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1 s2.0 S0016236123021488 Main
1 s2.0 S0016236123021488 Main
Fuel
journal homepage: www.elsevier.com/locate/fuel
Review article
A R T I C L E I N F O A B S T R A C T
Keywords: Biomass-based nanofibers prepared by electrospinning technology have the advantages of unique porous
Energy storage structure, high specific surface area, low cost and easy availability, hence they have wide applications in elec
Electrochemical properties trochemical energy storage devices. This review describes the characteristics of electrospun nanofibers prepared
Electrospinning
from various biomass components and their derivatives and introduces their application performances in elec
Biomass
trochemical energy storage devices. The preparation methods of electrospun nanofibers with excellent electro
Nanofibers
chemical properties are systematically introduced, and the differences of various biomass materials and their
applications in electrochemical energy storage devices are analyzed and summarized. Some development sug
gestions for the future application of biomass-based nanofibrous materials are given. These works provide some
important references for the application and expansion of biomass-based electrospun nanofibers in the field of
energy storage.
* Corresponding author.
E-mail address: jianghaifeng11@126.com (H. Jiang).
https://doi.org/10.1016/j.fuel.2023.129534
Received 18 June 2023; Received in revised form 5 August 2023; Accepted 14 August 2023
Available online 19 August 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
H. Jiang et al. Fuel 355 (2024) 129534
Fig. 2. (a) Schematic of electrospinning. Reproduced with permission [22]. (b) Schematic diagram of carbon nanofiber synthesis [23].
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H. Jiang et al. Fuel 355 (2024) 129534
technology not only provides an effective way for the utilization of nanofibers using lignin as a raw material requires purification. This is
biomass resources, but also realizes the preparation of energy storage mainly due to the heterogeneity of lignin and its cross-linked structure,
equipment with good electrochemical performance. For example, Tao which reduces its spinnability [51,52]. Purification of lignin can
et al. [40] used walnut shell as a raw material to synthesize an inde improve its binding effect with spinning aids and enhance its spinn
pendent carbon nanofiber mat with rich pore structure and mechanical ability. Du et al. [53] proposed to remove lignin with low molecular
flexibility, and applied it in the lithium ion battery. Their results showed weight from biomass feedstock by using gradient extraction method,
that the electrodes had a specific capacity of 380 mAh g− 1 at 0.03A/g, their results indicated that lignin with high molecular weight had low
and the specific capacity was higher than 280 mAh g− 1 after 200 cycles dispersion index and high linear structure, and the prepared lignin-
at 0.1 A/g. Chen et al. [34] carried out homogeneous esterification re based carbon nanofibers had a specific surface area of 1052.8 m2 g− 1
actions of bagasse with acid anhydride. After using the esterified bagasse and an energy density of 53.7Wh kg− 1 when the power density was 600
as a feedstock, the structure of electrospun nanofibers became more W kg− 1. In the work of Berenguer et al. [37], Alcell®-lignin/ethanol
uniform, and the thermal stability of the nanofibers was improved. The solution was used to prepare sub-micron diameter carbon fibers by
uniform and stable structural characteristics of the fibers are conducive electrospinning technology. The power and energy density of the
to expanding the electrochemical active area and improving the fast assembled supercapacitors were 61 kW kg− 1 and 10Wh kg− 1. Schlee
ionization/electron transport path [41], so that the fibers exhibit et al. [51] prepared high-purity eucalyptus kraft lignin by using the
excellent electrochemical performance. solvent extraction method, dichloromethane and methanol were used as
extraction solutions. The work obtained a yield of 52.3% for electro
2.2. Advances in electrospun nanofibers prepared by biomass thermal spinning precursors. In addition, Du et al. [54] found that the electro
conversion products chemical properties of lignin-based carbon nanofibers prepared from
various biomass were different. Compared with other nanofibers pre
In recent years, researchers have pointed out that tar produced in pared from biomass(e.g. softwood and grass), poplar lignin-based car
thermal process(e.g. pyrolysis, gasification) can be regarded as soft bon nanofibers represented by hardwood had larger specific
carbon with good graphitization properties [42], which can be used as a capacitance. They believed that this was mainly because hardwood
raw material to prepare carbon nanofibers with excellent electro lignin had more linear structures and less branched chains than other
chemical properties. For instance, Li et al. [43] used biomass tar and feedstocks, which promoted the formation of graphitized carbon struc
glucose as raw materials to prepare carbon materials with hierarchical tures in nanofibers. Moreover, the small crystallite size of hardwood
pores and oxygen-rich functional groups. In their work, the specific lignin-based carbon nanofibers further enhanced its electrochemical
capacitance of the capacitor reached 175F/g. Wang et al. [44] prepared performance(Fig. 3).
a three-dimensional porous carbon membrane from microalgae-derived
oil and used it as an electrode material for supercapacitors. They found
that when the amount of the oil was 30%, the specific surface area of the 3.2. Advances in electrospun nanofibers prepared by the modified lignin
obtained carbon nanofibers was 2.1 times that of pure PAN carbon
nanofibers. Further, the specific capacitance of 272F/g at a scanning In addition to purifying lignin, modifying lignin with solvent is one
speed of 10 mV s− 1 was given. They sumarrized that the high charge of the most effective ways to improve the electrochemical performance
storage capacity of the material was mainly due to the abundant mi of nanofibers. Zhu et al. [55] obtained the modified lignin with large
cropores on the fiber surface that provided enough space for the rapid molecular weight and low heterogeneity by reacting lignin with iso
transport of electrolyte ions, while the mesopores on the fiber surface phorone diisocyanate(Fig. 4a). Their work indicated that this method
improved the accessibility of electrolyte ions. Li et al. [45] prepared effectively improved the spinnability of lignin and reduced the carbon
nitrogen-doped carbon materials for supercapacitors using bio-oil loss of fibers. The energy storage density of the material was 442.2F/g.
distillation residues as raw materials and KOH as an activator, their Dai et al. [56] noted that the esterified lignin had a lower glass transition
work also indicated that rich pore structure was an important factor for temperature, and the obtained carbon nanofibers had a fiber-to-fiber
obtaining desired electrochemical performance. bonding structure, high heteroatom content and good wettability, thus
Although some excellent work has been reported by researchers, forming an effective electronic transport network and generating pseu
there are some problems that need to be further broken through in the docapacitance. The preparation process of the fibers is shown in Fig. 4b.
process of preparing nanofibers. For instance, there are many kinds of In another of their work [57], it reported that lignin/polyacrylonitrile-
biomass in the world, and the content of various components(e.g. lignin, based carbon nanofibers were prepared by modifying lignin with ni
cellulose) in different biomass is not uniform. These lead to different trogen and sulfur co-doped graphene(Fig. 4c). The specific surface area
physicochemical properties of biomass-based nanofiber materials. For of carbon nanofibers reached 2439 m2 g− 1, and it had a typical three-
the application of biomass tar, the composition of biomass tar is complex dimensional porous network structure. After 5000 charge–discharge
and its molecular weight is low [46], which causes the viscosity of the cycles, the supercapacitor still retained 96.7% of the specific
precursor solution to decrease. This brings difficulties to the preparation capacitance.
of electrospun nanofiber materials. Currently, researchers have begun to Other techniques for preparing nanofibers have also been reported.
use biomass components as raw materials to prepare nanofibers. The For example, Li et al. [58] prepared two-dimensional lignin-derived
following sections systematically introduce the development status of carbon nanosheets with hierarchical porous structure by using metal-
biomass-based nanomaterials for electrochemical energy storage lignin assembly method. Wang et al. [59] proposed to integrate Ag
devices. loaded lignin nanoparticles into the hydrogel matrix of the poly
acrylamide for solving the limitation of weak interfacial adhesion be
3. Lignin-derived electrospun nanofiber materials for energy tween adjacent layers of flexible supercapacitors(Fig. 5a). Beaucamp
storage et al. [60] proposed a method for preparing highly swollen hydrogels
using lignin and polyethylene glycol diglycidyl ether(Fig. 5b). In addi
3.1. Advances in electrospun nanofibers prepared by lignin tion, simple template method [61], one-step solvothermal method [62]
and self-assembly method [63,64] for preparing high-performance
Lignin is one of the main components of biomass, accounting for lignin-based electrochemical materials are also reported in many
15–30% of plants [47,48]. Raw lignin is an amorphous phenolic polymer excellent works(Fig. 5c-f). These methods can be coupled with electro
formed from phenylpropane structural units through ether bonds and spinning technology to prepare electrochemical energy storage mate
carbon bonds [49,50]. Generally, the preparation of electrospun rials with better performance in the future.
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H. Jiang et al. Fuel 355 (2024) 129534
Fig. 3. Extraction process of lignin from different plants and electrochemical properties [54].
Fig. 4. (a) The modification principle [55]. Reprinted (adapted) with permission from {Electrospun Lignin-Based Carbon Nanofibers as Supercapacitor Electrodes}.
Copyright {2020} American Chemical Society. (b)Schematic illustration of the fiber preparation [56]. (c)The process for supercapacitor based on lignin-based carbon
nanofibers [57].
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H. Jiang et al. Fuel 355 (2024) 129534
Fig. 5. (a)Design of the hydrogel matrix [59]. (b)A method for preparing highly swollen hydrogels [60]. (c)A facile template strategy for preparing porous carbon
materials [61]. (d)Schematic illustration of the composite materials [62]. (e)Preparation of lignin-based materials by self-assembly and chemical activation [63]. (f)
Preparation of nitrogen-doped hierarchical porous lignin-derived carbon materials [64].
4. Cellulose-derived electrospun nanofiber materials for energy roughening of the fiber surface, reduced the activation energy of cellu
storage lose oxidation and increased the crystallite size, structural order and
electrical conductivity of nanofibers, which in turn improved the
4.1. Advances in electrospun nanofibers prepared by cellulose microstructure and electrochemical capacitance of nanofibers. Their
work showed that the specific capacitance was increased by 1.38 times
Cellulose is a linear macromolecular polysaccharide formed by than the blank sample.
connecting glucose structural units through β-1,4-glycosidic bonds
[65,66]. Cellulose contains a large amount of oxygen-containing
chemical structure, which causes high autoxidative weight loss during 4.2. Advances in electrospun nanofibers prepared by cellulose derivatives
the carbonization process, resulting in the collapse of the shape and
structure of carbon nanofibers [67–69]. These greatly weaken the Various investigations on the preparation of excellent electro
electrochemical performance of nanofibrous materials, and thus it is chemical energy storage elements using cellulose derivatives as raw
quite difficult to directly prepare electrospun nanofibers from cellulose materials are reported, including cellulose acetate [73–75], hydrox
to meet the needs of practical applications. In order to solve these ypropyl methylcellulose [76] and ethyl cellulose [77,78]. As an
problems, Cao et al. [70] proposed the technical idea of using epichlo important cellulose derivative, cellulose acetate has good thermal sta
rohydrin to introduce covalent bonds. The work showed that the bility, strong hydrophilicity and excellent biocompatibility [79,80], so it
introduction of covalent bonds not only retained the characteristics of is widely used as a raw material for preparing nanofibers. Zhang et al.
cellulose itself, but also increased the thermal stability of the fibers. Lalia [81] prepared cellulose acetate/PVDF composite membranes(Fig. 6a-b),
et al. [71] prepared composite materials by doping polyvinylidene the obtained results indicated that the battery using the prepared
fluoride-co-hexafluoropropylene, the work showed that the tensile membranes have higher electrochemical performance to that of Celgard
modulus of the material was increased by about 75%, and the electrolyte 2500 membranes. The work of Huang et al. [82,83] showed nanofibers
retention was increased by about 63%. In addition, adding carbon which used cellulose as the core material and poly(vinylidene fluoride-
nanotubes is also considered to be an effective method. Deng et al. [72] co-hexafluoropropylene) (PVDF-HFP) as the shell material(Fig. 6c-d).
pointed out that the addition of carbon nanotubes promoted the The reason that lithium-ion batteries showed excellent performance was
attributed to the good interfacial compatibility of the electrode
5
H. Jiang et al. Fuel 355 (2024) 129534
Fig. 6. (a)The preparation of cellulose acetate/PVDF composite membranes [81]. Reprinted (adapted) with permission from {Renewable and superior thermal-
resistant cellulose-based composite nonwoven as lithium-ion battery separator}. Copyright {2013} American Chemical Society. (b)SEM image of the cellulose/
PVDF-HFP composite materials [81]. (c)Thermal treatment test [82]. (d)SEM and TEM images of nanofibers [82].
materials. It was conducive to improving the cycle performance and rate at 1.0A/g. Furthermore, Kebabsa et al. [91] prepared corn starch carbon
performance of the electrodes. In addition, their work indicated that the nanofibers with cross-linked Co3O4 particles, their results indicated that
cellulose/PVDF-HFP separator exhibited good flame retardancy, which the specific capacitance of supercapacitors was more than three times
enhanced the safety of the battery. Moreover, Zhu et al. [84] studied the that of pure carbon fiber electrodes.
electrochemical performance of membranes prepared by cellulose Protein is often considered to make nitrogen-doped carbon fiber
acetate/L-polylactic acid, and pointed out that L-polylactic acid chains materials. However, the challenges are how to form the expected ma
improved the migration efficiency of lithium ions in energy storage terial structure and obtain high nitrogen content after carbonization. To
devices, while cellulose acetate enhanced its thermodynamic perfor solve these problems, Yang et al. [92] incorporated calcium salt into the
mance. Their coupling effects greatly improved the electrochemical precursors of plant protein, and they found that calcium salt could
performance of the material. ensure that the nanofibers maintained a good fiber structure during
carbonization, and some positive effects on the synthesis of nanofibers
5. Electrospun nanofibers prepared by other biomass with high nitrogen content were also found. The results of electro
components chemical tests showed that the specific capacitance of 64μF cm− 2 at
0.5A/g. The work of Wang et al. [93] indicated that the addition of
Starch, protein, and other components contained in biomass are also cellulose acetate to the solution of soybean protein isolate improved the
widely used to prepare electrochemical energy storage devices. Some physicochemical properties of membranes, and the presence of hetero
researchers [85–87] have noted that carbon nanofibers produced by atoms enhanced the pseudo capacitance. After 50,000 cycles, the cycle
starch have high crystallinity and large specific surface area. Although stability of electrodes still maintained 98.9%.
the nanofibers prepared by starch have significant advantages, the
preparation of electrospun nanofibers directly from starch still has some 6. Differential analysis of various biomass materials for
problems, including poor solubility, low tensile strength and high sur electrochemical application
face tension [88,89]. Some methods have been reported to improve the
characteristics of starch-based carbon nanofibers: 1)Cross-linking Biomass and its derivatives are various and complex in composition
modification with organic polymers, biopolymers; 2)Mixing organic [94]. The morphology and structure of nanofibrous materials prepared
polymers with starch to prepare composite precursors for spinning. from different biomass feedstocks are diverse, so that they exhibit
Jackapon et al. [90] believed that polyvinyl alcohol was a desired pre different electrochemical performances in electrochemical energy stor
cursor solution due to its good thermal stability, biocompatibility and age devices. Table 1 summarizes the typical characteristics and elec
hydrophilicity. Wang et al. [87] prepared a carbon nanofiber with hi trochemical performances of the electrospun nanofiber materials
erarchical micro/meso porous structure using high amylose starch, their prepared using different biomass feedstocks. Considering the properties
work indicated that the specific capacitance of the electrode was 344F/g of the various biomass materials, lignin-based nanofibers are prone to
6
H. Jiang et al. Fuel 355 (2024) 129534
7
H. Jiang et al. Fuel 355 (2024) 129534
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