REVIEW

Biomass-Derived Materials

Biomass-Derived Materials for Electrochemical Energy

Storage and Conversion: Overview and Perspectives
Fang Yu, Shizhen Li, Wanru Chen, Tao Wu, and Chuang Peng*

features of various components in EESC technol-

Electrochemical energy storage and conversion (EESC) technology is key to ogy, as well as the preparation and perfor-
the sustainable development of human society. As an abundant and mances of the biomass-derived materials. It is
renewable source, biomass has recently shown widespread applications in not our intention to write an exhaustive review
because of the extremely high volume of
EESC, achieving both low environmental impact and high performances. This
research work published in this area. Instead,
article provides overview and perspectives on various types of biomass- this review is an exemplary one that aims to
derived materials, their preparation, the role in EESC and the desired cover the widespread applications and current
features, performances and limitations, and future research efforts. progress of biomass-derived materials in EESC
systems by reviewing selected representative
research articles. Furthermore, the authors’ per-
1. Introduction spectives on the advantages, limitations, and outlook are also included.
Climate change, the growing energy demand, and the pursuit of sus-
tainable development are the three grand challenges for humans at pre-
2. Biomass-Derived Carbon Materials for
sent and in the future. Electrochemical energy storage and conversion
Supercapacitor Electrodes
(EESC) devices, that is, batteries, supercapacitors, and fuel cells, play a
central role in addressing these challenges because EESC is the core
Acclaimed for their ultra-high power and cycle performance, supercapac-
enabling technology toward transport electrification, hydrogen econ-
itors store electric energy through an electrical double-layer or faradaic
omy, and efficient utilization of renewable energy. Recently, there are
pseudocapacitive reaction. The most successfully commercialized super-
growing concerns on the environmental impact of EESC technologies
capacitors use carbon materials with high specific surface area as elec-
throughout their entire life cycle.[1–3] To render more sustainable
trodes.[4,5] Biomass-derived carbon materials, through pyrolysis and
development of EESC, recycling, on the one hand, has been intensively
carbonization under oxygen-deficient conditions, have been extensively
researched and widely practiced in industry. On the other hand, a more
studied in academia and widely used in industry for supercapacitors,
proactive strategy is to use environmentally friendly and biodegradable
because of their high porosity, conductivity, capacitance, and versatility
materials to reduce environmental impact at the source. Biomass is a
for modification, as well as the abundance and renewable nature of the
renewable and abundant natural resource mainly produced by photo-
raw materials. Over the past decade, advanced biomass-derived carbons,
synthesis of plants. In a wider sense, biomass includes materials derived
particularly those with well-defined pore structures and heteroatom dop-
from all life species of plants, animals, fungi, and microorganisms. The
ing, have achieved record high specific capacitance and power capability.
preparation and application of biomass-derived materials for EESC have
been booming in recent years, with the pursuit of both high perfor-
mance and low environmental impact. Table 1 summarizes the applica-
2.1. Precursor and Synthesis of Biomass-Derived Carbon for
tions and desired features of biomass-derived materials in various types
Supercapacitor
of EESC systems and components. There are a number of review papers
focusing on certain aspects, for example, materials or applications of
Almost all biomass can be used as precursor for making porous carbon
this booming research field. But no effort has been made to cover vari-
for supercapacitors, such as wood, plant leaf, fruit shell, straw, or animal
ous EESC technologies using biomass-derived materials. The current
tissues. Typical biomass consists of hemicellulose, lignin, cellulose, oil or
work overviews how biomass-derived materials match with the desired
fat, protein, chitosan, etc. Lignin-rich biomass is the most widely used
precursor because of its abundance, low cost, high carbon yield, and pro-
F. Yu, S. Li, Prof C. Peng duct porosity. Different precursors vary in composition, microstructure,
School of Resource and Environmental Sciences, Shenzhen Research
Institute, Wuhan University, 299 Bayi Road, 430072 Wuhan, China and metallic and nonmetallic elements, all of which poses impact on the
E-mail: chuang.peng@whu.edu.cn properties of the carbon products. The microstructure of biomass also
W. Chen, T. Wu plays important role in product morphology and microstructure. The
New Materials Institute, The University of Nottingham Ningbo China, metallic element such as sodium and potassium in the biomass can serve
315100 Ningbo, China
as nascent activation agent during synthesis, while the nonmetallic ele-
F. Yu and S. Li contributed equally to this work
ments such as nitrogen, sulfur, and phosphorus can remain in the final
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/eem2.12030.
product as heteroatom dopant. Conventionally, the preparation of bio-
mass-derived porous carbon usually consists of drying and milling pre-
DOI: 10.1002/eem2.12030 treatment, pyrolysis, carbonization, and activation. Laboratory researches

Energy Environ. Mater. 2019, 2, 55–67 55 © 2019 Zhengzhou University

Table 1. Role of biomass-derived materials in electrochemical energy storage and conversion.

Type of EESC
Supercapacitor
Lithium–sodium ion battery
Lithium–sulfur battery
Lead–acid battery
PEM or microbial fuel
cell and metal–air battery
PEM fuel cell and metal–air battery
Lithium-ion/sulfur battery;
supercapacitor
Lithium-ion battery; supercapacitor
Supercapacitor
Lithium-ion battery, supercapacitor
Dye-sensitized solar cells
Dye-sensitized solar cells
Redox flow battery
Role of biomass-derived Type of biomass-derived Desired features of the biomass-derived materials
materials materials
Electrodes Porous/activated carbon Porous, conducting, high specific surface area, double-layer capacitance,
functional groups, heteroatom doping, engineered pore structure
Negative electrode Hard carbon, soft carbon Micrographite domain for Li/Na intercalation, conducting, porosity
Conducting agent and Porous/activated carbon Porous, conducting, high specific surface area, heteroatom doping
S host in cathode
Conducting agent and charge Porous/activated carbon Conducting, high specific surface area, double-layer capacitance
accepting material in anode
Electrocatalyst or catalyst support Porous/activated carbon Conducting, high specific surface area, heteroatom doping,
catalytic property for ORR
Gas diffusion layer Porous/activated carbon, Conducting, high porosity, hydrophobic
carbon cloth/felt
Electrode binder Cellulose, chitosan, other Polymer chain and binding ability, chemical stability,
polysaccharides functional groups
Separator Cellulose, fiber Electron insulator, thin film, wettability, flexibility, mechanical
strength, chemical stability
Electrolyte Organic acids and salts Ion conductivity, stability over a reasonably wide potential window
Current collector Carbon sheet/cloth/felt Conducting, thin sheet, flexible, mechanical strength, chemical stability
Photosensitizer Natural dyes High absorbance of visible light, affinity to TiO2, chemically stable
Counter (positive) electrode Porous carbon High specific surface area, catalytic effect for triiodide reduction reaction
Electrode Porous carbon High specific surface area, high conductivity, catalytic activity for the redox
reaction of the dissolved active species

have incorporated novel preparation methods such as hydrothermal and
microwave treatment. Although the biomass precursor itself is abundant
and renewable, the environmental impact does arise from the high
energy consumption in the production process, high amount of chemical
activation agent used, and the resulting wastewater. Biomass-derived car-
bon without using added activation agent has been reported using lotus
stem.[6] During its preparation, the nascent metal ions in the biomass
served as the activation agent. The as-synthesized porous carbon[6] has a
specific surface area of 1610 m2 g
1 and a specific capacitance of
174 F g
1 at a scan rate of 5 mV s
1 in aqueous alkaline electrolyte. The
embedded salts in the lotus stem acted as porogen even at relatively low
contents, which favor pore formation and produce desired electrochemi-
cal properties (Figure 1a–c). This self-activation method using the
embedded salts in biomass also improves the sustainability of the produc-
tion process because less wastewater is produced. But in almost all
research and industrial practice, physical or chemical activation, or a com-
bination of both is commonly used in order to achieve the desired prop-
erties of the carbon products. Physical activation uses steam or CO2 so it
is greener than chemical activation. But a higher temperature is often
required and the specific surface area of the produced carbon is often
lower. Table 2 summarizes the specific surface area, pore volume, and
specific capacitance of various biomass-derived carbon materials prepared
by different activation methods for supercapacitors.
2.2. Biomass-Derived Carbon with Engineered Pore Structures
for Supercapacitor
The pore structure of biomass-derived carbon has a tremendous influence
on its electrochemical properties as a supercapacitor electrode. Advances
in material preparation have resulted in carbons with well-defined
pore structures. The prevailing view is that mesoporous or hierar-
chically porous carbons have the optimum performance for super-
capacitors. The mesopores give rise to the high specific capacitance,
while the macropores serve as electrolyte reservoirs which improve
the diffusion kinetics and hence the power capability. Micropores
may also contribute to capacitance depending on its size in compar-
ison with that of the electrolyte ions.
As discussed above and in literature,[7] hierarchical porous carbons
(combination of macro-, meso-, and micropores) are expected to have
superior performance as supercapacitor electrode because of the com-
bined merits of high electrolyte accessibility, surface area, fast diffusion,
and transportation of electrolyte ions. The hierarchically porous struc-
ture could be generated by KOH activation of hydrothermally derived
carbonaceous biomass.[8,9] Similarly, porous carbon activated with
nano-ZnO also showed hierarchical structure, enhanced degree of
graphitization, and hence improved electric conductivity.[10] A recent
study showed that molten salt technology was able to produce carbon
nanobelts with controllable hierarchical pore structure. The ZnCl2 mol-
ten salt was capable of oriented swelling and splitting as well as produc-
ing hierarchical pores in biomass-derived carbon.[11] A combined
simultaneous carbonization activation and post-vacuum annealing
method was used to prepare shaddock skin-derived hierarchical porous
carbon with ZnCl2 and FeCl3 as activation agent. This carbon has a cage-
like structure consisting of interconnected nanosheets with graphene-
like structures (Figure 1d–e).[12] Its CV curves showed rectangular
shape at a scan rate ranging from 200 to 2000 mV s
1 (Figure 1f).
Symmetric supercapacitors displayed rate capability at current density of
100 A g
1 and 97.6% capacitance retention over 10 000 cycles in
ionic liquid mixture electrolyte.[12]

Energy Environ. Mater. 2019, 2, 55–67 56 © 2019 Zhengzhou University

 (a) (b) (c)

(f)

(d) (e)

(i)

(g) (h)

(l)

(j) (k)

Figure 1. SEM/TEM images and cyclic voltammetry of biomass-derived carbons for supercapacitors: a–c) self-activated porous carbon.[6] Copyright 2017,
Wiley; d–f) hierarchical porous carbon.[12] Copyright 2017, Elsevier; g–i) mesopore-dominant hierarchical porous carbon.[13] Copyright 2017, Elsevier; j–l)
porous monolithic carbon.[15] Copyright 2017, American Chemical Society.

The high percentage of mesopore volume in the hierarchical pore
structure of carbon is important for achieving both high capacitance
and rate performance in organic and ionic liquid electrolyte because of
the large electrolyte ion size compared to the aqueous counterpart.
Alkaline activation is capable of formation of interconnected pores, and
the concentration of alkali has a positive correlation with the specific
surface area, total pore volume, and particularly the mesopore volume.
Mesopore-dominant hierarchical porous carbon was prepared by
hydrothermal carbonization and KOH activation using corn straw as
precursor.[13] The obtained carbon had mesopore volume of
1.85 cm3 g
1, specific surface area up to 1771 m2 g
1, and specific
capacitance of 202 F g
1 at current density of 1 A g
1 in organic

Energy Environ. Mater. 2019, 2, 55–67 57 © 2019 Zhengzhou University

Table 2. Capacitance values, specific surface area, and pore volume of biomass-derived activated carbons for supercapacitors.

Biomass precursors Activators Activation method, SBET Vtot Electrolyte Measurement Maximum capacitance References
doped type (m2 g
1) (cm3 g
1) conditions (F g
1)
Puffed rice KOH Carbonization, activation 3326 0.34 6 M KOH 0.2 A g
1 349 [99]

1 [100]
Clover KCl Molten salt 2244 1.440 1 M 1Ag 436
H2SO4
Corn straw KOH Carbonization, activation 2790.4 2.04 KOH 0.2 A g
1 327 [24]

1 [25]
Silkworm excrement KOH Carbonization, activation 2258 1.25 6 M KOH 0.5 A g 401
Wheat straw Melamine, KCl/ Pyrolysis, N doped 1201 1.021 6 M KOH 5 mV s
1 223.9 [101]

ZnCl2
Bradyrhizobium ZnCl2 HTC, pyrolysis 1275 0.63 6 M KOH 1 A g
1 358 [102]

japonicum
Rice straw KOH Carbonization, activation 1007 – 1 M 0.5 A g
1 332 [103]

H2SO4
Garlic skin KOH Carbonization, activation 2818 1.327 6 M KOH 0.5 A g
1 427 [104]

Chitosan Acetic acid/KOH HTC, activation 3532 1.64 6 M KOH 0.5 A g
1 455 [105]

1
Ant powder KOH Activation, O-N-S doped 2650 – 6 M KOH 1Ag 576 [19]

1 [106]
Fish scales KOH Activation, O-N-S doped 962 0.41 6 M KOH 1Ag 306
Tobacco rods KOH HTC, activation, metal 2097 1.17 6 M KOH 0.5 A g
1 286.6 [107]

doped
Agar KOH Calcination 1672 0.81 6 M KOH 1 A g
1 226 [108]

electrolytes (Figure 1g–i). Despite the high rate performance and
capacitance of either hierarchical or mesopore-dominant porous carbon,
their mass density is commonly low, resulting in a low energy density.
This trade-off between the pore volume and energy density is a crucial
challenge yet to be explored in future research.
Originally derived from carbide materials,[14] monolithic carbon is high
in porosity and electric conductivity. As a supercapacitor electrode, it
shows high specific capacitance and does not require any polymeric bin-
der.[14] As a much cheaper alternative to carbide, biomass can also be used
to prepare monolithic carbon. The preparation is similar to powdery acti-
vated carbon but without milling pretreatment of biomass.[15] In some
cases, the biomass precursor is compressed in order to obtain a better con-
ductivity in the product carbon.[16] Monolithic carbon fiber aerogel
derived from cotton has specific area between 1536 and 2436 m2 g
1
with pore size in the range of 1.0–4.0 nm.[15] Its specific capacitance is up
to 283 F g
1 in aqueous alkaline solution with high capacitance retention
even at high current density of 100 A g
1. It is worth noting that bio-
mass-derived monolithic carbon possesses hierarchical pore structure, dif-
fering from the ordered micropores in carbide-derived monolithic carbon
(Figure 1j–l). Similar to the hierarchically porous carbon, monolithic car-
bon is also generally low in mass density and energy density. An effective
method to improve the energy density is to combine with a redox active
material with pseudocapacitance, because the structure, porosity, and con-
ductivity make monolithic carbon a superior scaffold for thin coatings.
charging process during negative polarization.[4,5] Heteroatoms with
high electronegativity introduce chemical polarity to the neighboring
carbon atoms and hence facilitate cation adsorption. Therefore, introduc-
tion of highly electronegative heteroatoms such as fluorine and nitrogen
into porous carbon may result in improved electrochemical performance
of the negative electrode.[18] Heteroatom doping can be combined with
the aforementioned pore structure engineering to achieve further
enhanced performance due to the synergistic effect of the two strategies.
Recently, O-N-S-co-doped 3D hierarchical porous carbons were synthe-
sized from ant powder by one-step simultaneous carbonization and acti-
vation.[19] Its specific capacitance reached up to 352 F g
1 at 0.1 A g
1
in a two-electrode prototype supercapacitor, together with a high-rate
capacitance of 225 F g
1 at 20 A g
1.[19] In addition to the electronega-
tive heteroatoms, phosphorus has also been reported as an effective
dopant to enhance the oxidation stability at positive potential and adsorb
hydrogen at negative potential, resulting in higher working voltages.[20]
Although heteroatom doping plays multifunctional roles in improving
materials properties, it remains difficult to control the content of heteroa-
toms in the carbon matrix. Generally, a lower carbonization temperature
is beneficial to heteroatom retention.[21,22] But a higher temperature
improves the electric conductivity of the carbon materials.[23]
2.4. Biomass-Derived Carbon with Functional Groups for
Supercapacitor

2.3. Biomass-Derived Heteroatom-Doped Carbon for
Supercapacitor
Heteroatom doping with nonmetallic elements such as N, O, B, S, and P
is a recently emerged method to improve the performance of porous car-
bon for supercapacitors.[17] Based on the energy storage mechanism of
supercapacitor, adsorption of cations in electrolyte dominates the
In addition to the pore structure engineering and heteroatom doping,
surface functional groups of carbon also affect the charge storage prop-
erties of supercapacitor electrode. Alkaline activation or treatment is the
most commonly investigated method to introduce oxygen-containing
functional groups on the surface of carbon.[24,25] These functional
groups, that is, hydroxyl, carbonyl, and carboxyl groups, not only
enhance the wettability of carbon surface with electrolyte, but also

Energy Environ. Mater. 2019, 2, 55–67 58 © 2019 Zhengzhou University

provide pseudocapacitance through reversible redox reactions.[26,27]
Carbon with functional groups derived from pine needle was prepared
by hydrothermal carbonization and KOH activation.[28] The product
was mainly composed of carbon nanosheets and showed a specific sur-
face area of 1175 m2 g
1. Its CV curves revealed combined double-
layer and pseudocapacitive behavior in aqueous alkaline electrolyte, and
the specific capacitance reached 348 F g
1. Aside from the improved
wetting and contribution of pseudocapacitance, the surface functional
groups also improved the ion transport kinetics.[28] Moreover, the func-
tional groups can broaden the capacitive potential window of the car-
bon electrode in neutral aqueous electrolyte because of the high over-
potential for hydrogen evolution.[29] Despite these merits of the surface
functional groups, it was reported their presence might lead to inferior
cycle performance and even gassing problem in organic electrolytes.[30]
3. Biomass-Derived Intercalating Carbon as
Negative Electrode for Lithium and Sodium Ion
Battery
Graphite, hard carbon, and soft carbon are the state-of-the-art negative
electrode material for lithium-ion batteries (LIBs) because of their low
(a) (b)
(d) (e)
(g) (h)
Figure 2. SEM/TEM images and cycling performance of biomass-derived intercalating carbon for LIB: a–f) graphitized carbon consisting of graphene-like
nanosheets.[33,34] Copyright 2016, Royal Society of Chemistry; Copyright 2018, Elsevier; g–i) heteroatom-doped graphitized carbon.[35] Copyright 2018, Elsevier.
Energy Environ. Mater. 2019, 2, 55–67
lithium intercalation potential and high capacity. These materials are
normally synthesized from carbonization and graphitization of poly-
mers and biomass materials. Aside from being renewable and cost-
effective, biomass-derived intercalation carbon had unique structural
and morphological properties.[31,32] For instance, graphene-like carbon
nanosheets were prepared through hydrothermal carbonization and
thermal activation from peanut skin and wheat stalk.[33,34] These
graphitized carbons exhibited higher porosity (Figure 2a,b,d,f) than
commercial hard or soft carbon, resulting in high rate capacity and
stable cycling performance (Figure 2c,f). Along with its success in
supercapacitor, heteroatom doping has also been used in biomass-
derived carbon-negative electrode for LIB, due to the defects and associ-
ated enhanced electric conductivity.[35] Soybean milk was used as pre-
cursor to fabricate nitrogen-doped carbon with 3D interconnection
network structure formed by ultra-thin carbon nanosheets (Figure 2g–
h).[35] The electrode delivered high initial reversible specific capacity of
1334 mAh g
1 at 50 mA g
1, with a capacity retention of
355 mAh g
1 at 1 A g
1 after 1000 cycles (Figure 2i). The intercon-
nected porous nanosheet structure and the nitrogen doping are favor-
able to lithium-ion transportation and lithium storage, respectively.
Besides single heteroatom, multiple heteroatoms, such as P and N,[36] S
and N,[37] have been combined to produce co-doped carbon for
(c)
(f)
(i)
59 © 2019 Zhengzhou University
negative electrodes. Egg yolk-derived P and N dual-doped carbon
showed a reversible capacity of 770 mA h g
1 at 0.5 A g
1 with
good cycling stability.[36] The desired performance of the dual-doped
carbon was attributed to the defects and disorder by heteroatom co-
doping, which created additional active sites for lithium insertion. Bio-
mass-derived carbon has also been used as scaffold for loading metal
oxides, resulting in various types of composite negative electrodes for
LIB.[38–40]
Sodium ion battery (SIB) is a promising alternative to LIB because of
the abundance and low cost of sodium. But electrode materials face
more challenges in SIB because of the more sluggish diffusion kinetics
and higher volume expansion compared with LIB. Hard carbon or por-
ous hard carbon materials derived from biomass, such as lotus stem,[41]
cherry petals,[42] corn straw piths,[43] waste apricot shell,[44] rice
husk,[45] have shown improved rate and cycle performances as negative
electrodes for SIB. One common strategy to cope with the large sodium
ion is to increase the carbon interlayer distance via chemical treat-
ment.[45] In general, the preparation of biomass-derived carbon as neg-
ative electrodes for LIB or SIB is similar to the supercapacitor-type
carbon. But a higher temperature is required to achieve higher degree
(a) (b)
(d) (e)
(g) (h)
Figure 3. SEM/TEM images of the biomass-derived carbons and their ORR activity in O2 saturated 0.1 M KOH: a–c) nitrogen-doped carbon.[48] Copyright
2014, Royal Society of Chemistry; d–f) N, S-doped carbon.[47] Copyright 2018, Elsevier. g–i) iron phosphide on N-S-doped carbon.[60] Copyright 2018, Wiley.
Energy Environ. Mater. 2019, 2, 55–67
of graphitization,[42,46] which is a prerequisite for Li intercalation. Bio-
mass-derived intercalating carbon generally has higher porosity than
commercial graphite or hard carbon, resulting in improved rate and
cycle performance as negative electrode for LIB and SIB. But high
porosity inevitably leads to low energy density, which limits their prac-
tical applications. This trade-off between energy density and cycle per-
formance is yet to be solved in future research.
4. Biomass-Derived Carbon as Electrocatalysts and
Gas Diffusion Layer for PEM Fuel Cells and Metal–
Air Batteries
PEM fuel cells allow efficient conversion of hydrogen to electricity,
while metal-air batteries provide theoretical energy density close to that
of petrol. They both rely on electrocatalysts for oxygen reduction reac-
tion (ORR) at the positive electrode. Platinum on carbon (Pt/C) is the
state-of-the-art electrocatalyst for ORR. But the resource scarcity and
high cost hinder its commercialization. Carbon-based metal-free elec-
trocatalyst is a promising alternative to noble metal because of its
(c)
(f)
(i)
60 © 2019 Zhengzhou University
catalytic activity, abundance, low cost, and high tolerance to carbon Biomass-derived carbon has also been used as gas diffusion layer
monoxide. Effective carbon-based ORR catalysts have been prepared (GDL) in PEM fuel cells and metal–air batteries.[63] The GDL plays
from various biomass materials such as basswood,[47] typha orien- important role in supporting the catalyst layer, collecting electric cur-
talis,[48] glucose,[49] cicada sloughs.[50] Biomass-derived ORR catalysts rent, and transporting reactants and water.[64] Commercial GDL com-
have shown ability to achieve comparable or even superior electrocat- monly uses carbon paper or cloth consisting of carbon fibers. A GDL
alytic activity to that of commercial Pt/C.[51,52] In principle, these car- consists of biomass-derived porous carbon was recently reported to
bon materials possess simultaneously high specific surface area and show alleviated mass transport loss during uninterrupted durability
abundant active sites, which is a prerequisite for heterogeneous electro- test.[63]
catalysis. Nitrogen doping further enhance the catalytic activity because
N atoms can endow the carbon matrix with desired polarity and induce
positive charge in adjacent carbon atoms.[53] Thermal treatment in 5. Biomass-Derived Carbon Materials for Lithium–
ammonia is a widely used method to simultaneously introduce nitro- Sulfur Battery
gen dopant and improve porosity in biomass-derived carbon for
ORR.[48] The doping mechanism has been attributed to the formation Lithium–sulfur battery (LSB) is a promising secondary battery with
of free radicals including -NH2, -NH, atomic hydrogen, and nitrogen, high theoretical specific capacity of 1675 mAh g
1 and energy density
which can replace oxygen-containing species on carbon skeleton and of 2600 Wh kg
1. Moreover, sulfur is an abundant, inherently safe,
[54,55]
yield nitrogen-based active sites for ORR. In a typical example, and low-cost material, which can meet the high demand of the next-
nitrogen-doped porous carbon derived from typha orientalis was syn- generation power and storage batteries.[65,66] However, the shuttle
thesized by a hydrothermal process, freeze-drying, and annealing in effect of the polysulfide ions, the poor conductivity, and volumetric
ammonia.[48] This carbon had specific surface area of 898 m2 g
1 and expansion of sulfur during the charge–discharge process results in poor
N content of 9.1 at%, showing electroactivity comparable to that of Pt/ cycle performance and thus hinders the commercialization of LSB.[67–
C in both alkaline and acidic media (Figure 3a–c). Recently, the co- 69]
To improve the cycle performance, a few strategies have been
doping strategy has been used to further improve the catalytic perfor- explored, including design of advanced composite cathode, separator
mance by combining N with B, S, or P atoms.[47,56] A nitrogen- and modification, and novel battery configuration.[70–72] As a versatile func-
sulfur-co-doped carbon with hierarchical pore structure (Figure 3d,e) tional material, porous carbon has found successful applications in all
exhibited low onset potential of 0.98 V and a half-wave potential of these three strategies. In particular, biomass-derived carbon materials
0.86 V versus RHE in alkaline medium, along with high durability and have been extensively studied in LSB, because of their low cost, facile
methanol cross-over tolerance (Figure 3f).[47] preparation, high specific surface area, and abundant surface functional
Biomass-derived carbon can also serve as catalyst support for both groups.
noble metal[57] and transition metal oxide/sulfide[58,59] to generate high
surface area and reduce the loading of metal
species. Heteroatom doping is also effective in
this case because the doped regions not only
provides anchoring sites for metal loading, but
also have strong metal–support interaction,[57]
which play a positive role in ORR catalytic per-
formances. In a recent study, iron phosphide on
N-, P-, and S-co-doped carbon was prepared
from human urine.[60] This hybrid material
showed a hierarchically porous structure (Fig-
ure 3g,h) with specific surface area of
1080 m2 g
1. As an ORR electrocatalyst, the
hybrid material showed highly efficient four-
electron transfer pathway, similar onset poten-
tial, and higher current density than commer-
cial Pt/C (Figure 3i).
Heteroatom-doped carbon opens a new
avenue for metal-free ORR electrocatalyst. But
the mechanism for the catalysis needs further
investigation. It still remains controversial
which type of nitrogen, that is, pyridinic, pyr-
rolic, or graphitic, is playing the major role in
the catalytic activity.[61,62] Developing bifunc-
tional electrocatalyst which can simultaneously
catalyze ORR and OER is also a challenge yet to
be solved in carbon-based electrocatalysts. An Figure 4. a) Cycle performance of LSB with 3-D structured carbon/S cathode at 0.2 C.[70] Copyright
effective bifunctional catalyst is key to reducing 2014, Elsevier; b) cycle performance of LSB with N and O dual-doped porous carbon/S cathode at 1 C.[71]
the polarization and hence improving the effi- Copyright 2016, Elsevier; c) cycle performance of LSB with activated carbon-coated glass fiber
ciency of rechargeable metal–air batteries. separator.[72] Copyright 2018, Elsevier.

Energy Environ. Mater. 2019, 2, 55–67 61 © 2019 Zhengzhou University

 Biomass-derived porous carbon has been rigorously studied as a and the current collector to form the electrode, and ensures it maintain
host material in sulfur cathode. The multifunctional carbon not integrity during electrode reaction. Polyvinylidene fluoride (PVDF) is
only increases the conductivity of the cathode and provides pores the most popular polymer binder due to its superior chemical and elec-
to accommodate sulfur particles, but also confines the polysulfide trochemical stability, and good adhesive property. Despite these merits,
anions in its porous structure. In a typical example, 3D structured PVDF requires the use of harmful organic solvent during processing
carbon material was prepared by carbonizing pomelo peel and acti- and induces additional difficulty for battery recycling at the end of its
vating with KOH.[70] The LSB with this novel host exhibited a life cycle.[73,74] Recent researches have shown that biomass-derived
high initial discharge capacity of 1258 mAh g
1 at 0.2 C and materials, that is, natural organic macromolecules or modified ones,
retained 750 mAh g
1 after 100 cycles with coulombic efficiency can be employed as electrode binder. Extensively studied biomass-
of 96% (Figure 4a). The host carbon played the role as both con- derived binders include sodium carboxymethyl cellulose
ducting agent and a reservoir, which adsorbs polysulfides. How- (CMC),[73,75,76] cyclodextrin,[74,77] natural gum,[78,79] and agar[80] or
ever, the cycle performance of this battery is still not satisfactory, their mixtures.[81,82] These environmentally friendly binders have
probably because the weak physisorption between the polysulfides shown great success in silicon and sulfur electrode because they can
and the nonpolar carbon matrix only provides moderate restriction offer desired properties to meet the additional demands of these newly
on lithium polysulfide shuttling. Recently, it is reported that func- emerged electrodes.
tional carbons, particularly heteroatom (such as O, N, B, and S)- CMC is a linear polymeric derivative of cellulose, consisting of
doped porous carbon, show the ability to chemically adsorb b-linked glucopyranoses with carboxymethyl substitution (Figure 5a).
lithium polysulfides. For instance, N and O
dual-doped porous carbon[71] was prepared
via a facile carbonization and activation pro-
cedure by using soybean residue as the pre-
cursor. The LSB constructed with this dual-
doped carbon as sulfur host exhibited a
good rate capability of 482.7 mAh g
1 at
2 C and excellent cycle performance of
435.7 mAh g
1 after 600 cycles at 1 C
(Figure 4b). The improved performance was
attributed to the synergistic effect of the
hierarchical porous structure and in situ N
and O co-doping, which effectively suppress
the shuttle effect by the combined physical
confinement and strong chemical adsorption.
Another effective method is to sandwich a
conductive interlayer between the sulfur cath-
ode and the polymer separator, which serves
not only as a physical barrier to hinder the
movement of lithium polysulfides, but also as
an embedded conductive network in the cath-
ode region to reduce the resistance. Porous car-
bon fulfills this purpose because of its
lightweight feature and high electric conduc-
tivity. Recent report showed that a porous car-
bon derived from oak tree fruit was used as
interlayer for LSB,[72] which exhibited
improved electrochemical performance of an
initial capacity of 1324 mAh g
1 at 0.2 C and
about 75% capacity retention after 50 cycles
(Figure 4c). Both the host carbon and the car-
bon interlayer could improve the performance
of LSB, but at a cost of the specific energy of
the whole battery particularly if the carbon
content is high.

6. Biomass-Derived Materials as
Electrode Binder
Electrode binder plays a major role in binding
together the active material, conductive agent,
Figure 5. a) Chemical structure of CMC and b) cycle performance of the silicon electrode with three
different binders.[76] Copyright 2006, Elsevier; c) chemical binding between silicon nanoparticles and c-
PAA-CMC binder and d) cycle performance of the silicon electrodes with different binders at a current
density of 300 mA g
1.[82] Copyright 2012, Wiley; e) chemical structure of water-soluble b-CD and f)
cycle performance of LSB with various binders at 0.2 C.[74] Copyright 2012, Wiley.

Energy Environ. Mater. 2019, 2, 55–67 62 © 2019 Zhengzhou University

Apart from being a sustainable material, CMC is water-soluble so there change for sulfur cathode than GG or XG alone, as evidenced by the
is no need for organic solvent during electrode fabrication. CMC can be notably improved cycle performance (Figure 6f).
used alone or in combination with elastic styrene butadiene rubber Numerous newly emerging biomass-derived binders have shown
(SBR) if extra flexibility is required. The mixture of CMC and SBR has the ability to improve the cycle performance, energy density, and econ-
been reported[76] to show elastomeric behavior, which could effectively omy of batteries. However, the aqueous solutions of certain binders are
endure the large volume changes during charge/discharge and signifi- in a gelled state because of their polar functional groups forming
cantly improve the cycle performance of silicon (Si) anode for lithium- hydrogen bonding with water molecules. The poor fluidity of the gel
ion battery (Figure 5b). This result can be attributed to the binder’s leads to inferior processability during electrode fabrication and poses a
elasticity, larger maximum elongation, stronger adhesion strength on negative impact on electrode performance. It was reported that guar
copper foil current collector, and lower solvent absorption in organic gum tends to gelatinize in water leading to poor dispersion of electrode
carbonate compared to conventional PVDF binder. materials and reduced electrochemical performance of the electrode.[83]
Because of the linear structure of CMC, the adhesion between CMC However, the electrode slurry containing retrograded guar gum shows
and the electrode active material can deteriorate during repeated improved fluidity, dispersion of materials, and cell performance, com-
charge and discharge. To overcome this drawback, CMC has been pared with the freshly prepared gel slurry.[83]
cross-linked with poly (acrylic acid) to form a 3D interconnected
network (c-PAA-CMC),[82] which exhibited high mechanical resistance
to strain, and particularly nonrecoverable deformation (Figure 5c). 7. Biomass-Derived Membranes as Battery
The Si anode with this novel binder showed a high reversible capacity Separator
of over 2000 mAh g
1 after 100 cycles at 30 °C, which is signifi-
cantly higher than those using pure CMC or PVDF binder Battery separator is a porous membrane placed between the positive and
(Figure 5d). the negative electrode to prevent electrical short circuits and allow rapid
Cyclodextrins are a family of compounds
consisting of cyclic oligosaccharides. They are
the product of enzymatic hydrolysis of starch
and are widely used in the food and pharma-
ceutical industry. Compared with other
starch-derived compounds, cyclodextrins are
chemically stable but have a lower solubility
in water. To improve its solubility, b-cyclo-
dextrin (b-CD) was modified through partial
oxidation with H2O2 to produce water-solu-
ble carbonyl-b-cyclodextrin (C-b-CD)[74]
(Figure 5e). The LSB with C-b-CD as the bin-
der exhibited high reversible capacity and sul-
fur utilization (Figure 5f). In another attempt,
polymerized b-cyclodextrin (b-CDp)[77] was
used as binder for Si anodes (Figure 6a). Due
to the multidimensional hydrogen-bonding
interactions between b-CDp and Si particles,
the battery showed notably improved cycle
performance compared with alginate and
PVDF binder (Figure 6b).
Natural gum such as guar gum (GG), xan-
than gum (XG), Acacia Senegal, and their
mixtures have also been exploited as an aque-
ous-processable electrode binder. For instance,
GG extracts from the seeds of Cyamopsis tet-
ragonoloba (Guar bean) show (Figure 6c) a
specific ability to conduct lithium ions.[78] A
sulfur cathode fabricated with GG binder dis-
played better cycling performance than that
with PVDF binder (Figure 6d). GG can also
be combined with another binder such as XG
[81] via intermolecular binding to yield a
functional dual binder (Figure 6e). Due to
Figure 6. a) Chemical structure of the b-CDp binder and b) cycle performance of the silicon electrode
the mechanically robust network and abun- with b-CDp (Si [77]
b‑CDp), alginate (SiAlg) and PVDF (SiPVDF)-based binders. Copyright 2014, American
dant functional groups, this novel binder Chemical Society; c) chemical structure of GG binder and d) cycle performance of the LSBs with
showed enhanced capability to suppress the different binders at 0.2 C.[78] Copyright 2016, Elsevier; e) chemical structure of XG and f) cycle
shuttle effect and accommodate the volume performance of the LSB with different binders at 0.5 C.[81] Copyright 2017, Royal Society of Chemistry.

Energy Environ. Mater. 2019, 2, 55–67 63 © 2019 Zhengzhou University

transport of ionic species. Polyolefin such as
polyethylene (PE), polypropylene (PP), and
their blends are widely used porous separators
due to their low cost, superior electrochemical
stability, and high tensile strength. However,
their inferior thermal stability at high tempera-
ture can affect the thermal shutdown property
and cause safety concerns. Moreover, these
polymer separators commonly suffer from poor
wettability with liquid electrolytes, which is
detrimental to the battery’s rate capability.[84,85]
Recently, it was reported that biomass-derived
materials including cellulose,[84–88] chitin,[89,90]
and alginate-based[91] separators can offset the
drawbacks of polyolefin-based polymer
separator.
As shown in Figure 7a, cellulose nanofiber
paper (CNP)[87] was prepared from cellulose
nanofiber (CNF) suspension. Due to the polar-
ity and thermal stability of CNFs, CNP separator
showed higher ionic conductivity, and
improved electrolyte wettability and thermal
stability than polyolefin-based separator in
lithium-ion battery (Figure 7b). However, the
large-size pores and low mechanical strength of
CNP separator influence the safety and cycle life
of lithium-ion battery due to the formation of
dendritic Li and battery self-discharge.[92,93] To
tackle these issues, some materials such as
dopamine and colloidal silica (SiO2) were
employed to improve the performance of CNP
separator. For example, dopamine was used to
coat the surface of microfibrillated cellulose
(CPD)[92] to form a composite membrane by Figure 7. a) Schematic illustration of the crystalline–amorphous structured CNFs and b) cycle
self-polymerization (Figure 7c). With abun- performance of the lithium-ion battery with PP/PE/PP separator and CNP separator.[87] Copyright
dant compact and tortuous nanopores, this 2012, Royal Society of Chemistry; SEM image of the polydopamine-coated microfibers c) and cycle
[92]
composite membrane exhibited enhanced performance d) of LiCoO2/graphite cells using various separators. Copyright 2014, Royal Society of
mechanical strength and improved electrolyte Chemistry; e) SEM image of SiO 2-CNP separator and f) cycle performance of lithium-ion battery using
different separators.[93] Copyright 2013, Elsevier.
wettability resulting in a high-performance
lithium-ion battery[92] (Figure 7d). In another
attempt, SiO2 filler was introduced to CNP membrane to control the alginate-based nonwoven separator (CA)[91] (Figure 8c) was used in
[93]
pore structure of the separator. It was found that the SiO2-CNP sep- lithium-ion battery and exhibited tensile strength of 37 MPa, thermal
arator with 5 wt% SiO2 content exhibited the highest ionic con- stability up to 150 °C, and ionic conductivity of 1.4 9 10
3 S cm
1,
duction due to the well-balanced combination of nanoporous all higher than commercial polyolefin separator. Moreover, the 5 V
structure and separator thickness (Figure 7e). The lithium-ion bat- high-voltage LiNi0.5Mn1.5O4/Li cell with this alginate nonwoven sepa-
tery using these modified separators showed better rate capability rator delivered much better cycling stability than that of PP separator
and cycling stability than using polyolefin or pure CNP separator at an elevated temperature of 55 °C (Figure 8d). The improved cycle
alone (Figure 7f). performance was attributed to its abundant carboxyl groups, which
Chitin [poly (b-(1, 4)-N-acetyl-D-glucosamine)] is the second most are able to chelate with and anchor the dissolved transition metal
abundant natural polysaccharide next to cellulose (Figure 8a). A ions.
chitin-based nonwoven fiber separator was designed by centrifugal
jet-spinning technique and exhibited excellent electrolyte-uptaking
capability and Li-dendrite mitigating performance in lithium metal 8. Other Applications of Biomass-Derived
batteries (Figure 8b).[89] Moreover, because of the unique coordina- Materials in EESC
tion with functional groups, the nonwoven fiber separator showed
stronger Li+ affinity, which makes it useful not only in Li+/Li sym- Dye-sensitized solar cells (DSSCs) are low-cost photoelectrochem-
metry cell but also in Li-O2 and Na-O2 batteries.[89] Alginate derived ical devices allowing direct conversion of sunlight to electricity.
from brown seaweeds is widely used as a binder to enhance the Natural dyes or pigments have been used as the photosensitizer in
cycling stability of the lithium-ion batteries. Recently, a commercial DSSC because they can absorb visible light and inject electron to

Energy Environ. Mater. 2019, 2, 55–67 64 © 2019 Zhengzhou University


Figure 8. a) Chemical structure of chitin and b) chronopotentiometry results of coin cell with various low mass density usually results in inferior
separators.[89] Copyright 2017, American Chemical Society; c) SEM image of CA separator and d) cycle energy density, which does not suffice practical
performance of the LNMO/Li cells with PP separator and CA separator at 55 °C.[91] Copyright 2017, applications. Biomass-derived carbons have also
American Chemical Society.
the conduction band of TiO2.[94] Despite being renewable and
abundant, DSSC with natural dyes normally show a power con-
version efficiency lower than 1.6%,[95] compared to over 10% for
synthetic dyes such as organic metal complexes. It is suggested
both the efficiency and stability of natural dye-sensitized solar
cells need to be improved in order to enhance the commercial
value of this technology.[94] The positive electrode or counter
electrode of a DSSC receives electrons from the external circuit


and reduces I
3 into I in electrolyte. Platinum is the state-of-the-
art counter electrode because of its electrocatalytic behavior for I

reduction. Recent research shows that biomass-derived porous
carbon doped with multi-heteroatoms can be used as an effective
counter electrode for DSSC.[96] The power conversion efficiency
of the solar cell reached 8.29%, slightly higher than the DSSC
with Pt counter electrode which exhibited efficiency of
8.24%.[96] This remarkable efficiency is attributed to the porosity,
specific surface area, heteroatom doping, which facilitates cat-
-
alytic reduction of I3 .
A lead–carbon battery uses blend of lead and carbon powder as
the negative electrode, that is, internal parallel connection of bat-
tery and supercapacitor. Compared with conventional lead-acid
battery, the lead–carbon battery shows improved power capability
and cycle performance, particularly at partial state of charge and
deep cycle operation mode. Recent research shows that biomass-
derived nitrogen-doped porous carbon improves the capacity and
lowers the polarization of the lead–carbon battery, owing to the
high specific surface area and high conductivity of the carbon
[97]
material.
Energy Environ. Mater. 2019, 2, 55–67
Biomass-derived porous carbon has also
found applications in all vanadium redox
flow batteries (VRFBs). A VRFB using cot-
ton-derived porous carbon with functional
groups as both positive and negative elec-
trodes showed higher capacity, enhanced
reversibility, and hence energy efficiency
compared with commercial carbon paper
electrodes, owing to the high surface area,
hydrophilic feature, and catalytic activity for
vanadium redox reaction.[98]
9. Conclusion
Biomass-derived materials find widespread
applications in electrochemical energy storage
and conversion technologies. Biomass-derived
carbon materials have shown enormous success
for supercapacitor electrodes, LIB-negative elec-
trodes, and negative electrode sulfur host for Li-
S batteries. Carbons with engineered pore struc-
ture and heteroatom doping have achieved
record high performances in terms of specific
capacitance and rate capabilities. However, its
shown promise as efficient electrocatalyst for
ORR because of its high specific area, as well as
the presence of heteroatom-induced active sites,
though the doping level is still hard to control during preparation and the
mechanism for enhanced property is still under debate. The high porosity
has also allowed these carbons to be used as host material in negative elec-
trode of Li-S batteries and gas diffusion layer in PEM fuel cells. Biomass-
derived natural polymers/macromolecules have been used as high-per-
formance electrode binder and battery separator due to their versatile
functional groups and hydrophilic feature in electrolyte solutions. In gen-
eral, biomass has established itself as a pivotal resource to produce various
key materials/components in electrochemical energy storage and conver-
3 sion technologies, not only because of its abundance and renewable nat-
ure, but also because of the high performances and desired features they
display in recent and ongoing research.
Acknowledgements
This work received financial support from the Science and Technology Bureau of
Shenzhen (Grant No. JCYJ20170306171540744) and the Science and Technology
Bureau of Ningbo (Grant No. 201501CX-C01006). F.Y. and S.L. contributed equally
to this work.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
biomass, battery, energy storage, fuel cells, supercapacitor
65 © 2019 Zhengzhou University
 Received: December 18, 2018
Revised: February 22, 2019
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