Progress in Energy and Combustion Science 76 (2020) 100788

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Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

A sustainable platform of lignin: From bioresources to materials and

their applications in rechargeable batteries and supercapacitors
Jiadeng Zhu a,∗, Chaoyi Yan a, Xin Zhang b, Chen Yang c, Mengjin Jiang c, Xiangwu Zhang a,∗
a
Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, College of Textiles, North Carolina State University, Raleigh,
NC 27695-8301, United States
b
State Key Laboratory of Chemical Resource Engineering and College of Life Science and Technology, Beijing University of Chemical Technology, Beijing
100029, China
c
College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, China

a r t i c l e i n f o a b s t r a c t

Article history: Lignin, as a renewable bioresource, has been widely explored in cellulosic biofuel and several other in-
Received 9 March 2019 dustries. There are limited applications of lignin in the energy industry, especially in rechargeable bat-
Accepted 16 August 2019
teries and supercapacitors, even though tremendous research work has been done regarding the use of
lignin in these fields. It is vital to take lignin into consideration because its usage not only improves the
Keywords: performance of these devices but also reduces the cost, contributing to obtaining more sustainable and
Lignin greener energy devices. This paper reviews recent developments of lignin-derived materials in recharge-
Renewable bioresource able batteries and supercapacitors. It starts with a brief introduction of the benefits of lignin, followed
Rechargeable batteries by the fundamental nature and preparation of lignin-derived materials. Significant attention is paid to
Supercapacitors
applications of lignin-derived materials in rechargeable batteries and supercapacitors including their use
as binders and electrodes for rechargeable batteries, and electrodes and electrolytes for supercapacitors
with a focus on the mechanisms behind their operation. The goal is to provide a detailed review of the
critical aspects related to lignin utilized as an important resource for researchers working in a diverse
range of fields dealing with energy storage and conversion. Lastly, a future vision on challenges and their
possible solutions are presented.
Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Nature of lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Origin and synthesis of lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Fundamental structures of lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.1. Monolignols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.2. Linkages between monolignols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2.3. Functional groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Preparation of lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.1. Lignin preparation in laboratory process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.2. Lignin preparation in pulping processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.3. Lignin preparation in biorefinery. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.4. Advantages of lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Applications in rechargeable batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Lignin in lithium batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.1. Anodes for lithium batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.2. Gel electrolytes for lithium batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

∗
Corresponding authors.
E-mail addresses: jzhu14@ncsu.edu (J. Zhu), xzhang13@ncsu.edu (X. Zhang).

https://doi.org/10.1016/j.pecs.2019.100788
0360-1285/Published by Elsevier Ltd.
2 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788

3.1.3. Binders for lithium batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.1.4. Cathode additives for lithium batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2. Lignin in sodium batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4. Applications in supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1. Electrode materials for supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1.1. Activated carbon electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.1.2. Templated carbon electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.1.3. Composite electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.2. Electrolyte materials for supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
5. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

1. Introduction structures including monolignol, linkages between monolignols

and functional groups. More details regarding the analysis of
Energy storage systems are essential for the extensive research various lignin preparation methods are provided. At last, the
of portable electronic devices, electric/hybrid vehicles, etc. due advantages of lignin are described, especially for applications in
to the continuously increasing demand of the world energy the area of rechargeable batteries and supercapacitors.
consumption caused by fast industrial developments and human
population growth [1–8]. However, the intensive use of fossil fuels
has led to environmental issues such as global warming and envi- 2.1. Origin and synthesis of lignin
ronmental pollution [9–12]. Renewable energy sources, which offer
an alternative to the consumption of fossil fuels while protecting Existing in most vascular plants, lignin is an amorphous
the environment and resolving these issues at the global level, are three-dimensional (3D) macromolecule which connects different
highly demanded in this regard [13–21]. kinds of methoxylated phenylpropanoid units by ether bonds and
Lignin, a heterogeneous and amorphous polymer that consti- carbon-carbon bonds [35–43]. As a main component of plants,
tutes a large portion of plants, is one of the prospective candidates lignin is interweaved chemically with hemicellulose and wrapped
because of its low cost and bio-renewable nature [22–24]. De- subsequently outside of cellulose fibers, as shown in Fig. 1 [43].
spite the huge potentials, lignin technologies have not been fully The range of lignin content in biomass is 15–30 wt.%, and softwood
developed so far, and lignin-based materials are not utilized as is supposed to have the highest lignin content among all the plant
high-value products [23,25]. Only a very tiny fraction, less than species, which can be up to 30 wt.% [37,39,40]. The content and
2 wt.%, of the approximately 70 million tons of lignin produced structure of lignin highly depend on the type (i.e., softwood,
during the extraction of cellulose for the paper industry is utilized hardwood, grass plant, etc.) and the part (i.e., stalks, leaves,
as concrete additives, stabilizing agents or dispersants and surfac- husks, seeds, etc.) of various plants, as well as lignin extraction
tants [25,26]. The remainder is simply discarded as waste or burnt methods [41,42]. The functionalities of lignin in plants include
as low-grade burning fuel. structural support with rigidity and strength, transportation corri-
Lignin is inexpensive and possesses numerous attractive dor of water and nutrient, a recalcitrant barrier against pests, and
properties, including high carbon content, high thermal stabil- microorganisms.
ity, biodegradability, antioxidant activity, and favorable stiffness Although lignin stock in biomass ranks second to cellulose, very
[27–30]. These advantages have motivated interests in developing less of annual lignin output in the whole world has been commer-
lignin into value-added products for various applications in energy cially utilized in the area of materials engineering and chemical
storage systems. Comprehensive research work has been carried industry [37,44]. The reason for this situation mainly attributes
out to concentrate on two imperative energy storage systems, to two sides: one is structural complexity and diversity of lignin
which are rechargeable batteries and supercapacitors, respectively, production, which exist in different biomass types and pretreat-
even though the strategy to design effective energy storage de- ment processes [45,46]; the other is the limitation of unmodified
vices with acceptable energy density, long-term durability, and lignin in the aspect of broad molecular weight distribution, poor
high safety is a challenging area of research [31,32]. solubility, and incompatibility with host matrices [38].
This review intends to provide an overview of recent research Owing to the aforesaid property of complicated structure, the
on the conversion of lignin to high-value products applied in the biosynthetic process of native lignin has been studied for more
fields of rechargeable batteries and supercapacitors. It starts with than a century, which is briefly described as follows: first, three
a brief introduction of the advantages of lignin, followed by the types of aromatic alcohol precursors, which are sinapyl alcohol,
fundamental nature and preparation of lignin-derived materials. coniferyl alcohol, and p-coumaryl alcohol, respectively, are biosyn-
The review then highlights the applications of lignin-derived ma- thesized from L-phenylalanine via catalysis of several enzymes
terials in rechargeable batteries and supercapacitors, focusing on [44,47]. These three precursors are then transported to the cell
mechanisms behind their operation. A future vision on challenges wall with the help of glucosides [48]. Later, lignin is polymerized
and their possible solutions are presented at the end. on the cell wall through the enzyme-mediated dehydrogenative
polymerization (namely lignification) of precursors by laccases and
2. Nature of lignin peroxidases [47]. Three types of corresponding monolignols are
finally formed from abovementioned aromatic alcohol precursors.
With the growing crisis of oil resources, lignin, as one of the Since the biosynthesis of lignin is a synergistic effect with several
main components in biomass, has attracted tremendous atten- enzyme-catalyzed reactions, no artificial approach is applied to
tion in the last few decades [33,34]. Fundamental properties of synthesize native lignin up to now [49]. Exploring the complete
lignin should be comprehensively understood prior to its practical synthesis mechanism of native lignin is still necessary to better
applications. Therefore, we first introduce the origin and biosyn- understand lignin structure and realize comprehensive applications
thesis paths of lignin in this section, then discuss its chemical of lignocellulosic biomass.
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788 3

Fig. 1. Typical structures of cellulose, lignin, and hemicellulose in lignocellulosic biomass [43]. Copyright 2012. Reproduced with permission from Royal Society of Chemistry.

2.2. Fundamental structures of lignin

Lignin structure analysis is complicated compared with other

polymers due to its random chemical bonding between various
monolignols [50–52]. Monolignol types, linkages between mono-
lignols and functional groups in lignin will be introduced in detail.

2.2.1. Monolignols
The chemical structures of three monolignols, which are sy-
ringyl (S unit), guaiacyl (G unit) and p-hydroxyphenyl (H unit),
respectively, are shown in Fig. 2 [50–52]. The differences among
them depend on the methoxylation degree on the benzene ring
[51]. Softwood lignin is mainly made up of G units with a per-
centage of 90–95 wt.% of the total monolignols, while hardwood
lignin includes both G and S units [37,41]. In grass lignin, all three
monolignol types can be observed [53]. The amounts of monolig-
nols in softwood and grass will be greatly different according to
plant species. Besides, the amounts and types of monolignols will
be affected by various pretreatments so that the ratio of S, G and
H units is an important index to analyze lignin properties during
the lignin isolation process.

2.2.2. Linkages between monolignols

During the lignification process, monolignols are connected
randomly by ether bonds or carbon-carbon bonds at different
locations, which generate several types of interunit linkages in
various lignin substructures (Fig. 2). β -O-4 ether linkage is the
most dominant linkage type in lignin, which accounts for 50% of
the whole interunit linkages [38]. Meanwhile, the β -O-4 linkage
is the most reactive linkage type during the depolymerization pro-
cess, and β -O-4 cleavage is a significant feature during the lignin
fragmentation. Therefore, the content variation of β -O-4 linkage is
a key criterion in most of lignin degradation studies [54]. Besides,
β -β  , β -5 , β -1 and 5-5 linkages also exit in lignin, but they Fig. 2. Monolignols (Syringyl; Guaiacyl; p-hydroxyphenyl) and lignin substructures
(I: β -O-4 substructure; II: β -O-4 , α -O-4 and 5-5 linkage in dibenzodioxocin sub-
are not as uppermost as β -O-4 linkage. β -β  linkage is abundant structure; III: β -5 linkage in phenylcoumaran substructure; IV: β -β  in resinol sub-
in syringyl-rich lignin probably due to the higher stability and structure; and V: β -1 linkage in spirodienone substructure).
longer lifetime of the sinapyl alcohol radicals [55]. β -5 exists
in phenylcoumaran substructure, which can be obtained from
4 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Fig. 3. Preparation of lignocellulosic biomass-derived lignin by various process scales.
dehydrogenation polymerization of coniferyl alcohol. In recent
studies, evidence has shown that rearrangement reaction happens
to form β -5 linkages after steam-explosion pretreatment [56,57].
5-5 linkage comes from a biphenyl structure and is confirmed as
a native linkage type in the milled wood lignin, reported by Pew
et al. [58]. β -1 linkage, mostly in spirodienone substructure, is
unstable in acidic conditions [59].
2.2.3. Functional groups
Lignin has abundant functional groups, such as hydroxyl, ben-
zyl, methoxyl, ether, carboxyl, etc., resulting in its amphiphilic
nature [60]. Hydroxyl is the most important functional groups
for lignin modifications including alkylation, esterification, phe-
nolation, hydoxypropylation, etc. [37,50]. There are two types of
hydroxyl groups which are aliphatic hydroxyl and phenolic hy-
droxyl, respectively. Hydroxyl content is a critical parameter to not
only estimate the etherification degree and condensation degree of
lignin but also influence the solubility of lignin [61]. In recent stud-
ies, 31 P NMR has been considered as a powerful method to char-
acterize the quantification of different hydroxyl types [50]. Benzyl
and methoxyl are two kinds of primary functional groups which
constitute the basic structure of monolignol, distinguishing lignin
from other main components in biomass. As mentioned above, the
monolignol type depends on the methoxyl substitution degree on
the aromatic ring. The methoxyl group in lignin is very stable un-
less severe depolymerization happens. For example, demethoxyla-
tion of lignin usually occurs at a high temperature (over 250 °C)
and high pressure (over 5 MPa) [62]. Ether bonds are common
bond types connected between monolignols, which mainly form β -
O-4 and α -O-4 linkages. In native lignin, carboxyl is believed to
be present in low concentration which increases significantly after
chemical modification in degradation processes [63]. The diversity
of functional groups shows great potential for lignin modification,
which prompt lignin applications in multiple areas such as mate-
rial synthesis and chemical catalysis, etc.
2.3. Preparation of lignin
As summarized in Fig. 3, based on production scales, lignin
preparation methods are classified into three sides: (i) laboratory
process, (ii) pulping process, and (iii) biorefinery. Discussion in
this section focuses on lignin properties resulted from various
lignin isolation procedures.
2.3.1. Lignin preparation in laboratory process
In laboratories, lignin is mostly extracted for structural char-
acterization research, and hence most methods are attempted to
maintain structures that are close to those of native lignin with
minimum destruction [46].
Milled wood lignin (MWL) was first prepared in 1957 by treat-
ing milled biomass stock under reflux reaction using a mixture of
water and neutral solvent like dioxane through extraction system
[64]. This method gives an advantage of relatively complete lignin
structure, which has been considered as a representative of native
lignin for decades [65,66]. However, the lignin yield of the MWL
method is less than 40 wt.% of the entire lignin content and is
generally limited by milling time for dozens of hours [46,67,68].
Additionally, MWL reserves certain amounts of carbohydrates due
to the unbreakable lignin-carbohydrate complex (LCC) between
lignin and carbohydrates (mainly hemicellulose) [69,70].
Cellulolytic enzyme lignin (CEL) has been developed subse-
quently by using cellulase to hydrolyze cellulose in biomass based
on the procedure of MWL [64]. Compared with MWL, CEL has a
higher lignin yield which is attributed to the removal of cellulose
while keeping an analogous structure and element constitution
[71–74]. For the viewpoint of Niu et al., the structures of lignin
derived from CEL are close to those of natural lignin, which makes
CEL suitable for green applications such as carbon dot preparation
for cellular imaging [72]. Additionally, lignin-based nanoparti-
cle preparation from CEL was reported by Tian et al., which
demonstrated that CEL with condensed structure after steam
pretreatment performed great potential for the core formation of
lignin nanoparticles by increasing the hydrophobic aggregation
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
[73]. Moreover, the well-preserved structure and better yield make
CEL competent for lignin structural characterization [75,76].
Enzymatic mild acidolysis lignin (EMAL) is an improved lignin
product which can be optimized based on CEL procedure by
adding a low concentration of hydrochloric acid to achieve lignin
yield up to 70 wt.% with a lignin purity around 90% in woody
plants, reported by Wu et al. [77]. Compared with MWL and CEL,
EMAL has fewer LCCs and higher molecular weight, which indi-
cates a unique extraction protocol of lignin fractions [78]. Recently,
EMAL is utilized in structural analysis of various plants and is no
longer limited to woody species. With concomitant advantages of
high yield, high purity, and complete structure, EMAL is popular
for lignin structural analysis with diverse treatments. For example,
both Sun et al. [79] and Sathitsuksanoh et al. [80] reported EMAL
characterization after ionic liquid pretreatment. Several other
studies utilized EMAL to analyze lignin change during steam
explosion pretreatment [56,59]. Meanwhile, EMAL can be applied
to accelerate pyrolysis processes to form chars and tars under
higher temperatures (from 600 to 900 °C) [81–83].
2.3.2. Lignin preparation in pulping processes
Distinctive from lignin isolation in a laboratory scale, the
extracted lignin product in industrial scale is termed as technical
lignin, which was first realized by the pulping process [84–86].
Primarily, four different types of lignin are classified according to
various pulping processes, namely kraft lignin, lignosulfonate, soda
lignin, and organosolv lignin.
Most of the lignin in the pulping industry is extracted from
kraft pulping [35]. Basically, alkaline solution system (such as
sodium sulfide and sodium hydroxide solution, etc.) is used in
this process, and lignin depolymerization mainly occurs in ether
linkages connected to α or β position of monolignols [44]. Lignin
polymers are broken into small chains by ether breakage and
dissolved in the alkaline solution to form a lignin solution system
named black liquor [35]. Kraft lignin is then recovered by acidi-
fication of black liquor, which creates advantages of regeneration
and reutilization of Na+ and S2− in the solution mixture [87]. Hy-
drophobic thiol groups are included in kraft lignin, which makes
the sulfur content of 1–2 wt.% [36]. However, most of kraft lignin
is sulfur-free, which can be precipitated in an acidic solution to
isolate lignin [44].
Sulfite pulping process utilizes a similar process to kraft
pulping but with acidic solution mediums [51]. The final lignin
products are called lignosulfonates because of massive sulfonate
group formation onto the side chains. Lignosulfonates are soluble
in water with hemicellulose, so external technique should be
applied to remove hemicellulose component [44]. In addition,
lignosulfonates have both high molecular weight and high ash
content [35]. All these features make lignosulfonates qualified
for many industrial applications, such as newspaper production,
adhesives, batteries, dispersants and surfactants [88,89].
Soda lignin is isolated from soda or soda anthraquinone pulp-
ing process [38]. This method has been performed for non-woody
species since the 19th century [85]. As a catalyst, anthraquinone is
also used to weaken the degradation of carbohydrates and dissolve
lignin simultaneously [54]. Although soda lignin exhibits very
high purity, its molecular weight is low [44]. Compared with kraft
pulping, soda lignin has no sulfur and is more like native lignin
than kraft lignin and lignosulfonate, which demonstrates soda
lignin as a good candidate for chemical modification [36,90]. So
far, soda lignin has been modified by a large range of reagents or
polymers, such as polyurethane [91], hexamethylene diisocyanate
[92], and ionic liquid [93], etc.
By using organic solvents such as acetic acid, formic acid,
ethanol, etc., the approach of organosolv pulping fabricates organo-
solv lignin with distinctive properties compared to the above three
5
lignin types. The most prominent distinction of organosolv lignin
is its excellent solubility. They can be dissolved in alkaline solu-
tions and a wide range of organic solvents [51]. Organocell lignin
and Alcell lignin are two familiar organosolv lignin types for com-
mercial production [94]. Organosolv lignin has a relatively uniform
molecular distribution mainly due to the dissolution effect of sol-
vents, but it contains several condensed structures [35,86]. Lately,
organosolv lignin is attractive to biomaterial synthesis because
of its high purity, sulfur-free, and less modification, reported by
Asawaworarit et al. [95] and Spiridon et al. [96].
2.3.3. Lignin preparation in biorefinery
In recent years, biorefinery has become a new concept for
biomass conversion to useful chemicals and fuels, thus realizing
part of the replacement of fossil energy and resource [39]. In the
biorefinery process with different biomass, three main components
(cellulose, hemicellulose, and lignin) are expected to be isolated
respectively to accomplish complete utilization. Biomass pre-
treatment is the core of biorefinery, which is aiming at reducing
biomass recalcitrance, improving enzyme digestion, and down-
stream product isolation [97]. Due to its irregular structure, lignin
is commonly treated as a byproduct in a biorefinery. Nowadays,
with improving understandings and ever-growing applications
of lignin, lignin recovery concepts, even lignin-first biomass
fractionation strategies, have been gradually developed [98,99].
It is common that biomass pretreatment technologies can be
classified into biological, physical, chemical, and physicochemical
approaches [100], while it is hard to extract lignin by using either
biological or physical pretreatment alone. Here, the discussion
aims at lignin extraction by using chemical and physicochemical
pretreatments, as well as combined pretreatments.
In terms of chemical pretreatment, the difference of lignin
deconstruction mechanism between alkali pretreatment and acid
pretreatment is apparent. Alkali-based pretreatment utilizes vari-
ous kinds of alkaline (e.g., NaOH, Ca(OH)2 , ammonia, etc.), causing
effects of lignin solubilization or degradation [39]. NaOH is the
most frequently used chemical for aqueous alkaline pretreatment.
It is similar to the soda pulping process, while the severity is
relatively low. During alkali-based pretreatment, the ether link-
ages between monolignols are partially broken to obtain lignin
oligomers, phenolic dimers, and monomers [39]. The degradation
degree of lignin highly depends on the biomass type and pretreat-
ment conditions. Another popular alkaline reagent is ammonia,
which is combined with several biomass pretreatments like am-
monia fiber explosion (AFEX), anhydrous ammonia pretreatment
(AAP) and ammonia recycled percolation (ARP). Ammonia is good
to preserve carbohydrates while dissolving/reorganizing lignin,
which is different from NaOH. It should be noted that ammonia is
easy to recover because of its high volatility [40]. β -O-4 linkages
are rather well preserved, and minor lignin degradation occurs
after all these ammonia-induced pretreatments. Previous studies
showed that lignin yields ranged from 31 wt.% to 65 wt.% of overall
lignin content by these ammonia-induced pretreatments with
1–2 wt.% nitrogen in these lignin products [101–103].
On the other hand, diluted hydrochloric acid, sulfuric acid, and
phosphoric acid are often applied in acid-based pretreatments.
This kind of pretreatment can be divided into two modes: one
is dilute acid solution (0–5 wt.%) at relatively high temperatures
(>180 °C), the other is concentrated acids at low temperatures
(<120 °C). In most cases, dilute acid hydrolysis depolymerizes
cellulose and hemicellulose prior to lignin extraction. Lignin
transformation during acid hydrolysis has been concluded to three
parts: lignin droplet formation and redeposit, lignin migrating,
and pseudo-lignin formation [39]. Moreover, highly concentrated
acid can be used for acid hydrolysis like Klason lignin, which
is generally applied to quantify lignin content in biomass [37].
6 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788

However, Klason lignin is highly condensed so that it is difficult

for chemical modification.
Besides alkali and acid pretreatments, organosolv pretreatment
is also an important technique for lignin extraction with two
aspects. On the one hand, organic solvents (e.g., alcohols, ethers,
esters, ketones, etc.) have excellent solubility to dissolve lignin
with slight chemical modification. Thus, lignin products with
lower ash content, lower molecular weight, and higher hydropho-
bic property can be achieved [39,104]. On the other hand, highly
reductive agents (e.g., H2 -donating solvents, etc.) or oxidants (e.g.,
O2 , O3 , H2 O2 , etc.) can be utilized in the organosolv pretreatment,
which significantly promotes cleavage of ether linkages and LCC
bonds, resulting in different lignin structures from native lignin.
The isolated lignin products also vary with different treating con-
ditions [39,40]. Therefore, organosolv lignin has been considered
as an excellent candidate for composite synthesis because of its
high quality and excellent reactivity [104].
Ionic liquid (IL) pretreatment is an emerging technique since it
was reported in 2007 [37]. The main advantages of IL include high
thermal stability, slight vapor pressure, low flammability, and a
broad liquidus temperature range [104]. Typical ionic liquids show
specific solubility to cellulose and lignin, which can be tuned by
changing viscosity with water or other solvents [105]. Two kinds
of primary lignin extraction pathway have been proposed. One
is complete biomass dissolution in ILs with subsequent lignin
precipitation by adding antisolvents; the other is a selective dis-
solution by specialized ILs for one of the components in biomass
and concomitant isolation steps [37]. However, the toxic property,
high reagent cost, and recyclability issue are intractable problems
which limit the practical applications of ILs. Recently, deep eutectic
solvent pretreatment regarded as a new class of ILs has become
effective to isolate lignin with high purity [106–108]. The results
showed that this pretreatment could dissolve lignin at about 60 °C
and realized extracted lignin with a purity of over 90% [108].
Physicochemical pretreatment is popular in biorefinery plants
attributed to combined strengths with physical pretreatment and
chemical pretreatment. However, lignin extraction by physico-
chemical pretreatment has not been fully investigated. Up to date,
aside from the abovementioned AFEX pretreatment, lignin extrac-
tion research during the steam explosion pretreatment and hot
water pretreatment are frequently proposed. These two types of
pretreatments are also called autohydrolysis, which is a typical
kind of acid hydrolysis since water can be treated as an acid at
high temperatures [109]. Hot water pretreatment utilizes vapor at
high temperatures of 160–240 °C and high pressures for hemicellu-
lose hydrolysis [110]. Steam explosion pretreatment, which is also
operated under high temperatures and pressurized steam/water,
mostly break cellulose or hemicellulose. During these two pre-
treatments, part of lignin is dissolved in hydrolysates, and the
rest of lignin remains in the pretreated residues. Acid-catalyzed
hydrolysis and acid-catalyzed condensation occur on lignin, which
causes the loss of β -O-4 linkages and the formation of condensed
structures [40].
In order to increase production yield and efficiency to a higher
level, combined pretreatments have been applied in biorefinery
frequently. Lignin isolation during combined pretreatments has
been reviewed by Wang et al. [39]. Physical pretreatment is
indispensable to treat biomass material into suitable sizes, while
biological pretreatment (especially enzymatic hydrolysis) is an
effective pretreatment to improve hydrolysis yield. These two pre-
treatments are always cooperated in chemical and physicochemical
pretreatments. Besides, physicochemical pretreatment can com-
bine with chemical pretreatment. There is no doubt that lignin
extraction in biorefinery is a comprehensive task since a balance
should be kept between lignin extraction and produced chemi-
cals/fuels from cellulose and hemicellulose. Moreover, combined
Fig. 4. Schematic image showing the advantages of lignin.
pretreatments are also adopted during the biorefinery process,
making lignin characterization and extraction more complicated.
Further studies on lignin isolation using different biorefinery pro-
cesses are still necessary to realize the full utilization of biomass.
2.4. Advantages of lignin
Due to the origin of a wide range of plant resources and
industrial processes, lignin has with the features of huge reserves,
low cost and favorable renewability, as summarized in Fig. 4 [39].
These are the most important prerequisites to broaden lignin ap-
plications for substituting other materials. In fact, lignin has been
researched in material science for quite a long time, not merely
because of the abovementioned features, but also some unique
properties like antioxidant ability, UV absorbance, biocompatibility,
antibacterial property, and autofluorescence [36,45]. These proper-
ties endow composite polymers with different functional features,
combining material science with other disciplines such as bio-
chemistry [52], medical treatment [38], artificial intelligence [36],
etc. Moreover, lignin depolymerization to high-value chemicals has
attracted lots of attention recently [40,64],
In the past few years, lignin application for energy storage de-
vices has developed immensely [51]. As an important component
in the preparation of rechargeable batteries and supercapacitors,
lignin and lignin-derived materials have numerous strengths.
With an increased output in commercial manufacturing, lignin
is globally available with low-cost, which effectively induces the
production costs of the devices [111,112]. It is noteworthy that
the major element in lignin is Carbon, with a high content of
above 60 wt.% [113]. Around 30 wt.% of the organic carbon in
the biosphere is originated from lignin which presents massive
potential applications of lignin as a promising carbon precursor
[44,114]. Functional groups (especially benzyl and phenolic groups)
in lignin provide active reaction sites, enabling the storage of ions
for supercapacitors. In specific conditions, lignin can be transferred
to quinone moieties and presents great redox activity [115,116].
It is obvious that different lignin types have different func-
tionalities to be applied in energy storage systems. For example,
lignosulfonate has a large amount of sulfur content, which can
be treated as a sulfur-doped agent in rechargeable batteries or
supercapacitors [117–122]. Compared with lignosulfonate, alkali
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Table 1
Overview of lignin-derived anodes in lithium batteries [138–146].
Materials Synthesis
Lignin hierarchical porous carbon Activation
KOH: lignin (2:5), HCl
Lignin porous carbon Activation
K2 CO3 : lignin (1:1), HCl
Lignin (hydrogen reduced) Used as received
N/S co-doped sisal fibers Sulfamic acid hydrothermal
treatment (140 °C)
PAN/lignin carbon fibers Electrospinning
PAN: lignin (1:1)
PVA/lignin porous carbon fibers Electrospinning
PVA: lignin (1:1)
Activation-KOH
Lignin fused carbon fibers Electrospinning
PEO: lignin (9:1)
Lignin carbon fibers Melt-blowing fiber
Lignin carbon fibers (Kraft pulp) Industrial Kraft
LignoBoost® procedure
lignin and organosolv lignin are good for electrospinning which
has been demonstrated as an excellent method to prepare nano-
materials. In addition, lignin is an environmental-friendly polymer
which is distinctive from traditional additives. Excellent renewable
and biodegradable characteristics of lignin can help solve pollution
issues existed in the manufacturing of energy storage devices, es-
pecially in the fields of rechargeable batteries and supercapacitors.
3. Applications in rechargeable batteries
To combat global warming and climate change, low carbon
economy has been raised with worldwide awareness [123,124].
Over the years, clean and renewable energy storage systems
have been rapidly developed to replace traditional fossil fuels
[125,126]. Among them, rechargeable batteries are regarded as the
most important energy storage devices owing to the high energy
density, high output voltage, and long cycle life [126]. To meet the
ever-growing demands in large-scale applications such as electric
vehicles and stationary energy storage grids, tremendous research
efforts have been devoted to investigating the electrochemical
performance of each component in rechargeable batteries (i.e.,
anodes, electrolytes, binders, cathode additives, etc.) [127]. Addi-
tionally, the cost and processing method are also critical for the
commercial implementation [128,129]. Herein, we provide a de-
tailed review of various applications of lignin as a renewable and
low-cost bioresource in recent rechargeable battery technologies,
especially as novel anode materials and promising additives in
lithium/sodium-ion batteries (LIBs/SIBs).
3.1. Lignin in lithium batteries
3.1.1. Anodes for lithium batteries
Carbon materials have been extensively studied as anode ma-
terials for LIBs due to their abundance, low cost, good chemical
stability, and Li+ storage ability [130,131]. Biomass-derived carbon
materials have received extensive attention due to their sustain-
ability and extremely low-cost [132–134]. Lignin, the second most
abundant polymer in nature, is a promising renewable carbon pre-
cursor since the large polyaromatic macromolecules of lignin re-
sults in a high char yield (over 50 wt.%) after pyrolysis [135,136].
Additionally, the high conductivity and excellent mechanical in-
tegrity of lignin-derived carbon are beneficial for high reversible
Li+ storage capacity and fast lithium storage kinetics [137]. Table 1
7
Carbonization Electrochemical performance Ref.
700 °C-2 h (N2 ) 470 mAh g−1 (400th cycle, 200 mA g−1 , 0.01–3.0 V) 138
250 °C-0.5 h (N2 ) 520 mAh g−1 (200th cycle, 200 mA g−1 , 0.001–3.0 V) 139
900 °C-2 h (N2 )
800 °C-1 h (H2 )
300 °C-2 h (N2 ) 222 mAh g−1 (200th cycle, 2 C, 0–2.5 V) 140
800 °C-1 h (H2 )
750 °C-1 h (N2 ) 525 mAh g−1 (50th cycle, 50 mA g−1 , 0.01–3.0 V) 141
250 °C-3 h (Air) 150 mAh g−1 (50th cycle, 8.5 C, 0.005–2.8 V) 142
1000 °C-1 h (N2 )
100 °C-12 h (I2 ) 290 mAh g−1 (100th cycle, 50 mA g−1 , 0.01–2.5 V) 143
600 °C-1 h (Ar)
500 °C-2 h (N2 ) 550 mAh g−1 (50th cycle, 30 mA g−1 , 0–3.0 V) 144
Urea solution
900 °C-2 h (N2 )
250 °C-3 h (Air) 349 mAh g−1 (70th cycle, 15 mA g−1 , 0.005–1.5 V) 145
1000 °C-1 h (Ar)
−1
200 °C-2 h (Vaccum) 348 mAh g (3rd cycle, 0.1 C, 0.002–1.5 V) 146
1000 °C-1 h (N2 )
summarizes recent work on various lignin-derived anodes in
lithium batteries, including synthesis methods, carbonization con-
ditions, and the corresponding electrochemical performance.
Zhang et al. first introduced a lignin-based hierarchical porous
carbon (LHPC) anode by facile preparation with alkali lignin
precursor [138]. A 3D macroporous carbon network (Fig. 5a) was
obtained by using KOH as a template and activating agent. With
abundant mesopores and micropores decorated on carbon walls,
LHPC had a high specific surface area of 907 m2 g−1 , which effec-
tively enhanced the storage capacity and shortened the diffusion
distance of lithium ions. Consequently, a much higher capacity
of 470 mAh g−1 was achieved for the cell with the LHPC anode
compared to that of pristine carbonized lignin anode (180 mAh
g−1 ) after 400 cycles at a current density of 200 mAh g−1 .
Later, Xi et al. studied the performance of lignin-based porous
carbon materials with different activation processes [139]. It is
found that K2 CO3 is superior to KOH in promoting the rear-
rangement of lignin carbon atoms and increasing the degree of
graphitization. In addition, K2 CO3 activated lignin carbon (ALC-
K2 CO3 ) had a higher porosity and continuous pore size distribution
from micro- to mesopores, leading to a high specific surface area of
2300 m2 g−1 . The cells with ALC-K2 CO3 anodes could maintain re-
versible capacities of 520 and 260 mAh g−1 after 200 cycles at cur-
rent densities of 200 and 10 0 0 mA g-1 , respectively. It is, therefore,
demonstrated that the multistage pore structures and graphitic
structure of lignin-based carbon are favorable for the intercala-
tion of lithium ions because of the fast diffusion of ions in the
materials. Chang et al. investigated the influence of reduction en-
vironment on lignin-based hard carbon performance in LIBs [140].
As illustrated in Fig. 5b, surface defects were created along with
the polymerization of lignin monomers during the carbonization.
Carbonization under N2 flow leads to the formation of dangling
bonds and oxygen-containing covalent bonds, which result in the
irreversible capacities due to the active reaction with lithium ions.
On the contrary, H2 reduction process benefits from removing
the surface defects containing O atoms and improving the degree
of graphitization through the inductive effect of H2 . Therefore,
the cell with H-reduced lignin carbon displayed a lower initial
irreversible capacity and higher Coulombic efficiency (62.4%). The
excellent capacity retention of 92.3% was achieved after 200 cycles
at 2 C. Wang et al. fabricated the nitrogen and sulfur co-doped
lignin-based carbon (NS-SFC) using sisal fibers via facile hydrother-
mal process followed by pyrolyzing with sulfamic acid [141]. By
8 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Fig. 5. (a) Schematic diagram of the formation process of lignin hierarchical porous carbon [138], and (b) reaction mechanism during the pyrolysis process of lignin under
H2 environment [140]. Source: (a) [138], Copyright 2015; (b) [140], Copyright 2015. Reproduced with permission from Elsevier Inc.
tuning the mass ratio of sisal fibers to sulfamic acid during
hydrothermal treatment, optimum nitrogen (4.5 wt.%) and sulfur
(0.9 wt.%) doping ratios were determined. High reversible capacity
(525 mAh g-1 ) and excellent cycling stability could be obtained
for the cell with the prepared NS-SFC anode, which is attributed
to the improved electrical conductivity with nitrogen doping and
increased interlayer distance and micropores with sulfur doping.
Carbon nanofibers (CNF) are considered to have higher rate-
capability because the 1D morphology provides extremely higher
surface area and enhanced electrical conductivity. Lignin-based
carbon nanofibers (L-CNFs) have also been studied. Due to its
low molecular weight, lignin is usually blended with other
polymers to prepare fiber materials [142–144]. Choi first fabri-
cated the PAN/lignin CNFs through electrospinning followed by
heat-treatments [142]. It is found that the carbon structure and
electrochemical performance of PAN/lignin CNFs were similar with
changing the lignin content from 0 to 50 wt.%. All PAN/lignin CNF
anodes showed stable capacity retention (∼99%, 150 mAh g-1 )
after 50 cycles at a high current density of 8.5 C, confirming the
PAN/lignin (1:1 by weight) CNFs are identical to pure PAN CNFs.
It is, therefore, demonstrated that lignin is a promising precursor
for low-cost production of carbon nanofibers for high-rate LIBs.
Similarly, PVA/lignin (1:1 by weight) porous CNFs were prepared
by Stojanovska et al. using the electrospinning method followed
by an activation process with KOH [143]. After 10 0 0 cycles at
a current density of 300 mAh g-1 , the cell could still deliver a
specific capacity of 110 mAh g-1 with the capacity fade of 16%.
Furthermore, Wang et al. introduced the fused carbon fibrous
mats using electrospun poly(ethylene oxide)/lignin (PEO/lignin)
nanofibers followed by carbonization and thermal annealing with
urea [144]. To further reduce the cost and enable the ability in
large-scale production, low content of PEO (10 wt.%) was uti-
lized for increasing the viscosity and spinnability of the solution.
After thermal annealing with urea, free-standing fused carbon
fibrous mats were obtained. A retained capacity of 445 mAh g-1
was delivered after 50 cycles at a current density of 50 mAh
g-1 , which is comparable to that of PAN-derived carbon fibers.
In addition, N-doped fused PEO/lignin CNFs exhibited further
improved electrical conductivity and specific capacity (550 mAh
Table 2
Overview of lignin composite anodes in lithium batteries [147–152].
Materials Synthesis
Lignin/SiNPs Self-assembly in phytic acid
Lignin/Si Mixing mixture
Lignin/SiNPs lignin-based azo polymer
Lignin/SiOx Mixing mixture
Lignin/SiNPs Mixing mixture (1 wt.%) PEO
Lignin/NiO Ni(OH)2 with porous lignin spheres
g-1 ) [144]. Furthermore, large-scale lignin carbon fibers derived
by melt-blowing and LignoBoost industrial Kraft production were
then investigated by Tenhaeff et al. and Nowak et al. [145,146]. A
satisfactory capacity of 350 mAh g-1 was achieved at the initial
cycles for those large-scale lignin carbon fibers.
Although the carbon materials show good cycling stability and
excellent rate capability, the relatively low theoretical capacity
(372 mAh g-1 ) prevents their further applications in high energy-
density LIBs. To improve upon the capacity, Li alloys, for example,
Li-Si (theoretical capacity 4200 mAh g-1 ), are being extensively
studied [147–152]. Nevertheless, the huge volume expansion
(∼400%) and the formation of unstable solid electrolyte interface
(SEI) on the Si anode during lithiation and delithiation lead to
severe pulverization of Si particles and fast capacity fade [153,154].
Structural designs based on carbon-Si composites can poten-
tially alleviate or avoid the pulverization of Si particles. Various
lignin-based composite anodes, including their synthesis methods,
carbonization conditions, and electrochemical performance, are
summarized in Table 2.
Niu et al. utilized biomass lignin to form a functional conformal
network crosslinking with silicon nanoparticles (SiNPs) via self-
assembly in phytic acid [147]. SiNPs were first treated and func-
tionalized with phytic acid. The plentiful functional groups in pri-
mary monolignol precursors endowed abundant action sites for
in-situ modification of lignin with phytic acid-treated SiNPs.
Benefiting from the excellent mechanical properties of cross-
linked lignin, the novel lignin/SiNP composite accommodated
large volume change during the charge/discharge process. Dif-
ferent mass ratios of SiNPs to lignin (SiNPs/lignin=1:2, 2:1,
5:1) were investigated. It was found that thin functional lignin
coating (SiNPs/lignin=5:1) was not sufficient for stabilizing the
Si electrodes, while thick conformal lignin network coating
(SiNPs/lignin=1:2) greatly influenced the total electrical conductiv-
ity of the anode, resulting in a lower specific capacity. The opti-
mum mass ratio was determined to be SiNPs/lignin = 2:1, and the
resultant cell exhibited remarkable cycling performance with 89%
capacity retention after 100 cycles at a current density of 300 mAh
g-1 , which was attributed to the stable SEI layer formed on the
lignin/SiNP anode. Pyrolyzed lignin/SiNP composites were also in-
Carbonization Electrochemical performance Ref.
N/A 2670 mAh g−1 (100th cycle, 300 mA g−1 , 0.01–1.5 V) 147
600 °C-5 h (Ar) 969 mAh g−1 (50th cycle, 300 mA g−1 , 0.015–1.0 V) 148
750 °C-5 h (Ar) 882 mAh g−1 (150th cycle, 200 mA g−1 , 0.01–1.0 V) 149
600 °C-2 h (Ar) 900 mAh g−1 (250th cycle, 200 mA g−1 , 0.005–1.2 V) 150
800 °C-2 h (Ar) 1391 mAh g−1 (100th cycle, 540 mA g−1 , 0.005–1.2 V) 151
450 °C-2 h (N2 ) 863 mAh g−1 (100th cycle, 200 mA g−1 , 0.01–2.5 V) 152
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Fig. 6. (a) Schematic illustration of morphology changes of Si-Lig (upper) and Si-LigCel (lower) composite anodes during cycling [148], and (b) schematic diagram of the
formation process of the SiOx -Lignin composite anode [150]. Source: (a) [148], Copyright 2018. Reproduced with permission from American Chemical Society; (b) [150],
Copyright 2017. Reproduced with permission from Elsevier Inc.
vestigated by Chou et al. [148]. Carbon-coated Si structure (Si-Lig)
was obtained with lignin, while an interconnected carbon structure
with Si particles (Si-LigCel) was formed with lignocellulose precur-
sor. The cell with Si-LigCel anode showed better cycling stability
(capacity retention 83.4%) than that of the cell with Si-Lig anode
(38.5%). As illustrated in Fig. 6a, the Si-Lig composite with carbon
coating enhanced the overall electrical conductivity and hence im-
proved the initial capacity. However, the repeatedly swelling and
shrinking of Si particles eventually destroyed the electrode struc-
ture, leading to the poor cycle life. In contrast, the Si-LigCel com-
posite formed an interconnected carbon network, and Si parti-
cles were embedded on this fibrous carbon structure, which could
accommodate significant volume changes during cycling. Chen et
al. added PEO (1 wt.%) in lignin/Si blend precursor, tuning the Si-
carbon in a core-shell structure with the void (Fig. 6b) [150]. Con-
sequently, the synthesized Si-lignin composite anode demonstrated
stable cycling (capacity retention 89.3%) over 100 cycles and high
rate capability up to 1.44 A g-1 . In addition, replacing Si with SiOx
could also improve the cycle life of Li-Si batteries by introducing
the buffer components of Li4 SiO4 generated during the first lithi-
ation process between SiOx and Li. Carbon-coated SiOx was pre-
pared by Chen et al. using a lignin-based precursor to improve the
electrical conductivity of SiOx [150]. With smaller volume changes
(∼160%) in SiOx particles, the SiOx -Lignin composite anode exhib-
ited superior cycling stability. A retained capacity of 900 mAh g-1
could be still obtained after 250 cycles at a rate of 200 mAh g-1 ,
corresponding to a nearly 99% capacity retention. The results above
display that low-cost but high-performance electrodes can be pre-
pared via using those biomass derived materials which provide an
environmentally friendly approach for their practical applications.
3.1.2. Gel electrolytes for lithium batteries
The usage of isolated organic liquid electrolyte in LIBs may
cause serious safety problems including leakage, flame, and blast
[155–157]. Gel polymer electrolytes (GPEs) with limited liquid
electrolyte uptake, as promising alternatives, greatly reduce the
safety hazards of LIBs, however, the current polymers used in
GPEs are difficult for biodegradation, including polyethylene oxide
(PEO), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), and
polyvinyl acetate (PVA) [158–164]. Consequently, the massive use
of GPEs in commercial LIBs and the huge degradation resistance
of these polymer matrixes will eventually result in serious “white
pollution” in a natural environment. Therefore, as the second
abundant biopolymer on the earth, lignin has great potential as
the GPE matrix for replacing the synthetic polymers.
9
Gong et al. first explored the lignin-based GPE to develop
truly green and environmental-friendly LIBs [165]. The membrane
shown in Fig. 7a was obtained by simply drying the suspension
of lignin in distilled water. With high liquid electrolyte upholding
(230 wt.%) properties, the lignin-based GPE demonstrated an ex-
cellent ionic conductivity of 3.73 mS cm−1 at room temperature.
More importantly, the lignin-based GPE was thermally stable up to
250 °C with a high lithium transference number of 0.85 owing to
the strong interactions between the massive phenol hydroxyl units
in lignin and anions in lithium salts [165]. Moreover, the lignin-
based GPE exhibited favorable compatibility with the lithium an-
ode and outstanding electrochemical stability up to 7.5 V. All these
remarkable properties endow lignin with application potential in
GPEs for LIBs. However, the mechanical property of the pure lignin
membrane is poor, which greatly limits the practical application of
many GPEs. To improve the mechanical properties, Liu et al. intro-
duced PVP/lignin composite membrane, which has enhanced me-
chanical rigidity in terms of Young’s modulus and better thermal
stability with a mass content of PVP (22 wt.%) [166]. As a powerful
viscidity macromolecule polymer, PVP is contributed to obtaining a
dense composite membrane with lignin under the incorporation of
γ -aminopropyltriethoxysilane (KH-550) to improve the compatibil-
ity (Fig. 7b). Consequently, the PVP/lignin composite GPE presented
a better mechanical strength and higher safety toward harsh de-
mands for high-performance LIBs with desired sustainability and
environmental protection. In addition, the Li-ion cells assembled
with PVP/lignin composite GPE demonstrated a good capacity re-
tention of 95.3% with a specific capacity of 135 mAh g-1 after 100
cycles at a current density of 0.2 C, which is superior to that of the
cell with commercial Celgard separators. Similarly, PVA/lignin com-
posite GPEs also showed improved mechanical properties [167].
Xiong et al. further extended the lignin GPE in lithium hybrid
aqueous batteries by using an aqueous solution as the electrolyte
instead of commonly-used, highly flammable organic solvents. The
rechargeable lithium aqueous batteries (ReLABs) are believed to
be the most attractive alternatives for highly safe, low-cost, and
environmentally friendly energy storage systems [168]. In a typical
ReLAB, fumed silica-based aqueous gel electrolyte is commonly
used but facing severe problem on the corrosion of zinc anode
due to the existence of ionized silanol groups (Si-O-) on the
surface of silica nanoparticles as a solid acid. In Xiong’s work, the
lignin molecules were grafted with cationic quaternary ammonium
groups to provide strong electrostatic interaction with fumed silica
(Fig. 7c). Since some of the acidic groups (Si-O-) on the surface
of fumed silica were covered by lignin molecules, the acidity of
fumed silica was weakened, which fundamentally suppressed the
10 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788

Fig. 7. (a) Digital images of lignin-based GPEs [165], (b) synthesis procedures of lignin-PVP GPEs and the corresponding digital images [166], and (c) chemical structures of
fumed-silica (FS) and the prepared lignin-FS composite [168]. Source: (a) [165], Copyright 2016. Reproduced with permission from Elsevier Inc.; (b) [166], Copyright 2017.
Reproduced with permission from Springer Nature; (c) [168], Copyright 2018. Reproduced with permission from Elsevier Inc.

corrosion of zinc anode. With the optimum coating concentration
of lignin molecules (5 wt.%), the cells exhibited excellent cycling
stability for 10 0 0 cycles with 82% capacity retention at 4 C.
3.1.3. Binders for lithium batteries
Polymer binders are another important component in batteries.
Currently, the most frequently used binder, PVDF, is not biodegrad-
able. This fluorinated polymer can easily deteriorate the cycling
performance of the batteries due to the formation of stable LiF
and double bonds (C=CF-) after reacting with lithium metal [169].
Therefore, lignin has been investigated as an alternative candidate
for a non-fluorinated and environmentally friendly binder.
Lu et al. explored the possibility of using lignin as the binder
material for both the cathode (LiFePO4 ) and anode (graphite), and
demonstrated relatively high specific capacity and good stability
[170]. Reversible capacities of 148 and 305 mAh g-1 could be
delivered at 0.1 C for the lignin-binded cathodes and anodes,
respectively. Noted that, the pretreatment of lignin prior to the
slurry preparation is critical to obtain good battery performance,
which removes the low-molecular-weight lignin molecules that
can be dissolved in electrolytes. Addition to the benefit of sus-
tainability, electrodes with the lignin binder showed improved
compatibility in high-voltage LIBs using LiNi0.5 Mn1.5 O4 as cathode
materials [171].
Generally, carbonate-based electrolytes are prone to oxidative
decomposition when the cathode voltage exceeds 4.3 V, which
generates alkyl free radicals and leads to polymerization of solvent
and formation of cathode/electrolyte interphase (CES) [172–177].
Therefore, biomass-based lignin with predominant phenolic groups
could serve as a free radical scavenger to suppress the electrolyte
decomposition and extend the battery lifespan (Fig. 8a) [171].
Compared to the cells using PVDF binder (capacity retention
46.2%), the cell with the lignin-based binder exhibited significantly
higher capacity retention of 94.1% (110.8 mAh g-1 ) after 10 0 0 cy-
cles, and the overall Coulombic efficiency was maintained at 99.5%.
High performance and durable silicon composite anodes were
developed in which the conventional binder and conductive addi-
tives were replaced by lignin as well [177]. As shown in Fig. 8b, Si
nanoparticles are uniformly coated with the heavily cross-linked
lignin that forming a 3D flexible framework surrounding the Si
nanoparticles. After studying the structural and electrochemical
performance of Si-lignin composites at different heat treatment
temperatures (Fig. 8c), Si-lignin composite carbonized at 600 °C
showed the balanced properties between high conductivity and
retaining polymer flexibility, leading to high initial discharge
capacity of 3086 mAh g-1 and retaining capacity of 2378 mAh g-1
after 100 cycles at a current density of 1 A g−1 . In conclusion,
the aforementioned advantages would rank lignin as a promising
binder for renewable and high-performance LIBs, which can not
only enhance batteries’ electrochemical performance but also
reduce the manufacturing cost.
3.1.4. Cathode additives for lithium batteries
As a renewable and low-cost material with abundant ac-
tive C=O functional groups, lignin has been studied in primary
(disposable) lithium batteries as cathode-active materials [51].
Bioextracted lignin was developed in low-cost primary lithium
batteries since the heterogeneous morphology of the lignin
particles greatly facilitated the diffusion of Li+ [178–180]. The
oxygen-containing groups were directly associated with the
specific capacity of Li/lignin cells, where the carbonyl groups
(C=O), hydroxly groups (-OH), and ether groups (C-O-C) in lignin
demonstrated strong electroactive redox properties with Li+
[178]. A maximum capacity of 600 mAh g-1 could be obtained
in practical Li/lignin cells. In addition, owing to the availability
of plentiful oxygen-containing functional groups in polymeric
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Fig. 8. (a) Diagram illustration of the free radical scavenging ability of lignin and PVDF [171], (b) schematic drawing of lignin-Si composite, and (c) cycling performances
of lignin-Si composites treated at 40 0, 50 0, 60 0, and 80 0 °C [177]. Source: (a) [171], Copyright 2019. Reproduced with permission from Royal Society of Chemistry; (b,c)
[177] Copyright 2016. Reproduced with permission from American Chemical Society.
backbones, lignin is also applied as a preferred precursor for
the fabrication of mesoporous carbons for use as conductive
additives in cathode materials. For instance, encapsulating sulfur
into conductive carbon materials has been demonstrated as an
effective method to improve the cycling stability of Li-S batteries
by improving the electrical conductivity of sulfur and limiting the
diffusion of polysulfides during cycling. Yu et al. synthesized the
sulfur-carbon composite using lignin-derived macro-/micro-porous
carbon [181]. The high specific surface area of 1211.6 m2 g−1 and
abundant oxygen-containing functional groups on the surface of
lignin-derived carbon framework functionalized for the chemical
adsorption of polysulfides. Consequently, with the optimum sulfur
loading (50 wt.%), a high reversible discharge capacity of 1241 mAh
g-1 was delivered initially at a current density of 0.5 C, and the
capacity retention was 64% after 100 cycles.
3.2. Lignin in sodium batteries
SIBs have been considered as a promising alternative for LIBs
because of the potentially low-cost and abundant sodium resources
[182–184]. However, the standard anode material (graphite) for
LIBs displays limited ability to store Na+ owing to the larger ionic
size of Na+ (55% larger than Li+ ) [182]. Therefore, the recent
development of SIBs is mainly focused on finding a suitable
anode material to host Na+ [185]. It is recently found that hard
carbons with hierarchical pore structures and enlarged interlayer
lattice distance are favored for Na+ storage and transport, and
biomass-derived hard carbon materials received much attention
due to the abundant pore structures and cost-efficiency [185–187].
11
As a promising biomass precursor for hard carbon, lignin-based
carbon anodes have been extensively studied for SIBs, and Table 3
summarizes the work on various lignin-based carbon anodes,
including the source of lignin materials, carbonization conditions,
and their electrochemical performance [143,188–198].
As shown in Table 3, most lignin-based hard carbon anodes
derived from biomass materials (rice rusk, pitch, oak leaves,
peat moss, etc.) or industrial wastes (Kraft black liquor, etc.) could
deliver satisfactory capacities (∼300 mAh g-1 ) and exhibit good cy-
cling stability at low current densities. The unique pore structures
of these carbonized lignin-based biomaterials make them promis-
ing candidates for use as the anodes of SIBs. Nitrogen doping can
further improve the cycling performance of lignin-based carbon
anodes. Du et al. introduced the N-doped lignin porous carbon
structure by adding SiO2 nanoparticles (100 nm) in the precursor
and etching after pyrolyzation in N2 (Fig. 9a) [196]. The obtained
N-doped carbon materials showed a honeycomb-like morphology
with uniform nanopores, resulting in a high rate capability due
to the low ion-diffusion resistance and the short distance of ionic
migration. Consequently, a high reversible capacity of 100 mAh
g-1 was achieved after 1100 cycles at a high current density of
1 A g-1 , and the corresponding capacity fade was only 8%.
Navarro-Suarez et al. investigated the temperature effect on the
synthesis of lignin-derived carbon anodes for SIBs [197]. As can
be seen in Fig. 9b, hard carbon with a large number of buried mi-
cropores was formed when carbonizing the lignin at above 700 °C,
while further increasing the carbonization temperature led to a
decrease in interlayer distance. At a low temperature of 400 °C,
the carbonization and activation process occurred simultaneously,
12 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788

Table 3
Overview of lignin-based anodes in sodium batteries [143,185–195].

Materials Source Carbonization Electrochemical performance Ref.

PVA/lignin carbon fibers Alkali lignin 600 °C-1 h (Ar) 122 mAh g−1 (350th cycle, 50 mA g−1 , 0.01–2.5 V) 143
Lignin (hard carbon) Rice husk 1600 °C-1 h (N2 ) 276 mAh g−1 (100th cycle, 30 mA g−1 , 0–2.0 V) 188
Lignin (amorphous carbon) Pitch and lignin 1400 °C-2 h (Ar) 254 mAh g−1 (150th cycle, 0.1 C, 0.01–2.0 V) 189
Condensed lignin Concentrated acid hydrolysis of lignin 1300 °C-6 h (N2 ) 112 mAh g−1 (500th cycle, 2500 mA g−1 , 0.005–2.5 V) 190
Lignin carbon nanosheet Compressed peat moss 1100 °C-1 h (Ar) 255 mAh g−1 (200th cycle, 100 mA g−1 , 0.1–2.0 V) 191
Lignin carbon membrane Oak leaves 1000 °C-1 h (Ar) 325 mAh g−1 (200th cycle, 20 mA g−1 , 0.1–2.2 V) 192
Lignin lamellar carbon Holly leaves (sophora japonica) 800 °C-2 h (Ar) 318 mAh g−1 (10th cycle, 20 mA g−1 , 0.01–3 V) 193
Lignin (hard carbon) Lignin and epoxy resin 1400 °C-1 h (Ar) 285 mAh g−1 (150th cycle, 0.1 C, 0–2.0 V) 194
Lignin (hard carbon) Pilot-scale delignification apparatus 1200 °C-6 h (N2 ) 392 mAh g−1 (100th cycle, 50 mA g−1 , 0.005–2.5 V) 195
N-doped lignin porous carbon Alkali lignin 700 °C-4 h (N2 ) 100 mAh g−1 (1100th cycle, 1000 mA g−1 , 0.01–2.0 V) 196
Lignin porous carbon Kraft black liquor 900 °C-2 h (Ar) 250 mAh g−1 (75th cycle, 0.06 C, 0.002–2.0 V) 197
PAN/lignin carbon fibers Hardwood lignosulfonate 250 °C-1 h (Air) 247 mAh g−1 (200th cycle, 100 mA g−1 , 0.01–2.7 V) 198
700 °C-0.5 h (N2 )

Fig. 9. (a) Schematic drawing of synthesis procedures of N-doped porous carbon anodes with lignin precursor [196], (b) illustration of development of the internal and
external porosities during the carbonization at different temperatures [197], and (c) schematic drawing of the Na+ storage mechanism in the lignin-derived hard carbon
[195]. Source: (a) [196], Copyright 2019. Reproduced with permission from Electrochemical Society; (b) [197], Copyright 2018; (c) [195], Copyright 2019. Reproduced with
permission from Elsevier Inc.

resulting in the increase of porosity distribution
mesopores) because of the natural gas evolution
sium precursor. Alvin et al. further established
between the carbonization temperature and Na+
of lignin-based anodes [195]. As summarized in
cycle discharge capacity increased from 333.52
(from micro- to g−1 when the carbonization temperature increased from 10 0 0 to
from the potas- 1200 °C. The reduction in surface area and micropore volume from
the relationship L-10 0 0 to L-120 0 indicated the micropore filling mechanism was
storage capacity not the dominant in Na+ storage for lignin-based anodes, while
Table 4, the 1st the enhanced storage capacity from L-10 0 0 to L-120 0 was mainly
to 392.27 mAh attributed to the improvement of graphitization degree (decrease
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788 13

Table 4
Structural properties and electrochemical performance of carbonized lignin samples at different carbonization temperatures.195 .

Sample Spacing d002 (nm) ID /IG Surface Area (m2 g−1 ) Micropore Volume (%) 1st Discharge Capacity (mAh g−1 ) ICE (%)

L-1000 0.383 1.87 124.9 76.6 333.52 61

L-1100 0.382 1.51 92.1 74.9 363.68 63
L-1200 0.376 0.85 54.9 72.6 392.27 65
L-1300 0.375 0.72 48.3 65.7 377.99 69
L-1400 0.374 0.56 29.5 58.8 349.19 71
L-1500 0.365 0.47 14.7 48.0 301.59 72

in ID /IG ratio), which provided more active sites between the

interlayer spacing of the graphitic regions for Na+ intercalation.
However, because of the large radius of Na+ , the further increment
of carbonization temperature (L130 0-L150 0) resulted in a huge
decrease in Na+ storage capacity due to the formation of desirable
graphite structure with a reduced interlayer spacing (d002 ). In addi-
tion, because of the severe collapse of micropores, the surface area
decreased at higher carbonization temperatures (L130 0-L150 0),
which was also not favored in Na+ intercalation. The reduction of
surface area could improve the initial Coulombic efficiency (ICE)
Fig. 10. Schematic image of hydroxyl and quinone redox reaction.
owing to the lower degree of SEI formation on the anode surface.
Therefore, an optimized carbonization temperature is critical for
lignin-based anode to achieve high Na+ storage capacity and
Coulombic efficiency. The graphitization degree and lattice spacing 60 wt.%, which has been considered as a promising candidate
are more important than the surface area for lignin-based anodes. for preparing porous carbon materials [203,205]. Moreover, each
As studied, a fine structure with microporosity demonstrated structural unit in lignin contains highly reactive hydroxyl groups
better cycling performance for lignin-based carbon anodes in SIBs. which can provide pseudocapacitance by reversibly conversion
Alvin et al. investigated the Na+ storage mechanism in hard carbon between hydroxyl and quinone, as shown in Fig. 10. Therefore,
in light of the physicochemical properties of the lignin-derived lignin has been tremendously studied as the carbon precursor and
hard carbon including graphitization degree, interlayer spacing, electrolyte additives for supercapacitors. Here we summarize the
micropore size distribution, and specific surface area [195]. By research and application progress of lignin-based electrode and
carefully tuning the carbonization conditions of lignin-based hard electrolyte materials for supercapacitors in recent years.
carbon materials and using various electrochemical analysis and
ex-situ experimental techniques, a clear mechanism of sodiation
4.1. Electrode materials for supercapacitors
process was presented with the relationship to carbon structures.
As illustrated in Fig. 9c, Na ions are adsorbed on surface defects
Structures and properties of lignin-based carbon electrodes
and edge sites at the initial sodiation process (1–0.2 V), followed
can be manipulated by tuning preparation processes [206–209].
with micropore filling process in the discharge sloping region
Depending on the structures and processing methods, we classify
between 0.2 and 0.1 V. Then, Na+ ions are intercalated into the
the lignin-based porous carbons into three categories, which
graphitic layers in plateau region below 0.1 V. At the final cutoff
are activated carbon, templated carbon, and composite carbon,
potential (0.05 V), Na+ ions are further adsorbed and form clusters
respectively. More details regarding these three types of carbon
in micropores due to relatively high concentration in micropores.
electrodes are presented in this section.
Therefore, the physicochemical properties of hard carbon mate-
rials directly control the behavior of Na+ storage. Similar to LIBs,
4.1.1. Activated carbon electrodes
fiber-shaped lignin-based hard carbon materials show improved
Activated carbon, as a common electrode for supercapacitors,
rate-capabilities [198,199]. Electrospun PAN/lignin (1:1 by weight)
is generally fabricated by carbonizing carbon precursors followed
carbon nanofibers were applied in SIBs by Jin et al. [198]. At a
by activation processes. Lignin-derived activated carbon can be
high current density of 1 A g−1 , the cell with PAN/lignin anode
easily prepared by carbonizing and activating lignin precursors
maintained a reversible capacity of 80 mAh g−1 .
[210]. During the carbonization process, lignin is transformed
into lignin-based char by pyrolysis at a high temperature. Then,
4. Applications in supercapacitors lignin-based char is passed through an activation process to
form porous activated carbon materials. In general, the activa-
Supercapacitors, also known as electrochemical capacitors or tion process of lignin is usually divided into physical activation
ultracapacitors, have been widely used in electric/hybrid vehicles and chemical activation. Physical activation is the activation of
and other devices due to their high power density, long cycle life lignin-based char at high temperatures by CO2 or steam. While
(>105 cycle) and broad working temperature range of −40∼80 °C chemical activation is that lignin-based char mix with chemical
[200,201]. The storage of energy for supercapacitors is primarily activation agents (such as KOH, ZnCl2 , K2 CO3 , etc.) followed by
achieved by electrostatic adsorption of ions onto the electrode- heating the mixture under an inert atmosphere [211]. It should
electrolyte interface or by a faradaic reaction of active materials be noted that both carbonization and activation processes would
[202]. influence the structures of activated carbon materials dramatically.
Among various electrode materials for supercapacitors, porous Zhao et al. used lignin-rich black liquor as a carbon precursor
carbonaceous materials have received significant attention not only and KOH as an activator to explore the effects of carbonization
because of their high surface areas but also due to their superior temperature, activation temperature and activation time on the
electrical conductivity and high chemical stability [203,204]. Lignin structures and properties of lignin-derived carbon electrodes [212].
is an abundant aromatic polymer with a carbon content of about In their study, the carbonization temperature was set between 500
14 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Table 5
The basic properties of three carbon electrodes. LAC-Z, LAC-K, and LAC-K2 repre-
sent lignin-based carbon activated by ZnCl2 , KOH, K2 CO3 ; SBET : BET surface area;
Vtot : total pore volume; De : average pore diameter; Capacitance: capacitance of the
electrode tested at a current density of 40 mA g−1 .
Materials SBET (m2 g−1 ) Vtot (m3 g−1 ) De (nm) Capacitance (F g−1 )
LAC-Z 866 0.47 2.91 142.09
LAC-K 1191 0.82 2.75 251.04
LAC-K2 1585 0.79 1.99 263.46
and 900 °C. More components of lignin were thermally degraded
with the increment of carbonization temperature, which led to
a decline in the yield. Meanwhile, the specific surface area of
the carbon electrode also decreased, resulting in degradation
of the capacitance of the prepared electrodes. The increment of
activation temperature and extension of activation time would
enhance the specific surface area of the lignin-based activated
carbon. However, the high specific surface area of an electrode
does not always lead to high specific capacitance. Moreover, they
found that the material with an average pore size of 1.92 nm could
have the highest capacitance. Excessive activation could lead to
too many sub-nano pores, which are unfavorable for electrolyte
ions to enter. Eventually, the electrode carbonized at 600 °C with
a 2 h activation at the same temperature possessed the highest
specific capacitance of 41.4 F g−1 at 10 mA g−1 .
Currently, compared with physical activation, the chemical
activation process is the main approach for preparation of lignin-
derived electrodes because the temperature for chemical activation
is low and a high carbon yield can be achieved [212]. The activator
is a critical factor which significantly affects the specific surface
area and pore structure of the lignin carbon electrode in this
process. Therefore, it is important to select a suitable process
condition and activator for fabricating lignin-based activated
carbon electrodes. Fang et al. explored how the amount of KOH
activator would influence lignin-based electrodes [213]. Elevating
the amount of KOH would increase the pore volume of carbon
materials, but excessive KOH would cause the mergence of orig-
inal pores. The best performance of a carbon electrode could be
achieved with an optimum weight ratio (KOH/C) of 3. A specific
capacitance of 267.8 F g−1 at 50 mA g−1 and high retention of
83.3% even after 20 0 0 cycles could be obtained. In addition to the
amount of activator, the type of activator is also of concern. Gen-
erally, most activators have catalytic effects on dehydration of the
lignin matrix, which result in forming porous structures of lignin.
However, there are still differences in the activation mechanisms
of various activators, which contribute to different structures
and properties. Wu and his co-workers selected three different
activators (ZnCl2 , KOH, K2 CO3 ) to study the effect of activators on
lignin-based carbon materials [211]. The basic properties of carbon
electrodes activated by three different activators are summarized
in Table 5. The specific surface area of lignin-based electrode acti-
vated by ZnCl2 was the smallest since ZnCl2 only played a role of
catalyzing dehydroxylation and dehydration during the activation
process, while KOH and K2 CO3 both acted as dehydrating and
oxidant agents. K2 CO3 existed in the extra process of CO2 physical
activation compared to KOH because K2 CO3 would decompose to
produce CO2 during the activation process. Therefore, lignin elec-
trode obtained by K2 CO3 activation reached optimal performance
with a specific surface area of 1158 m2 g−1 and a capacitance of
263.46 F g−1 at 40 mA g−1 .
Since lignin exists in most plants, many researchers use
lignin-rich plants to synthesize activated carbon electrodes for
supercapacitors. The structures of these activated carbon ma-
terials highly depend on the structure and composition of the
precursor plants. Recently, Senthilkumar et al. synthesized the
activated carbon material from tamarind fruit shell using KOH as
the activator [214]. A high specific surface area of 1042.31 m2 g−1
with a pore volume of 0.61 m3 g−1 was achieved. They used this
high-surface-area electrode with PVA (polyvinyl alcohol)/H2 SO4
gel polymer electrolyte to fabricate a solid-state supercapacitor
which had no leakage and corrosion problems and possessed
better cycling stability. The obtained cell exhibited high specific
capacitance and energy density of 412 F g−1 and 9.166 Wh kg−1 ,
respectively, at a current density of 1.56 A g−1 . When sodium
molybdate (Na2 MoO4 ) was introduced into PVA/H2 SO4 electrolyte
for the redox-active reaction, the specific capacitance and energy
density of the supercapacitor increased dramatically, reaching
648 F g−1 and 14.4 Wh kg−1 , respectively.
Due to the diversity of lignin-rich plants, the chemical compo-
sition of the electrode obtained by pyrolysis is also different. For
example, alginic acid, which is a fibrous material located in the
cell wall of seaweeds, has a large amount of oxygen after pyrolysis,
making it easier for the electrode to adsorb electrolyte ions [215].
Pintor’s group utilized turbinate seaweeds as a carbon source
to obtain a carbon electrode by pyrolysis at 800 °C [216]. The
electrode with some oxygen-containing functional groups had a
specific surface area of 812 m2 g−1 . The symmetric supercapacitor
with the electrode could deliver a specific capacitance of 74.5 F
g−1 in 1 M tetraethylammonium tetrafluoroborate (TEABF4 ) not
only due to the increase of active sites of the electrode but also
because of the pseudocapacitance contributed by those oxygen-
containing functional groups. Other biomass resources, such as
sisal fiber [217], eucalyptus leaves [218], cornstalk [219], bamboo
[220], coconut leaves [221] and mung bean husks [222], have
been performed as activated carbon electrodes for supercapacitors
as well. This not only resolves these bio-wastes effectively but
also provides renewable, inexpensive precursors for commer-
cial activated carbon electrodes, further enhancing the practical
applications of supercapacitors.
In hierarchical porous carbon electrodes, the macroporous core
provides high buffer volume for electrolyte ions, the mesoporous
channels are beneficial to the fast ion transportation, and micro-
pores can further enhance the ion-accessible surface area for the
construction of electric double layer, which helps them obtain
excellent electrochemical performance [203]. Lignin has a loose
structure which is good for forming porous structures during
pyrolysis. Therefore, many efforts have been made on utilizing
lignin as a precursor to prepare hierarchical porous activated car-
bon electrodes by appropriate pyrolysis and activation processes.
Guo et al. reported a lignin-based 3D hierarchical porous carbon
prepared via carbonization and activation processes [223]. As
shown in Fig. 11a, lignin-derived carbon materials with abundant
interconnected large pores were prepared by hydrothermal car-
bonization, and then 3D porous carbon could be achieved through
the subsequent KOH activation. The porous carbon electrode ex-
hibited a high specific surface area of 1660 m2 g−1 , good electrical
conductivity of 5.4 S cm−1 and multiple pore sizes (shown in
Fig. 11b), which resulted in a high specific capacitance of 420 F
g−1 at 0.1 A g−1 , good rate performance (67% retention when
the current density increased from 0.1 A g−1 to 100 A g−1 ), and
excellent cycle stability (99% capacitance retention after 10,0 0 0
cycles at 5 A g−1 ) in 6 M KOH electrolyte. Symmetric supercapac-
itor assembled by using this carbon electrode had an outstanding
energy density of 46.8 Wh kg−1 which could maintain an energy
density of 22.9 Wh kg−1 at an ultrahigh power density of 25,400 W
kg−1 in ionic liquid systems.
In the preparation of hierarchical porous electrodes, suitable
treatments create oxygen-containing groups which could fur-
ther enhance their electrochemical performance as discussed
previously. Zhang et al. reported a kind of hierarchical porous
carbon (LHPC) with 12.27 at.% oxygen-containing groups from
lignin in the existence of KOH [224]. The material delivered a
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788 15

Fig. 11. (a) Schematic illustration of the preparation of lignin-based hierarchical porous carbon materials; (b) SEM images of hierarchical porous carbons [223]. Copyright
2017. Reproduced with permission from the Royal Society of Chemistry.

Fig. 12. (a) O 1 s spectrum of the lignin-derived hierarchical porous carbon; (b) specific capacitance of lignin-derived hierarchical porous carbon and solely carbonized lignin
in 1 M H2 SO4 aqueous solution with various scanning rates [224]. Copyright 2015. Reproduced with permission from the John Wiley and Sons Inc.

much higher specific capacitance of 168.2 F g−1 compared with
the solely carbonized lignin (LC, 25.7 F g−1 ) at 10 mV s−1 in 1 M
H2 SO4 due to the high specific surface area and the pseudocapac-
itance provided by a redox reaction of oxygen-containing groups
(shown in Fig. 12a). As can be seen in Fig. 12b, this porous carbon
electrode (LHPC) had excellent rate performance (a maintained
capacitance of 123.5 F g−1 at 10 A g−1 ) and cycling stability
(capacitance retention of 97.3% after 50 0 0 cycles). Lignin-based
hierarchical porous carbon electrodes of many other structures
including hollow spherical carbon and interconnected hierarchical
porous carbon are also reported [225,226].
4.1.2. Templated carbon electrodes
The templating method has been considered as an effective ap-
proach for designing the pore size, porosity, and other structures of
carbon materials to enhance their electrochemical properties [227].
A large amount of oxygen-containing functional groups in lignin
and the soft template can self-assemble into precursors through a
hydrogen bond interaction, and finally, form mesoporous materials
by carbonization. Moreover, a hard template can also be well
dispersed in the lignin matrix. Therefore, lignin-derived templated
carbon electrodes can be simply obtained by uniformly filling tem-
plates into the lignin matrix followed by carbonizing and removing
the templates through chemical or physical approaches. After
removing templates, templated electrodes exhibit uniform meso-
pores which can provide fast-moving channels for electrolyte ions,
endowing excellent rate performance for supercapacitors. Saha et
al. synthesized mesoporous carbon electrodes with a surface area
of 1148 m2 g−1 and mesoporosity of nearly 66% from lignin by us-
ing Pluronic F127 as a pore-forming agent [228]. The synthesized
mesoporous carbon electrode activated by CO2 exhibited a capac-
itance of 102.3 F g−1 and excellent rate performance in 6 M KOH.
Multiple templates have also been utilized by others to prepare
lignin template carbon electrodes since the hierarchical porous
structure can be designed by selecting different templates, which
may realize both high energy density and fast ion transfer prop-
erties of obtained carbon materials. Li and co-workers synthesized
a large-scale hierarchical porous carbon monolith using lignin as a
carbon source via a dual-template approach, as shown in Fig. 13a
[229]. Briefly, the carbon monolith was obtained by carbonizing
the mixture of P123, lignin and mesoporous silica (KIT-6) followed
by removing the templates. The symmetric supercapacitor with
16 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788

Fig. 13. (a) Schematic illustration of the synthesis of hierarchical porous carbon monolith from lignin [229]; (b) Lignin structure model and schematic illustration of the
preparation process of lignin-derived carbon through the freeze-casting method [230]. Sources: (a) [229], Copyright 2016. Reproduced with permission from Elsevier Ltd; (b)
[230], Copyright 2017. Reproduced with permission from the Royal Society of Chemistry.

Fig. 14. (a) Micropore and mesopore size distribution of the lignin-based hierarchical porous carbon; (b) rate performance of the lignin-based carbon electrodes [231].
Copyright 2018. Reproduced with permission from the John Wiley and Sons Inc.

this carbon electrode had an outstanding areal capacity of 3.0 F
cm−2 and a volume capacity of 97.1 F cm−3 at a current density of
1.4 mA cm−2 even without using a binder and conductive additive.
In addition, the supercapacitor also achieved a high areal energy
density of 0.16 mWh cm−2 at 1.75 mW cm−2 and excellent cycling
performance of ∼95% retention after 10,0 0 0 cycles.
However, most of the templates are too costly to be operated
on a large scale. Therefore, selecting low-cost and convenient
materials as templates is extremely important to minimize the
total cost of the resultant supercapacitors. Liu et al. performed ice
crystals as a layered template for the synthesis of 2D lignin sheet
using freeze-drying liquid-nitrogen-quenched lignin dispersion, as
shown in Fig. 13b [230]. The carbonized lignin sheet with a surface
area of 857.4 m2 g−1 and a high electrical conductivity of 2.5 S
cm−1 could deliver a specific capacitance of 281 F g−1 at 1 A g−1 .
For lignin, some templates not only create pores but play other
roles (i.e., a catalyst for graphitization [220], pH regulator and acti-
vator [231], etc.). Zhang’s group reported lignin-based hierarchical
porous carbon microspheres (HPCM) by inverse phase dehydration
and further K2 CO3 activation, which played three important roles
in synthesizing microporous carbon microspheres [231]. Firstly,
K2 CO3 acted as a pH regulator to make lignin better dissolved in
water. Secondly, K2 CO3 crystals became the hard template to form
uniform mesopores in the carbon spheres. Thirdly, K2 CO3 , acting
as an activating agent, promoted the formation of a large number
of micropores with a size around 4 nm (Fig. 14a), which served
as channels for connecting mesopores to reduce the movement
distance of electrolyte ions. The performance of the electrode
(HPCM-0.75) was the best when the mass ratio of K2 CO3 to
lignin was 0.75. Due to the structure design of hierarchical porous
electrodes, the supercapacitor assembled by HPCM-0.75 achieved
a high capacitance of 140 F g−1 and retention of 70%, when the
current density increased from 0.05 A g−1 to 10 A g−1 , as shown in
Fig. 14b. Even though large-scale applications of template carbons
are limited due to the complexity of the process and expensive
templates, lignin-based template carbon is very promising for
preparation through selecting proper low-cost templates [227,232].
4.1.3. Composite electrodes
Pure lignin-derived materials have been performed as electric
double layer electrodes, whose electrochemical performance is
mainly affected by their specific surface areas and pore structures.
Besides that, some materials with pseudo-capacitive properties
(such as metal oxides, heteroatoms, etc.) or high-performance
carbon materials (such as graphene, carbon nanotubes, etc.)
have been introduced into lignin-derived electrodes to fabricate
composite electrodes with improved performance [233–237].
Inspired from recent research [238] which demonstrated that
introducing nitrogen into activated carbon could induce additional
pseudo-capacitance via reversible redox reactions and improve the
wettability between the electrodes and electrolytes, Jurewicz et al.
employed a lignin-containing coconut shell as a carbon source and
melamine as a nitrogen source [239]. The prepared electrode could
have a high nitrogen content of up to 5.9 at.% with a surface area
of 30 0 0 m2 g−1 and outstanding total pore volume of 2 cm3 g−1 ,
respectively. The cell with such electrodes owning excellent struc-
tural properties and abundant nitrogen and oxygen atoms achieved
high capacitance of 368 F g−1 at a current density of 0.2 A g−1 and
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Fig. 15. (a) Elemental mapping and (b) N2 sorption-desorption isotherms of the lignin-based composite electrode [240]. Copyright 2016. Reproduced with permission from
Elsevier Ltd.
low leakage current in the alkaline solution. Urea-modified lignin-
derived carbon electrodes were obtained by Wang and co-workers
to obtain a uniform distribution of nitrogen (Fig. 15a) and a large
number of mesopores (Fig. 15b) [240]. The symmetric supercapac-
itor fabricated by the electrodes exhibited specific capacitances of
273 F g−1 and 306 F g−1 at 0.1 A g−1 in 6 M KOH solution and
KOH-PVA gel electrolyte, respectively. In addition to the above-
mentioned natural nitrogen-containing materials, PPy [241] and
nitrogen-containing organic salts [242] are also effective nitrogen
sources. The addition of nitrogen-rich materials not only introduce
nitrogen into the electrodes but also help control the structure of
the electrodes. Through controlling the conditions of synthesizing
aniline and carbonization temperatures, N-doped rod-shaped
porous lignin-based carbon was fabricated by Wang’s group [243].
This material had a specific capacitance of 336 F g−1 and a tiny
resistance of 0.9  in a 6 M KOH solution since the N-doped ma-
terial had a large specific surface area, providing more active sites
to improve the wettability between the electrode and electrolyte.
N-doping has been demonstrated as an effective way to im-
prove the capacitance of electrodes, but the basic properties of
lignin may change when introducing nitrogen-rich materials which
can interact with lignin. This change is beneficial to the molding
process of lignin-derived materials. Yang et al. produced the N-
doped carbon fiber electrode by pyrolysis of plant protein−lignin
electrospun fibers [244]. Due to the low molecular weight and low
viscosity of lignin solution, it was easier to create "beading" during
electrospinning, while the addition of protein was able to promote
the lignin to form better electrospun fibers and provide nitrogen
source. The prepared electrode possessed a high capacitance of
410 F g−1 at 1 A g−1 in 6 M KOH with a 95% capacitance retention
after 30 0 0 cycles. In addition to simple physical interactions,
highly reactive hydroxyl groups of lignin can react with some
nitrogen-containing functional groups of nitrogen-rich materials.
These nitrogen-doped materials, as nitrogen sources and cross-
linking agents, not only provide nitrogen contents but also regulate
the structure of lignin by a suitable crosslinking process. Zhang
et al. fabricated a 3D nitrogen-doped hierarchical porous carbon
through pyrolysis and activation of crosslinked carbon precursor
formed by crosslinking lignin with 1.6-hexanediamine [237]. The
N-doped hierarchical electrode obtained a large specific surface
area of 1867.4 m2 g−1 and a nitrogen content of 3.6 wt.% with a
structure that contained a large amount of micropores, favorable
mesopores, and interconnected macropores. Benefiting from this
17
unique structure, a high specific capacitance of 370 F g−1 at 0.5 A
g−1 and excellent capacitance retention of ∼95.1% retention after
30 0 0 cycles could be achieved.
Although transition metal oxides can provide high capacitance
through redox reactions, they generally have low electrical con-
ductivity, poor cycle stability, low rate performance, and high cost,
which limit their applications for high-performance supercapaci-
tors. An effective method is to incorporate transition metal oxides
with nanostructures into the conductive matrix. The lignin-based
carbon material is such an excellent conductive matrix with a
low cost for this purpose. Chen et al. reported a liquid-crystalline
phase-templating approach to obtain NiO-containing mesoporous
carbon materials [245]. Fig. 16a shows the process of preparing
NiO/lignin composite electrode (G-NiO/C) by in-situ carbonization
of nickel salt and lignin crosslinked with glutaraldehyde. As shown
in Fig. 16b and c, the NiO/lignin composite (G-NiO/C) exhibited
a high specific surface area of 802 m2 g−1 with a uniform hole
size of ∼3.7 nm and 70.6 wt.% metal oxide contents, which led to
an outstanding specific capacitance of 880.2 F g−1 at 1 A g−1 and
good rate performance (retention of 90.9% when the current den-
sity is from 1 A g−1 to 10 A g−1 ). Additionally, Xu and co-workers
prepared Cu-doped hierarchical porous carbon aerogels materials
by pyrolysis and CO2 activation of Cu-doped lignin-based aerogels
[246]. The results showed that the incorporation of Cu played an
important role in improving the performance of the electrode. Cu
could produce a redox reaction in KOH solution to provide faradic
pseudocapacitance, which delivered a high specific capacitance of
285.97 F g−1 at 0.5 A g−1 . The redox reaction could be expressed
using the following Eqs. (1), (2):
Cu(0 ) + 2OH− = Cu(OH )2 + 2e− (1)
Cu(OH )2 + OH− = CuOOH + H2 O + e− (2)
In addition to the abovementioned composite electrodes, some
other transition metal oxide modified lignin-based carbon mate-
rials, such as iron oxide decorated lignin-based carbon nanofibers
[247] and hollow carbon nanofibers [234], NiCo2 O4 modified
PAN/lignin-based carbon nanofiber [248] have been studied,
which all have shown better electrochemical performance than
their unmodified counterparts. For example, Yu et al. fabricated
lignin-based hollow carbon nanofibers decorated by iron oxide
using poly(styrene-co-acrylonitrile) solution as the core, acetic
acid lignin as the shell and iron (III) acetylacetonate as the iron
18 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
Fig. 16. (a) Schematic illustration of preparing the NiO/lignin composite, (b) N2 adsorption-desorption isotherms, and (c) pore size distribution curves of NiO/lignin composite
materials [245]. Copyright 2013. Reproduced with permission from the Royal Society of Chemistry.
oxide-precursor additive in the shell [234]. The obtained iron
oxide/hollow carbon nanofiber composite exhibited a specific
capacitance of 121 F g−1 at 0.5 A g−1 , which was 2.18 times that
of unmodified hollow carbon nanofibers.
As mentioned previously, lignin is rich in phenol groups which
can store energy through a reversible faradaic redox reaction.
However, the insulating nature of lignin hinders the utilization
of these functional redox groups. Similar to the strategy of metal
oxides/carbon composite electrodes, some scholars have tried to
prepare composite electrodes with lignin and conductive polymers.
The conductive polymers can transport charge to lignin where the
charge could be stored by a reversible redox reaction of the phenol
groups. Meanwhile, lignin sulfonates contained sulfonate groups,
which play a similar role to the sulfonate groups in PSS and could
improve the electrical conductivity of poly(3,4-ethylene dioxythio-
phene) (PEDOT) [249]. Ajjan et al. synthesized PEDOT/lignin com-
posite electrodes by using PEDOT as a conductive network [249].
Due to the contribution of pseudo-capacitance, the PEDOT/lignin
composite electrode had a capacity of 170.4 F g−1 which was twice
that of the PEDOT electrode (80.4 F g−1 ). Later on, Navarro-Suarez
et al. fabricated full-cell supercapacitors by using PEDOT/lignin as
the positive electrode and reduced graphite oxide as the negative
electrode to explore the application of electrode of PEDOT/lignin
in the device [250]. The asymmetric supercapacitor had a capac-
itance of 34.6 F g−1 at 0.1 A g−1 . However, the supercapacitor
maintained 52.2% of its initial capacitance after 10 0 0 cycles,
which was explained by the consumption of quinone groups.
Then they prepared a composite electrode with PEDOT/lignin and
reduced graphite oxide. Since the addition of reduced graphite
oxide retarded the oxidation of quinone groups and improved the
electrical conductivity of the electrode, the symmetric superca-
pacitor assembled by this electrode had a higher capacitance of
36 F g−1 at 0.1 A g−1 and superior cyclability (maintain 79% of its
capacitance after 10 0 0 cycles). Moreover, the composite electrode
of lignin/conductive polymer could increase the capacitance by
introducing a third component which can provide more pseudo-
capacitance as studied by Ajjan’s group [251]. They prepared a
trihybrid electrode composed of poly(aminoanthraquinone) (PAAQ),
lignin, and PEDOT, which had an excellent specific capacitance of
418 F g−1 at a current density of 1 A g−1 .
Graphene and carbon nanotubes are excellent carbon materials
for energy storage systems because of their high electrical conduc-
tivity, large specific surface area, and excellent chemical stability.
However, it is extremely difficult to realize such high capacitance
for the reason that single-layer graphene and carbon nanotube
are prone to restack with each other via strong Van der Waals
interactions [252]. Lignin consists of phenylpropanoid subunits in
3D spatial structure, which helps prevent the irreversible agglom-
erates of graphene and carbon nanotubes by the π –π interaction
[236]. Therefore, the combination of lignin with graphene and car-
bon nanotubes is an effective strategy to improve the performance
of lignin-based electrodes. Ye et al. utilized lignin as the reductant
and morphology directing agent to obtain lignin/RGO composite
aerogel electrode through hydrothermal carbonization [236]. The
prepared lignin/RGO composite electrode had a high surface area
of 1804 m2 g−1 and exhibited a good rate capability with a
specific capacitance of 190 F g−1 at 0.5 A g−1 and 133.9 F g−1 at
10 A g−1 . Peng et al. fabricated a flexible solid supercapacitor by
 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788
using Lignin/SWCNTHNO3 gel as the electrode and cellulose/Li2 SO4
gel as the electrolyte [235]. The Lignin/SWCNTHNO3 gel electrode
exhibited a 3D network structure due to hydrogen and π –π in-
teraction between lignin and SWCNT. Moreover, the high electrical
conductivity and capacitance of SWCNT and the electrochemical
activity of lignin equipped the electrode with superior electro-
chemical performance. The assembled supercapacitor achieved a
high specific capacitance of 292 F g−1 at 0.5 A g−1 , excellent rate
capability, and outstanding energy density of 17.1 Wh kg−1 with a
power density of 324 W kg−1 .
4.2. Electrolyte materials for supercapacitors
Few studies regarding the application of lignin as electrolytes
for supercapacitors have been reported. Currently, lignin is mainly
studied as an additive in electrolytes. Milczarek et al. found that
lignosulfonate could be adsorbed on the surface of the carbon
electrode, and the lignosulfonate exhibited redox characteristics
after the initial redox reaction [253].
Meanwhile, the lignosulfonate could promote the movement of
electrolyte ions due to the presence of a sulfonic acid group. Lota
et al. added lignosulfonates as an additive to the H2 SO4 electrolyte
[254]. The addition of lignosulfonates increased the specific capac-
itance by 33%, which was resulted from the redox reaction. As an
electrolyte additive, lignin can effectively increase the capacitance
of the supercapacitor through the faradaic reaction. However, the
solubility of lignin in water limits the content of phenol groups
contributed by pseudocapacitors since it has been demonstrated
that lignosulfonates, which could be adsorbed on various carbon
electrodes, can form a redox active biofilm, resulting in an increase
in the pseudocapacitance [254–256]. More work regarding how to
increase the contents of pseudocapacitors through the addition of
lignin should be further explored.
5. Conclusions and perspectives
We have thoroughly reviewed and discussed the benefits, the
nature and production, and the recent progress in lignin-derived
materials for advanced rechargeable batteries and supercapacitors.
The renewable bioresource, lignin, is considered as one of the
most promising candidates for high-performance energy storage
system due to its low cost and environmental-friendly nature. Un-
fortunately, the practical application of lignin-derived high-value
materials is still greatly limited owing to some obstacles and
challenges.
Firstly, applications in the area of lignin-based rechargeable
batteries and supercapacitors will significantly improve complete
high-value utilization of biomass, which can realize seamless joint
to the biorefinery. So far, only limited lignin sources (mostly alkali
lignin, lignosulfonate, and organosolv lignin) have been investi-
gated in these areas. Therefore, it is crucial to research intensively
on lignin products of various plant types in different biorefinery
processes, especially for energy storage applications.
Secondly, lignin is mainly utilized as anode materials in LIBs
and SIBs. As a promising hard carbon precursor derived from
biomass, lignin-based anodes exhibit high specific capacity and
good cycling stability. Because of the intercalation mechanism, the
storage capacities of lignin-based anodes by controlling the surface
area, morphology, and crystallinity of the lignin derived materials.
However, the high surface area of lignin derived material resulted
in a low initial Coulombic efficiency due to the closed micropores
in the hard carbon matrix. Therefore, optimum carbonization con-
ditions with high electrical conductivity and limited surface area
are favored in providing high storage capacity and high Coulombic
efficiency. Additionally, the accessible and low-cost prelithiation
approach can also be a practicable technique to compensate for
19
the initial irreversible capacity. Fibrous-shaped carbon anodes
are favored toward high power and high-energy-density devices.
However, the fabrication cost of lignin-based carbon nanofibers
is high due to the addition of high content (>50 wt.%) of other
synthetic polymers. High-performance biomass-derived carbon
anodes with industrial-capable manufacturing process are required
to enable the further application of lignin in large-scale produc-
tion. Additionally, the rate capability of lignin-based anodes needs
to be further improved to achieve a remarkable breakthrough
in LIBs and SIBs. On the other hand, composite anodes with
alloying materials can provide even higher capacity but poor cycle
life. Therefore, advanced and sophisticated carbon structures are
mostly required to overcome the huge volume expansion during
the lithiation process. An inexpensive and effective method for the
mass production of these composite carbon anodes is necessary
to realize the true benefits of biomass materials and industrial
wastes. As a non-fluorinated and environmentally friendly binder,
lignin displays a great applied potential as binders and polymer
electrolytes. While the broad molecular weight distribution and
low mechanical strength of lignin remain the major challenges for
use in recharge batteries. Efficient pretreatments to remove low-
molecular-weight lignin molecules are required to be developed to
improve the viscosity of lignin-based binder. In addition, structural
modification of lignin with synthetic polymers (e.g., PVA, PVP, etc.)
or inorganic particles (e.g., SiO2 , TiO2 , etc.) can efficiently improve
the mechanical strength of composite lignin membrane, which is
critical for its practical application as a robust matrix for polymer
electrolytes [166,168].
Thirdly, the plentiful oxygen atoms in lignin are beneficial
for increasing electrolyte ions adsorption and producing redox
reactions for supercapacitors. Nevertheless, lots of oxygen atoms
in lignin would be lost during the pyrolysis at high temperatures.
Therefore, it is important to develop optimum carbonization and
activation processes which can provide lignin derived electrodes
with high degree of carbonization and appropriate amount of
oxygen atoms. Appropriate amount of oxygen atoms can not only
enhance the compatibility between the lignin derived materials
and other functional additives, but also increase electrolyte ion ad-
sorption and produce redox reactions for supercapacitors, making
lignin a useful material for preparing composite electrodes with
high performance [254–256]. Though there are several reports
about lignin being used as redox additives for electrolytes, its
limited performance contribution makes this approach be im-
practical in a short term unless if its solubility in water could be
tremendously improved.
Overall, the progress achieved during the past decades has
been significant, even though there are still many challenges to
overcome before realizing the commercial application of lignin in
the energy storage field. Major advances have been made in both
enhancing the performance and understanding the mechanisms
of using lignin-derived materials. We believe that further studies
by the research community will lead to more exciting results and
eventually practical high-value lignin-derived materials.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
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24 J. Zhu, C. Yan and X. Zhang et al. / Progress in Energy and Combustion Science 76 (2020) 100788

Chaoyi Yan earned a B.S. in Material Science and Engi-

[235] Peng Z, Zou Y, Xu S, Zhong W, Yang W. High-Performance biomass-based
neering in 2014 from Shanghai University of Engineering
flexible solid-state supercapacitor constructed of pressure-sensi-
Science, and a M.S. in Material Science and Engineering
tive lignin-based and cellulose hydrogels. ACS Appl Mater Interfaces
in 2016 from the University of Maryland. He is currently
2018;10:22190–200.
completing his Ph.D. in Fiber and Polymer Science in the
[236] Ye W, Li X, Luo J, Wang X, Sun R. Lignin as a green reductant and morphol-
Wilson College of Textiles at North Carolina State Univer-
ogy directing agent in the fabrication of 3D graphene-based composites for
sity. His research work focuses on synthesis and applica-
high-performance supercapacitors. Ind Crop Prod 2017;109:410–19.
tion of composite solid electrolytes in lithium batteries.
[237] Zhang W, Yu C, Chang L, Zhong W, Yang W. Three-dimensional nitrogen–
doped hierarchical porous carbon derived from cross-linked lignin derivatives
for high performance supercapacitors. Electrochim Acta 2018;282:642–52.
[238] Si W, Zhou J, Zhang S, Li S, Xing W, Zhuo S. Tunable N-doped or dual N, S–
doped activated hydrothermal carbons derived from human hair and glucose
for supercapacitor applications. Electrochim Acta 2013;107:397–405.
[239] Jurewicz K, Babel K. Efficient capacitor materials from active carbons based
on coconut shell/melamine precursors. Energ Fuel 2010;24:3429–35.
[240] Wang K, Xu M, Gu Y, Gu Z, Fan QH. Symmetric supercapacitors using ure-
a-modified lignin derived N-doped porous carbon as electrode materials in Xin Zhang received her B.E. degree in Light Indus-
liquid and solid electrolytes. J Power Sources 2016;332:180–6. try Engineering from Shaanxi University of Science and
[241] Bober P, Gavrilov N, Kovalcik A, Micusik M, Unterweger C, Pasti IA, Technology in 2013, and she is now a Ph.D. candidate
Sedenkova I, Acharya U, Pfleger J, Filippov SK, Kulcek J, Omastova M, in the College of Life Science and Technology at Bei-
Breitenbach S, Ciric-Marjanovic G, Stejskal J. Electrochemical properties of jing University of Chemical Technology. Currently, she
lignin/polypyrrole composites and their carbonized analogues. Mater Chem is working on biomass structural analysis and efficient
Phys 2018;213:352–61. lignin product extraction based on steam explosion pre-
[242] Jiang T, Sun Q, Xu W, Zhao G, Shi J. Preparation of nitrogen doped treatment by using non-woody biomass resources. Her
lignin derived porous carbon for supercapacitors. Int J Electrochem Sci research interests are mainly focusing on biomass pre-
2018;13:11480–90. treatment and conversion, lignin extraction and character-
[243] Wang K, Cao Y, Wang X, Castro MA, Luo B, Gu Z, Liu J, Hoefelmeyer JD, Fan Q. ization, and value-added application of nano-structured
Rod-shape porous carbon derived from aniline modified lignin for symmetric lignin particles/lignin-derived materials.
supercapacitors. J Power Sources 2016;307:462–7.
[244] Yang J, Wang Y, Luo J, Chen L. Facile preparation of self-standing hierarchi-
cal porous nitrogen-doped carbon fibers for supercapacitors from plant pro-
tein-lignin electrospun fibers. ACS Omega 2018;3:4647–56.
[245] Chen F, Zhou W, Yao H, Fan P, Yang J, Fei Z, Zhong M. Self-assembly of nio Chen Yang is currently a second-year graduate student
nanoparticles in lignin-derived mesoporous carbons for supercapacitor appli- in Polymer Science and Engineering at Sichuan University,
cations. Green Chem 2013;15:3057–63. China. He joined Professor Mengjin Jiang’s group in 2017.
[246] Xu J, Zhou X, Chen M. Microwave-assisted synthesis of cu-doped hierarchical His current research focuses on the preparation and ap-
porous carbon aerogels derived from lignin for high-performance supercapac- plication of gel electrolytes for supercapacitors.
itors. Mater Res Express 2018;5:1–11 095502ǀ.
[247] Wang L, Aorigele, Sun Y. Preparation of iron oxide particle-decorated lign-
in-based carbon nanofibers as electrode material for pseudocapacitor. J Wood
Chem Technol 2017;37:423–32.
[248] Lei D, Li X-D, Seo M-K, Khil M-S, Kim H-Y, Kim B-S. NiCo2 O4 nanos-
tructure-decorated PAN/lignin based carbon nanofiber electrodes with ex-
cellent cyclability for flexible hybrid supercapacitors. Polymer (Guildf)
2017;132:31–40.
[249] Ajjan FN, Casado N, Rebi ˛ ś T, Elfwing A, Solin N, Mecerreyes D, Inganäs O.
High performance PEDOT/lignin biopolymer composites for electrochemical
supercapacitors. J Mater Chem A 2016;4:1838–47.
[250] Navarro-Suarez AM, Casado N, Carretero-Gonzalez J, Mecerreyes D, Rojo T.
Full-cell quinone/hydroquinone supercapacitors based on partially reduced Mengjin Jiang received his Ph.D. degree in Polymer Sci-
graphite oxide and lignin/PEDOT electrodes. J Mater Chem A 2017;5:7137–43. ence and Engineering from Sichuan University, China in
[251] Ajjan FN, Vagin M, Rebi˛ ś T, Aguirre LE, Ouyang L, Inganäs O. Scalable asym- 2008. He has been an Assistant and Associate Professor
metric supercapacitors based on hybrid organic/biopolymer electrodes. Adv of Polymer Materials Science at Sichuan University since
Sustainable Syst 2017;1:1–8 170054ǀ. 2008. His current research interests include the prepara-
[252] Cai Z, Jiang C, Xiao XF, Zhang YS, Liang L. Lignin-based biochar/graphene tion, characterization and application of gel polymer elec-
oxide composites as supercapacitor electrode materials. Mater Sci Eng trolytes, and the design of flexible compact energy stor-
2018;359:1–4 012046ǀ. age devices.
[253] Milczarek G. Lignosulfonate-Modified electrodes: electrochemical properties
and electrocatalysis of NADH oxidation. Langmuir 2009;25:10345–53.
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on the electrochemical performance of supercapacitors. Electrochem Commun
2011;13:470–3.
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sant of coal water slurry. Energy Convers Manag 2007;48:2433–8.
[256] Liu Y, Gao L, Sun J. Noncovalent functionalization of carbon nanotubes with
sodium lignosulfonate and subsequent quantum dot decoration. J Phys Chem Xiangwu Zhang is a Professor in the Department of Tex-
C 2007;111:1223–9. tile Engineering, Chemistry, and Science in the Wilson
College of Textiles at North Carolina State University. He
Jiadeng Zhu received his B.S. degree in Macromolec- is currently serving as the Associate Dean for Research
ular Materials & Engineering from Soochow University and Professor in the College. Zhang earned a B.S. in Poly-
and Ph.D. in Fiber and Polymer Science from North Car- mer Materials and Engineering in 1997 and a Ph.D. in
olina State University. His research interests span from Materials Science and Engineering in 2001, both from
materials synthesis, electrochemistry, and cell design to Zhejiang University, China. Zhang‫׳‬s research interests fo-
advanced characterization with the goal of understand- cus on nanostructured and multifunctional polymer, fiber,
ing the synthesis-structure-performance relationship in and textile materials with an emphasis on energy storage
energy-related materials and their underlying reaction and conversion applications. His research encompasses
mechanisms. His current research focuses on applications both fundamental materials studies such as synthesis and
of smart polymers in the fields of energy, engineering, physical characterization, as well as system design and
and environment. fabrication.