring the consuming of fruits and nectar, some lizard species can disperse seeds and pollinate flowers. The main contribution of the lizards in the dispersal of seeds is on the deposition pattern of seeds. More studies are needed in order to investigate the dispersion syndrome in other species and draw a general profile of seed dispersal by lizards.
\nThe pollination by lizards is rare, but very relevant, because the occurrence of such events is carried out on islands. These environments may have reduced diversity of other animal groups and are isolated. The interactions of the plants with lizards are fundamental to the maintenance of species on islands.
\nTherefore, the research conducted so far about herbivory by lizards have shown interesting results, but many hypotheses have yet to be formulated and tested.
\nPertaining to the day-to-day energy usage increases, various technologies were addressed to satisfy the current energy demand. Based on this circumstance, the electronic devices for energy conversion (solar cells and fuel cells) and energy storage (batteries and supercapacitors) were extensively studied throughout the world [1]. Basically, the performance of these devices depends on the materials’ design with different nanostructures and material interfaces. In particular, advanced materials including carbon nanomaterials, viz., carbon black, carbon nanotubes, carbon nanofibers, graphene, and so on, play a vital role in an attempt to lead the breakthrough and challenges from laboratory scale to technology ideas [2].
Among them, graphene, since its discovery, has been stirring enthusiasm among the scientific community owing to its attractive properties. Properties such as high electrocatalytic activity, good conductivity with immense surface area, and low costs make it an ideal candidate to implement in electrochemical application. Subsequently, graphene has been utilized as a promising candidate in energy storage applications such as battery and supercapacitors (SCs) [3, 4]. Due to its high electrical conductivity, charge carrier mobility, and transparency, it has been potentially used as an electrode for electrochemical energy device application [5, 6]. Processing of graphene electrodes differs according to their application by fabrication techniques and synthetic strategies. As graphene is an electrode focusing on rechargeable battery application, the device performance is based on the presence of electroactive sites in graphene sheets [7, 8]. Therefore, graphene sheets composited with suitable electroactive materials like metal chalcogenides, metal oxides/hydroxides, metal nanostructures, and even the heteroatom-doped graphene provide better activity for rechargeable batteries [9, 10, 11]. Conventionally, the electrode materials were deposited on metal foils by doctor-blade technique, drop-casting, spray-coating, or spin coating to construct the batteries. This electrode material was mixed with foreign materials (binders and conducting agent) to make into ink, paste, colloidal dispersion, etc., for deposition purposes. In the case of self-supported graphene foams or FSGs, the foreign materials are avoided, and on the whole, they act as electrodes directly [12]. This chapter outlines few reported literature on FSG performance for rechargeable battery applications. Moreover, we summarized the synthetic strategies and fabrication of free-standing graphene/hybrid functional materials for particular device application.
Graphene is a 2D one atom thin sheet that consists of hexagonal sp2 carbon, which is densely packed into honey-comb lattice and large benzene-like aromatic hydrocarbon. It is considered as fundamental basis for all carbon allotropes, and their conceptual depiction are shown in Figure 1. It represents that 2D graphene sheet can be enclosed into 0D like fullerene structure and rolled up into 1D-like carbon nanotube structure, and 10 layers of graphene can be stacked up into 3D graphitic-like structure. Hence, it is considered as “mother of carbon allotropes” [13]. The fabrication of graphene film by different synthetic routes was adapted accordingly to its required properties for many applications. Current technologies addressed to synthesize graphene via several routes are as follows: mechanical exfoliation (liquid exfoliation and scotch tape method), epitaxial growth (chemical vapor deposition (CVD) and from organic molecules method), unzipping CNT (chemical and electrochemical methods), and wet chemical process (oxidation of graphite) [14].
Carbon allotropes in different forms: 0D Bucky ball, 1D nanotubes, 2D sheets, and 3D graphite form (without permission from Ref. [13]).
Graphene possesses exclusive chemical, physical, mechanical, and thermal properties, which focuses on the field of electrochemical applications as an electrode material to enhance the stability and durability of the devices. Graphene application in any devices is adopted according to its properties as shown in Figure 2. Prominently, the conductivity of anode and cathode electrodes plays a vital role in batteries, which collect or disperse the electrons that tune up the performance to device. The conjugated sp2 carbon networks of 2D graphene sheet exhibit high conductivity around 104–106 S/cm than any other carbon materials depending on the number of layers [15, 16]. Additionally, the electrode surface area is an essential part for batteries, which has high theoretical surface area of graphene, and is reported to be ∼2600 m2/g [17]. For suspended graphene sheets below 10 nm thickness, the spring constants were observed between 1 and 5 N/m, and pristine graphene exhibits Young’s modulus of 1.05 TPa and intrinsic strength of 110 GPa, which has high mechanical property [18, 19]. The electrochemical property is a perspective for energy storage and generation technologies. The rate of heterogeneous electron transfer occurs on graphene materials; in the meantime, the rate of reaction varies selectively at edges and basal plane according to their electroactive sites by adding impurities or doping. Graphene-based materials were potentially applied in electrochemical devices due to their inherent electrochemical activity nature [20]. These amazing properties of graphene such as electrical, mechanical, and electrochemical were attracted for rechargeable batteries.
Properties of graphene and its appropriate application.
It is well known that graphene can be synthesized by several routes and named according to the recovered final product. Graphene research has elevated gradually in the past 5 years for its tremendous properties, but the scientific community ends up with the confusion in naming the material. Even though researchers have synthesized up to 100 layers of carbon sheets, they were naming them as graphene. This provides different changes in properties compared with the single-layer graphene sheet for their practical applications [21]. Hence, carbon journal community raised a nomenclature for graphene family, which is shown in (Table 1).
Materials | Description |
---|---|
Graphene | Two-dimensional sheet with one atom thickness |
Turbostratic graphene | Arrangement of graphene sheets in rotational fault structure |
Bi-,tri-, or multilayer graphene | Stacking of graphene sheets (2 - bi, 3 - tri, & 4 - 10 – multi) in AB, ABA, or rotational order |
Few layer graphene | Subset of multilayer graphene |
Graphite nanosheets, nanoflakes, and nanoplates | Lateral/thickness of graphene sheets <100 nm. |
Exfoliated graphite | Exfoliation of bulk graphite |
Graphene nanoribbon | Length dimension in micron and width in the range of nanometer |
Graphene quantum dots | Lateral dimension less than 10 nm with photoluminescence property |
Graphene oxide | Graphene sheets that contain functional groups (epoxy, hydroxyl, and carboxyl) |
Graphite oxide | Exfoliation of bulk graphite by strong oxidation process |
Reduced graphene oxide | Reduction or restoration of sp2 carbon of graphene oxide |
Graphenization | Growth of graphene by small molecules (bottom-up approach) |
Free-standing graphene, graphene foam, hydrogel, and aerogel | Graphene sheets arranged in 3D forms |
Nomenclature of graphene based on the structure.
The descriptive term is an essential thing for researchers in the area of graphene material because the properties will change accordingly with recovered product with different synthetic strategies. For example, the graphene-based transparent conducting film adopted by the CVD method obtained 600 ohms/sq. at 96.5% transmittance at 550 nm, whereas solution processed graphene increases above 10 K ohms at the same transmittance [22, 23, 24]. Even the electrochemical behavior fluctuates according to the synthetic strategies; for instance, the presence of oxygen functional groups in graphene oxide (GO) shows an excellent electrochemical behavior rather than the pristine graphene [25]. Hence, the electrochemical device applications based on graphene electrodes depend on the architecture and hybrid composites to improve the active sites. Recently, 3D architecture like graphene materials such as foams, hydrogel, aerogel, and free-standing was utilized in electrochemistry-oriented topics.
For designing and fabricating large scale macroscopic or microscopic architecture like materials, the choice of precursor signifies the synthetic strategies. Graphene sheets synthesized by wet chemical process commenced for several applications due to the presence of functional groups. As discussed in the previous section, the methods utilized for the preparation of graphene sheets conclude their suitable application based on their properties. Noteworthy, there is a challenge for high dispersion of graphene either in aqueous or in organic solvents. It has been achieved by dispersing agent introduced into hydrophobic graphene sheets for good dispersion, whereas it submerges the graphene properties [26]. In the view of fact, large scale solution processable GO has several advantages such as cost effective, eco-friendly solvent and facile to introduce any foreign material due to the presence of functional groups [27, 28]. The copious amount of functional groups attached to the graphene surface contains hydroxyl and epoxy groups at basal planes and carboxyl groups at edges. This leads to affinity with water molecules, which provides a higher dispersion and further it assists with other inorganic or organic molecules for facile composite preparation. In the choice of precursor for free-standing material preparation, GO dominates as a building block due to its features of large scale solution processable with high colloidal dispersion. The resultant macroscopic FSG holds as an excellent mechanical, electrical, and light-weight material. Further, the 3D architecture of FSG enhances the surface area, porous nature, and structural active sites by merging with other functional host materials such as semiconducting material, metal nanoparticles, and polymers. The synergy of graphene sheets and functional host materials in the 3D macroscopic architecture attracted wide variety of applications due to the tuning of their properties.
In 1998, Smalley prepared CNT buckypaper by vacuum filtration, in prior it is well dispersed in Triton X-100 surfactant to break up the pi-pi interaction between the bundled ropes of CNT [29]. Further, CNT buckypapers were prepared by domino pushing technique, and they are strong, robust, and flexible. The obtained paper exhibits 26 micron thickness; the electrical conductivity was found to be 2.0 × 104 S/m and thermal conductivity shows 153 W/mK [30]. These papers were directly applied for supercapacitor application. Thus, the carbon paper–like materials were potentially applied in a variety of applications due to their light-weight, highly flexible, robust, and eco-friendly nature. On the basis of cost, the CNT papers lag behind for the practical applications, and they have been replaced by graphene sheets. Similar to CNT buckypaper, GO paper was fabricated by flow-assisted vacuum filtration or evaporation techniques. Figure 3a and b shows the photograph of flexible GO paper and mechanical properties comparison chart of GO paper, buckypapers, vermiculite paper-like material, and graphite foil, respectively. Young’s modulus is as high as in GO papers with 42 GPa for vacuum-assisted technique, and similar tensile strength but lowest Young’s modulus (12.7 GPa) was obtained for evaporation-induced self-assembly technique [31, 34]. Thus, the high mechanical properties of GO paper can be used in several applications such as supercapacitors and other flexible substrates [35]. Moreover, the mechanical properties of GO papers depend on the alignment of GO sheets by any chemical modification between the layers and at the edges. The modifications are made either by crosslinking or grafting between the two sheets as GO has several functional groups that covalently attached to other molecules [36, 37]. The intercalation, functionalization, and interaction between the GO sheets provide high mechanical stiffness for paper-like material. Moreover, the atmospheric humidity affects the mechanical property of the GO paper, increase in the relative humidity to 100%, the GO colloidal solution absorbs water from moisture and it bulges to 70% which decreases the tensile strength [34]. The functionalization on graphene surface also affects the mechanical properties depending on the functional moieties as well as the bonding nature [38, 39, 40]. The electrical properties of GO papers depend on the synthetic methods as several changes were observed in structures and reduction ratios of C/O. Upon exposing to the hydrazine vapor, the conductivity of GO papers increased by four order of magnitude from 8.5 × 10−4 to 170 S/cm. Further enhancement in conductivities of GO paper was developed by treating the paper with mixture of argon/hydrogen/hydrazine vapors [41]. The removal of the oxygen group is the main factor to restore the sp2 carbon network by chemical or thermal treatment. The chemical reductive treatment efficiently removes the oxygen moieties from the GO paper, whereas the thermal treatment shows high restoration of sp2 carbon network but less removal of oxygen functional groups. Recently, a rapid reduction treatment was proposed by immersing the GO papers in hydrohalic acids, viz., HI and HBr, which shows a remarkable electrical conductivity around 298 and 3220 S/cm, respectively [32, 42]. Based on the facile chemical treatment, the electrical conductivity of FSG improvement was shown by treating the GO papers in metal halides like MgI2, AlI3, ZnI2, and FeI2 that exhibit 550 S/cm [33].
(a) Photograph of flexible graphene oxide paper, (b) comparison chart of mechanical properties of GO paper with other flexible paper materials, (c) effect of FSG electrical conductivity changes w.r.t its properties upon HI treatment in different scale of time, and (d) electrical conductivity versus the Raman and XPS data of GO paper reduced by different metal halides (without permission from Refs. [31, 32, 33]).
Owing to these attractive mechanical and electrical properties of FSG material, it played vital role in flexible device technologies based on electrochemical energy storage and generation, actuators, sensors, and catalysts. Based on the attractive graphene properties and its nomenclature, the graphene oxide has fascinating properties which has layered structure similar to graphene that containing oxygen functional groups such as carboxyl, hydroxyl and epoxy. These functional groups were highly dispersed in DI water; hence, it is well aligned over vacuum filtration process. The GO paper is peeled off after vacuum drying and subjected to reducing treatment, as synthesized FSG material is directly utilized as current collector in place of Al, Cu, Ni foam, etc., for energy storage applications.
Battery is an electrochemical energy storage device that is cost-effective and eco-friendly and with cyclic durability, excellent overall performance, and long-term stability. In this decade, lithium ion battery (LIB) is successfully commercialized worldwide for portable electronic devices, and it has approximately 200 kWh scale for transportation and stationary storage [43]. On comparison with other secondary-based batteries such as sodium sulfur, redox flow, Ni-Cd, etc., Li ion cells have gathered the most commercial interest because they provide high energy and power densities, respectively. In contrast, other secondary batteries are under development stage for consideration in commercial package over LIB due to its major drawback as follows: large scale storage, cost of materials, toxicity, cyclic performance, or stability issues. However, the better system in secondary batteries credited for LIB because the redox potential of −3.04 V vs. SHE (standard hydrogen electrode) for Li/Li+ which has high electropositive in periodic table and light weight material with small ionic radius. Henceforth, the charge-discharge rates enhance and power densities vary in the ranges of 500–2000 W/kg [44]. In commercialized LIBs, the existing negative electrode is a graphite-layered structure material coupled with the host material and LiCoO2 has positive electrodes. Similar to LIBs, the other systems were also focused since it lags behind to reach the theoretical specific capacity (400 Wh/kg) that requires for electric vehicles for long term usage. Hence, other kinds of secondary batteries have been discovered such as Li-sulfur, sodium-ion battery (SIB), sodium-sulfur, Li-air, Zn-air, and flow batteries.
Conventionally, LIBs are made up of graphite anode and LiCoO2 layered material as cathode sandwiched between LiPF6 (1.0 mol/L) as an organic electrolyte dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC) in 1:1 volume ratio [45]. While LIB is charging, deintercalation happens at cathode, where the Li ions are removed from the layered LiCoO2 by releasing electrons to cathode. The released Li ions are transported to anode with the help of the electrolyte system and finally intercalated into graphite by gaining electrons. The same process is reversed during the discharging process.
Designing of anode materials for LIBs has focused much attention on retaining large reversible specific capacity. Beyond the graphite anode, few metal oxides and metal alloys were developed as anode material, and the lithiation and delithiation processes were investigated. Specifically, FSG paper outpaces the other candidates such as carbon nanotube (CNT) paper or graphite foil due to their tremendous properties as discussed earlier. Importantly, the electrical and mechanical properties of FSG are potentially applied for flexible device application. However, the FSG electrode itself does not provide higher capacity (approximately 100 mAh/g), which is not applicable as anode in LIB; instead, it has good cycling stability. Therefore, the host material that has high electrochemical active sites is incorporated into FSG for improvement of capacity in the device. This extends the large volume expansion in FSG electrodes for an efficient Li ions intercalation. One of the advantages of this FSG hybrid electrode is that it excludes the nonconducting polymer binders as additives. Conventional electrode-based materials were obtained as powders and coated on the metal foils in the form of ink using additives like polymer binders and conducting additive, whereas the FSG hybrid electrode plays dual role as a current collector and conductive additive.
In 2005, LIBs were fabricated with free-standing electrode based on CNTs prepared by vacuum filtration method [46]. Significantly, the free-standing electrode fabrication is a facile route in comparison with the conventional electrode since the mixture of active material, polymer binder, and conductive additive in solvent coated on metal foils. The CNT free-standing electrode provides reversible discharge capacity of 200 mAh/g at 0.08 mA/cm2. Further, the specific capacity was enhanced by the CVD grown free-standing CNT that delivers 572 mAh/g at 0.2 mA/cm2 [47]. This is a quite interesting result obtained for free-standing electrodes rather than the conventional electrodes. Meanwhile, the usage of high-cost material CNTs as free-standing electrodes lags behind manufacturing process. From this point of view, inexpensive material graphene prepared by chemical methods provides large scale production as dispersion in many solvents. This dispersion is readily subjected to vacuum filtration to prepare FSG paper with desired thickness. Usually, the discharge capacity of 298 mAh/g decreased to 240 mAh/g after 50 cycles for graphite electrodes with 81% retention capacity. But the FSG paper itself as anode provides huge irreversible discharge capacity, i.e., 680 mAh/g at initial cycle dropped to 84 mAh/g second cycle. The retention capacity is very poor compared to graphite electrode and therefore it is concluded to be not a suitable candidate for anode material [48]. This helps infer that solid electrolyte interface (SEI) formation is a significant parameter to reduce the storage capacity in FSG electrodes.
To potentially apply FSG as anode material in LIBs, the second phase material with highly electrochemical active sites should be composited to enhance the capacity. In this regard, Lee et al. composited Si NPs on GO sheets, vacuum filtered, and followed by thermal treatment to produce FSG/Si nanoparticle (NP) paper. This work delivers high Li ion storage when compared to pristine FSG electrodes. Si NPs intercalated between the graphene sheets of FSG paper that facilitates good 3D graphite-like framework and provides high Li ion storage even at high current density [49]. Another work has been reported with similar hybrid FSG/Si NPs, whereas a facile route has been introduced to fabricate. The specific capacity of 708 mAh/g was observed without any loss even after 100 cycles and this is mainly due to the larger volume change in graphene-Si composite. It also denotes the performance of device with an efficient electron and charge transfer contributed by graphene sheets that minimize the internal resistance of the electrodes [50]. Zhang et al. prepared Si hollow nanosheets using Mg as template and connected with graphene sheets to obtain free-standing electrodes by layer-by-layer method followed by HI reduction treatment. The specific capacity was examined during flat and bent state, which delivers similar results without any loss. Remarkably, Si/FSG paper anodes retain high reversible capacities even at long cycles, which reveals their retention capacity. They exhibit specific capacity of 660 mAh/g at 0.2 A/g current density after 150 cycles with 99% coulombic efficiency [51]. As mentioned earlier, all the Si NPs are highly expensive in terms of manufacturing process and hence a low cost method plays a significant factor. To tackle this issue, Cai et al. prepared Si NPs on CNT surface using low-cost Al-Si alloy as starting material and further inserted with graphene sheets to form a self-standing hybrid anodes for LIBs. Comparing with bare Si/CNT or Si/Graphene anodes, Si-CNT/FSG hybrid electrode, it delivers 1100 mAh/g at 0.2 A/g current density after 100 cycles. Addition of CNT was involved to disperse the Si NPs on the surface and provide network between the graphene sheets for conductivity enhancement as well as improved Li ion intercalation for efficient charge transfer [52].
Metal oxides (MOs) play an important role in LIBs as anode material and their poor conductivity restricts their application. Hence, introducing the conductive phase into MOs provides high retention capacity with long-life cycling stability. The theoretical reversible capacity of SnO2 is 782 mAh/g and its poor performance is due to low cycling with serious volume expansion. With this regard, SnO2 NPs dispersed on GO surface, followed by vacuum filtration to obtain free-standing electrodes and used as two different LIB anodes by thermally reduced and chemically reduced respectively [53, 54]. The specific capacity of 438.5 mAh/g at 0.1 A/g and 700 mAh/g at 0.2 A/g has been delivered for the two different reduction methods for SnO2 NPs/FSG electrodes. In both the cases, capacity fading is not observed even after the 50 cycles owing to the good anchoring of SnO2 and graphene sheets. Further, other metal oxides TiO2, Mn3O4, Fe3O4, and CuO nanostructured materials are incorporated into the FSG and are investigated for their performance in anode application for LIBs that delivers 269 mAh/g at 0.2 A/g, 692 mAh/g at 0.05 A/g, 544 mAh/g at 10 A/g, and 698.7 mAh/g at 0.67 A/g capacities, respectively [55, 56, 57, 58, 59]. Commonly, all these metal oxides’ specific capacity shows a reasonable capacity with the long-life cycling after incorporating the MOs into FSG electrodes due to the following aspects: (1) Interaction of GO and MO precursors increases, which enhances the well dispersive growth of MO NPs on graphene sheets. (2) Anchoring of MOs and graphene enhances the volume expansion/contraction for lithiation/delithiation process. (3) The cycling stability increases compared to pristine MO anodes even after several cycles owing to its structural phase remain stable after alloying/de-alloying process of lithium ions. (4) MOs avoid the aggregation of graphene stacking that leads to larger void space to penetrate the electrolyte and make a strong interface with the electrochemical active MOs for an efficient Li ion storage.
Further, with the controlled synthesis of oxygen, functionalized CNT/FSG electrodes were fabricated for anode application in LIBs. The battery performance is based on the oxygen functional groups in the electrodes that have been investigated. An optimization in weight ratios of CNT/FSG and heat treatment improves the volumetric and gravimetric capacitances. The CNT/GO hybrid at a ratio of 1:1 shows higher volumetric capacity of 260 mAh/cm3 that reduced at 200°C, while lower capacity of 43 mAh/cm3 for 900°C treated CNT/GO. Whereas, at high current densities, the role of oxygen in capacity role suppress for 200°C larger than the 900°C [60]. This implies the importance of CNT intercalation between the graphene sheets of FSG electrodes. Zhang et al. demonstrated the defect-rich MoS2 NSs/graphene/CNT hybrid paper as anode material for LIBs. In this design, MoS2 facilitates the lithium ion storage due to the high active sites at the edges and the electrical conductivity improved by the network of CNTs attached to the graphene sheets. In addition to the conductivity enhancement, the porosity of the FSG electrodes increased by the network of CNT sandwiched graphene sheets. On the whole, the binder-free and substrate-free hybrid anode papers deliver high reversible capacity of 1137.2 mAh/g at 0.1 A/g current density with good cycling stability [61]. This framework induces a novel pathway to incorporate other host materials to understand the CNT/FSG electrodes. Recently, several transition metal oxides provide high reversible theoretical capacities compared with the commercialized graphite anode. To the CNT/FSG electrode network, transition metal oxides such as Fe2O3 [62], CuO [63], MnO [64], and CoSnO3 [65] were incorporated as electrochemical active phase into the framework and investigated as anode material performance for LIBs. All these hybrid papers exhibit high reversible capacity of 716 and 600 mAh/g at 0.5 A/g current density more than 50 cycles for Fe2O3 and CuO nanobox, respectively. Apart from this, an enhanced capacity was observed for CoSnO3 and MnO NPs at high current density of 2 A/g, which delivers 676 and 530 mAh/g, respectively. Individually, the CNT/FSG and transition metal oxide anodes were found to have a drastic decrease of specific capacity upon increasing the current density, whereas a slight decrease of specific capacity was observed after hosting the metal oxides into CNT/FSG framework. Reasons for high reversible capacity and good cyclic stability of metal oxide-CNT/FSG electrodes are very similar due to the following merits: (1) incorporation of metal oxides improves the Li ion kinetics and enhances the charge transfer due to highly conductive CNT network between the graphene sheets; (2) 3D framework of CNT/FSG has highly porous nature, large specific surface area, and large volume change, which has well dispersion of metal oxide NPs onto the carbon surfaces; and (3) long cycling due to good attachment of metal oxide with CNT/FSG, whereas greater the volume expansion, higher the Li ion intercalation.
Interestingly, Cao et al. designed a unique layered nanostructure of porous ternary ZnCo2O4 on graphene sheets and fabricated as flexible anode and investigated its electrochemical performance. And also they constructed full cell with LiFePO4 as cathode material that deposited on FSG paper as slurry by homogenous mixing of conductive additive and polymer binder [66]. Figure 4a shows the photograph of flexible Li-ion battery fabricated by FSG hybrid electrodes. The half-cell of ZnCo2O4/FSG anode delivers higher specific capacity of 791 mAh/g at 1 A/g after 1000 cycles with 97.3% of capacity retention and concludes that it has an excellent cycling stability. Figure 4b shows the rate capability of the flexible battery with different current densities ranging from 0.5 to 10 C. This full cell delivers 40 mAh/g even at 10 C rate and the specific capacitance remains the same after the current density decreased to 2 C, which shows a good reversibility. The full cell has FSG paper as current collector for both the anode and cathode that are composited with ZnCo2O4 and LiFePO4 as host materials, respectively. It operates at 2 V with initial charge of 143 mAh/g and coulombic efficiency of 97.2%, which is comparable to existing LIB. The specific capacity is maintained at 90 mAh/g with high capacity retention under flat and bent states over 100 cycling process, which implies the flexibility of the device as shown in Figure 4d. It represents that graphene conductivity is unchanged while bending the device.
(a) Photograph of flexible full cell Li-ion battery with FSG/ZnCo2O4 as anode and FSG/LiFePO4 as cathode, (b) charge-discharge curve of full cell at 0.5 C rate, (c) charge-discharge rate capability at different rates, and (d) capacity variation on flat and bent state during cycling at 2 C rate (without permission from Ref. [66]).
Ahead of LIBs, SIBs have attracted the research community as the resources of Na are inexhaustible across the globe. In comparison with LIBs, the redox potential is −2.71 V vs. SHE and only the radius is 55% larger than the Li ions. Larger radius influences to focus on suitable material for insertion/extraction of Na ions effectively. The researchers focused on developing an efficient anode material for SIBs that involves carbon-based families and Na intermetallic compounds. The first cycle-specific capacity of sodium-antimony and sodium-phosphorous shows 600 and 2596 mAh/g, respectively [67, 68, 69]. Specific capacities drop after first cycles due to the internal cracking in the electrodes upon Na ion insertion. It leads to hinder the electrical properties and dissolution of electrode materials to electrolyte. The hard carbon with large interlayer distance that functions as anode material for SIBs and delivers more than 200 mAh/g of capacity even after 100 cycles was reported elsewhere.
The porous nature and structure of the FSG could facilitate the accommodation of host materials such as transition metal chalcogenides (TMCs), which are electrochemically active for the Na ions for alloying process. David et al. reported that the MoS2/FSG composite papers exhibit an excellent cyclic stability with high reversible capacity of 338 mAh/g at 0.025 A/g. It is the first report and opens the pathway to apply free-standing electrodes for SIB anode [70]. The cyclic stability was enhanced in flower-like MoS2 incorporated on graphene foam prepared by one-step microwave-assisted synthesis. It offers stable capacity of 290 mAh/g at 0.1 A/g after 50 cycles compared to previous MoS2/FSG electrode. The cycling performance is enhanced due to highly conductive 3D graphene foam and well-dispersed MoS2, which shields as well as avoids the strain during the sodiation/desodiation process at anode [71]. With the significance of MoS2 TMC for SIB anodes, further investigation was followed by incorporating other TMCs such as WS2 and Co0.85Se into FSG [72, 73]. As mentioned in LIBs, the electrochemical behavior can be increased by introducing the heteroatoms into the graphene sheets. Heteroatom-doped FSG electrode performance was investigated for SIB anode, where the nitrogen improves the electronic conductivity and fluorine expands the interlayer for an efficient accommodation of Na ions. This delivers a reversible capacity of 56.3 mAh/g at 1 A/g for 5000 cycles. It indicates that the doping of heteroatoms enhances the cycling stability of SIB anodes. Figure 5a shows the discharge/charge profile before and after the bent state, which remains with the same capacity at current density of 0.05 A/g. It reveals the mechanical strength of the FSG electrodes that is suitable to fabricate flexible pouch cell [74]. Even though the above said materials show an excellent cyclic stability, still it is necessary to improve the specific capacity of SIBs. It is well known that Na3P has theoretical capacity of 2600 mAh/g, where its demerits are very similar to those of Si electrode in LIBs. Because of high pulverization, fast capacity fading and also it hinders the electrical contact which lags behind in the electrochemical stability. Lots of effort have been made by assembling red P into carbon matrix to overcome these problems. Red P was composited on carbon nanofibers (CNFs) and dipped in GO solution followed by HI treatment providing P-CNF/FSG electrodes. In this architecture, CNF network enhances the pathway of electron transport rapidly and the role of graphene sheets to improve the conductivity as well as to avoid the breakup of bonds P–P from electrodes. This work demonstrates a significant capacity of 406.6 mAh/g at 1 A/g after 180 cycles [77]. Moreover, the graphene sheets have been utilized as a multifunctional conductive binder, and hard carbon/FSG as anodes for SIBs was constructed. It delivers high reversible capacity of 372.4 mAh/g and shows capacity retention of 90% over 200 cycling. A superior performance is observed in the absence of PVDF binder with higher rate capabilities and converting the rigid nature of hard carbon into flexible graphene sheets [78].
(a) Discharge/charge profile of heteroatoms (N and F)-doped FSG electrode at bent and normal state for SIBs. (inset: The photograph of FSG pouch cell illuminated with LED), (b) comparison of specific capacity and coulombic efficiency of bare FSG and N-doped FSG for Li-S battery. Cross-sectional SEM images of (c) discharged and (d) re-charged macroporous FSG electrodes (without permission from Refs. [74, 75, 76]).
Akin to SIBs, FSG electrodes play a major role in other rechargeable secondary batteries such as Li-S, Li-air, and Zn-air. The higher specific energy is a significant parameter for transportation and stationary applications, and in that case, Li-S batteries offer advantages but it is limited with few challenges discussed later. The highest theoretical capacity of Li-S system is 2600 Wh/kg, which is highest than the LIB due to highest capacity of Li-S cathode sulfur has 1675 mAh/g. The most challenging part is to improve the electronic conductivity of cathodes of Li-S as the sulfur exhibits poor conductivity of 10–17 S/cm as well as the formation of polysulfides at cathodes. These polysulfides oxidize the Li anode and get back to cathodes and re-oxidize, thus lowering the performance of Li-S system. An extensive effort has been made to improve the cathodes by incorporating the carbon additives to sulfur to minimize the unnecessary reactions. Initially, mesoporous FSG was prepared and the sulfur was deposited by vapor treatment and was utilized as cathodes for Li-S system. It delivers charging capacity of 1288 mAh/g with high coulombic efficiency that reveals the restriction of sulfur to dissolute polysulfides in mesoporous FSG framework [79]. Similar to LIB and SIBs, the electrochemical behavior of cathode in Li-S system enhanced for heteroatom-doped FSG electrodes. Figure 5b shows the comparison of FSG and N-doped FSG capacity and coulombic efficiency with different cycle number. The heteroatom-doped FSG shows superior performance than the bare FSG due to the high interaction of polysulfides with heteroatoms that increase specific capacity. The nitrogen doping effect in FSG minimizes the concentration of polysulfides and forms a uniform layer of Li2S at cathode. This system delivers 1000 mAh/g at 0.335 A/g after 100 cycles [75]. In another work, Zhu et al. developed free-standing cathodes by CNTs that were interconnected with the sulfur-graphene walls and investigated the electrochemical behavior that delivers 1346 mAh/g at 0.17 A/g current density. It is due to sulfur at graphene walls that deals to provide dual response as follows: (i) hinder the dissolution of polysulfides minimizing the shuttle phenomenon and (ii) offer volume expansion even at high quantity of sulfur. Moreover, its capacity retention shows 40% when current density is increased to 16.7 A/g owing to the good electron pathway by CNTs connected with graphene nanosheets [80]. Further, nanosized Li2S (25–50 nm) particles incorporated into FSG papers by vacuum filtration process demonstrated an excellent cycling and rate capability with reversible capacity of 816.1 mAh/g at 0.1675 A/g (150 cycles) and 597 mAh/g at 11.7 A/g (200 cycles). This shows excellent performance in electrochemical behavior due to the uniform distribution of Li2S particles on graphene sheets that minimize the barrier for Li ion transport and particularly it has superior wetting nature to interconnect the polysulfides with graphene network into the paper electrodes [81]. Similarly, Chen et al. designed an efficient hierarchical nanostructure like nanobundled forest with Li2S/few-walled CNTs at FSG obtained solution processing followed by self-assembly method as cathodes. In this design, CNTs assembled in shaft-like structure and Li2S as active material, whereas the graphene sheets act as barrier for Li2S. It achieves high capacity of 868 and 433 mAh/g at current density of 335 and 16.7 A/g, respectively. This originates from the good framework between CNTs and graphene sheets as well as the uniform distribution of Li2S, and moreover, the barrier of graphene sheets for Li2S reduces the dissolution of polysulfides. Overall, the influence of void space enhances the volume change and thus improves the cycling stability of Li-S battery [82].
Recently, metal-air batteries have inspired much attention apart from the above said battery systems due to their high theoretical capacity than the metal-ion and Li-S batteries. The metal-air batteries can be operated in aqueous or nonaqueous medium based on the selection of metals. The nonaqueous medium is well suited for the Li-air batteries that deliver high capacity than in aqueous medium but still there are some issues when it comes to the practical application. The development of cathode in Li-air is significant as it is the main compartment to breathe oxygen for delivering high capacity of the system. There are a lot of reports for cathode development based on metal oxides grown on Ni foam as binder-free electrodes. The role of FSG electrodes was also investigated as cathodes for Li-air batteries. First, Kim et al. developed graphene nanoplates (GNP)/GO composite paper-like electrodes as cathodes for Li-air battery system. The wrinkled nature of the paper electrodes induces the high surface area and also delivers higher discharge capacity of 9760 mAh/g at 0.1 A/g current density. This superior performance is due to the reduced overpotential, and the difference in consumption/evolution of O2 is minimized. On the whole, the system exhibits higher efficiency in OER (oxygen evolution reaction)/ORR (oxygen reduction reaction) of 87% [83]. The same group developed macroporous FSG paper with surface area of 373 m2/g and pore volume of 10.9 cm3/g with 91.6% of porosity that exhibits a high specific capacity of 12,200 mAh/g at 0.2 A/g. The rate capability is enhanced where it shows high cycling performance even at higher current density of 0.5 and 2 A/g that delivers approximately 1000 mAh/g. This is attributed to the minimized volume expansion that limits the decomposition and formation of Li2O2 at the macroporous nature of FSG. While discharging/charging the macroporous FSG, the nature of FSG electrode decomposes the discharge products completely that reveals its highly porous structure as shown in the Figure 5c and d [76]. Researchers investigated the effect of FSG cathodes in Li-air upon introduction of metal oxides, namely, α-MnO2 and NiCo2O4. Upon insertion of α-MnO2 into FSG electrodes, the overpotential decrease was caused during charge/discharge process. It delivers 2900 mAh/g for the higher content of α-MnO2 that was reported and shows the catalytic improvement in this study [84]. And Jiang et al. reported an excellent reversible capacity of 5000 mAh/g at 0.4 A/g by incorporating mesoporous NiCo2O4 into macropores of FSG. It also lowers about 0.18 and 0.54 V of overpotential for discharge and charge, respectively [85].
In this chapter, FSG electrodes in battery applications signify their potential advantages to the fabrication technology. The fabrication of FSG electrode is facile as well as it excludes some additives applied in conventional electrodes. At present, the electrode of spent batteries contains active materials, binder, and metal foil, which set hurdles for recycling process. Herein, the FSG hybrid electrodes provide good capacity and cycling for battery application without binder and metal current collector. This exclusion provides light weight and flexible batteries and also there is a pathway to discover a facile route to recover the materials from FSG hybrid–based spent batteries in future.
This work was supported by South China Normal University. F.C. thanks the support from Outstanding Young Scholar Project (8S0256), the Project of Blue Fire Plan (CXZJHZ201709), and the Scientific and Technological Plan of Guangdong Province (2018A050506078).
The authors declare that there is no conflict of interest.
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