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Yu 2019
Yu 2019
Yu 2019
Biomass-Derived Materials
Type of EESC Role of biomass-derived Type of biomass-derived Desired features of the biomass-derived materials
materials materials
Supercapacitor Electrodes Porous/activated carbon Porous, conducting, high specific surface area, double-layer capacitance,
functional groups, heteroatom doping, engineered pore structure
Lithium–sodium ion battery Negative electrode Hard carbon, soft carbon Micrographite domain for Li/Na intercalation, conducting, porosity
Lithium–sulfur battery Conducting agent and Porous/activated carbon Porous, conducting, high specific surface area, heteroatom doping
S host in cathode
Lead–acid battery Conducting agent and charge Porous/activated carbon Conducting, high specific surface area, double-layer capacitance
accepting material in anode
PEM or microbial fuel Electrocatalyst or catalyst support Porous/activated carbon Conducting, high specific surface area, heteroatom doping,
cell and metal–air battery catalytic property for ORR
PEM fuel cell and metal–air battery Gas diffusion layer Porous/activated carbon, Conducting, high porosity, hydrophobic
carbon cloth/felt
Lithium-ion/sulfur battery; Electrode binder Cellulose, chitosan, other Polymer chain and binding ability, chemical stability,
supercapacitor polysaccharides functional groups
Lithium-ion battery; supercapacitor Separator Cellulose, fiber Electron insulator, thin film, wettability, flexibility, mechanical
strength, chemical stability
Supercapacitor Electrolyte Organic acids and salts Ion conductivity, stability over a reasonably wide potential window
Lithium-ion battery, supercapacitor Current collector Carbon sheet/cloth/felt Conducting, thin sheet, flexible, mechanical strength, chemical stability
Dye-sensitized solar cells Photosensitizer Natural dyes High absorbance of visible light, affinity to TiO2, chemically stable
Dye-sensitized solar cells Counter (positive) electrode Porous carbon High specific surface area, catalytic effect for triiodide reduction reaction
Redox flow battery 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 in material preparation have resulted in carbons with well-defined
microwave treatment. Although the biomass precursor itself is abundant pore structures. The prevailing view is that mesoporous or hierar-
and renewable, the environmental impact does arise from the high chically porous carbons have the optimum performance for super-
energy consumption in the production process, high amount of chemical capacitors. The mesopores give rise to the high specific capacitance,
activation agent used, and the resulting wastewater. Biomass-derived car- while the macropores serve as electrolyte reservoirs which improve
bon without using added activation agent has been reported using lotus the diffusion kinetics and hence the power capability. Micropores
stem.[6] During its preparation, the nascent metal ions in the biomass may also contribute to capacitance depending on its size in compar-
served as the activation agent. The as-synthesized porous carbon[6] has a ison with that of the electrolyte ions.
specific surface area of 1610 m2 g1 and a specific capacitance of As discussed above and in literature,[7] hierarchical porous carbons
174 F g1 at a scan rate of 5 mV s1 in aqueous alkaline electrolyte. The (combination of macro-, meso-, and micropores) are expected to have
embedded salts in the lotus stem acted as porogen even at relatively low superior performance as supercapacitor electrode because of the com-
contents, which favor pore formation and produce desired electrochemi- bined merits of high electrolyte accessibility, surface area, fast diffusion,
cal properties (Figure 1a–c). This self-activation method using the and transportation of electrolyte ions. The hierarchically porous struc-
embedded salts in biomass also improves the sustainability of the produc- ture could be generated by KOH activation of hydrothermally derived
tion process because less wastewater is produced. But in almost all carbonaceous biomass.[8,9] Similarly, porous carbon activated with
research and industrial practice, physical or chemical activation, or a com- nano-ZnO also showed hierarchical structure, enhanced degree of
bination of both is commonly used in order to achieve the desired prop- graphitization, and hence improved electric conductivity.[10] A recent
erties of the carbon products. Physical activation uses steam or CO2 so it study showed that molten salt technology was able to produce carbon
is greener than chemical activation. But a higher temperature is often nanobelts with controllable hierarchical pore structure. The ZnCl2 mol-
required and the specific surface area of the produced carbon is often ten salt was capable of oriented swelling and splitting as well as produc-
lower. Table 2 summarizes the specific surface area, pore volume, and ing hierarchical pores in biomass-derived carbon.[11] A combined
specific capacitance of various biomass-derived carbon materials prepared simultaneous carbonization activation and post-vacuum annealing
by different activation methods for supercapacitors. 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-
2.2. Biomass-Derived Carbon with Engineered Pore Structures like structures (Figure 1d–e).[12] Its CV curves showed rectangular
for Supercapacitor shape at a scan rate ranging from 200 to 2000 mV s1 (Figure 1f).
Symmetric supercapacitors displayed rate capability at current density of
The pore structure of biomass-derived carbon has a tremendous influence 100 A g1 and 97.6% capacitance retention over 10 000 cycles in
on its electrochemical properties as a supercapacitor electrode. Advances ionic liquid mixture electrolyte.[12]
(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 surface area, total pore volume, and particularly the mesopore volume.
structure of carbon is important for achieving both high capacitance Mesopore-dominant hierarchical porous carbon was prepared by
and rate performance in organic and ionic liquid electrolyte because of hydrothermal carbonization and KOH activation using corn straw as
the large electrolyte ion size compared to the aqueous counterpart. precursor.[13] The obtained carbon had mesopore volume of
Alkaline activation is capable of formation of interconnected pores, and 1.85 cm3 g1, specific surface area up to 1771 m2 g1, and specific
the concentration of alkali has a positive correlation with the specific capacitance of 202 F g1 at current density of 1 A g1 in organic
Biomass precursors Activators Activation method, SBET Vtot Electrolyte Measurement Maximum capacitance References
doped type (m2 g1) (cm3 g1) conditions (F g1)
Puffed rice KOH Carbonization, activation 3326 0.34 6 M KOH 0.2 A g1 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 g1 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 s1 223.9 [101]
ZnCl2
Bradyrhizobium ZnCl2 HTC, pyrolysis 1275 0.63 6 M KOH 1 A g1 358 [102]
japonicum
Rice straw KOH Carbonization, activation 1007 – 1 M 0.5 A g1 332 [103]
H2SO4
Garlic skin KOH Carbonization, activation 2818 1.327 6 M KOH 0.5 A g1 427 [104]
Chitosan Acetic acid/KOH HTC, activation 3532 1.64 6 M KOH 0.5 A g1 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 g1 286.6 [107]
doped
Agar KOH Calcination 1672 0.81 6 M KOH 1 A g1 226 [108]
electrolytes (Figure 1g–i). Despite the high rate performance and charging process during negative polarization.[4,5] Heteroatoms with
capacitance of either hierarchical or mesopore-dominant porous carbon, high electronegativity introduce chemical polarity to the neighboring
their mass density is commonly low, resulting in a low energy density. carbon atoms and hence facilitate cation adsorption. Therefore, introduc-
This trade-off between the pore volume and energy density is a crucial tion of highly electronegative heteroatoms such as fluorine and nitrogen
challenge yet to be explored in future research. into porous carbon may result in improved electrochemical performance
Originally derived from carbide materials,[14] monolithic carbon is high of the negative electrode.[18] Heteroatom doping can be combined with
in porosity and electric conductivity. As a supercapacitor electrode, it the aforementioned pore structure engineering to achieve further
shows high specific capacitance and does not require any polymeric bin- enhanced performance due to the synergistic effect of the two strategies.
der.[14] As a much cheaper alternative to carbide, biomass can also be used Recently, O-N-S-co-doped 3D hierarchical porous carbons were synthe-
to prepare monolithic carbon. The preparation is similar to powdery acti- sized from ant powder by one-step simultaneous carbonization and acti-
vated carbon but without milling pretreatment of biomass.[15] In some vation.[19] Its specific capacitance reached up to 352 F g1 at 0.1 A g1
cases, the biomass precursor is compressed in order to obtain a better con- in a two-electrode prototype supercapacitor, together with a high-rate
ductivity in the product carbon.[16] Monolithic carbon fiber aerogel capacitance of 225 F g1 at 20 A g1.[19] In addition to the electronega-
derived from cotton has specific area between 1536 and 2436 m2 g1 tive heteroatoms, phosphorus has also been reported as an effective
with pore size in the range of 1.0–4.0 nm.[15] Its specific capacitance is up dopant to enhance the oxidation stability at positive potential and adsorb
to 283 F g1 in aqueous alkaline solution with high capacitance retention hydrogen at negative potential, resulting in higher working voltages.[20]
even at high current density of 100 A g1. It is worth noting that bio- Although heteroatom doping plays multifunctional roles in improving
mass-derived monolithic carbon possesses hierarchical pore structure, dif- materials properties, it remains difficult to control the content of heteroa-
fering from the ordered micropores in carbide-derived monolithic carbon toms in the carbon matrix. Generally, a lower carbonization temperature
(Figure 1j–l). Similar to the hierarchically porous carbon, monolithic car- is beneficial to heteroatom retention.[21,22] But a higher temperature
bon is also generally low in mass density and energy density. An effective improves the electric conductivity of the carbon materials.[23]
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. 2.4. Biomass-Derived Carbon with Functional Groups for
Supercapacitor
2.3. Biomass-Derived Heteroatom-Doped Carbon for In addition to the pore structure engineering and heteroatom doping,
Supercapacitor surface functional groups of carbon also affect the charge storage prop-
erties of supercapacitor electrode. Alkaline activation or treatment is the
Heteroatom doping with nonmetallic elements such as N, O, B, S, and P most commonly investigated method to introduce oxygen-containing
is a recently emerged method to improve the performance of porous car- functional groups on the surface of carbon.[24,25] These functional
bon for supercapacitors.[17] Based on the energy storage mechanism of groups, that is, hydroxyl, carbonyl, and carboxyl groups, not only
supercapacitor, adsorption of cations in electrolyte dominates the enhance the wettability of carbon surface with electrolyte, but also
(c)
(a) (b)
(f)
(d) (e)
(i)
(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.
(i)
(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.
6. Biomass-Derived Materials as Figure 5. a) Chemical structure of CMC and b) cycle performance of the silicon electrode with three
Electrode Binder 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
Electrode binder plays a major role in binding density of 300 mA g1.[82] Copyright 2012, Wiley; e) chemical structure of water-soluble b-CD and f)
together the active material, conductive agent, cycle performance of LSB with various binders at 0.2 C.[74] Copyright 2012, Wiley.
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
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. shown promise as efficient electrocatalyst for
ORR because of its high specific area, as well as
the presence of heteroatom-induced active sites,
the conduction band of TiO2.[94] Despite being renewable and though the doping level is still hard to control during preparation and the
abundant, DSSC with natural dyes normally show a power con- mechanism for enhanced property is still under debate. The high porosity
version efficiency lower than 1.6%,[95] compared to over 10% for has also allowed these carbons to be used as host material in negative elec-
synthetic dyes such as organic metal complexes. It is suggested trode of Li-S batteries and gas diffusion layer in PEM fuel cells. Biomass-
both the efficiency and stability of natural dye-sensitized solar derived natural polymers/macromolecules have been used as high-per-
cells need to be improved in order to enhance the commercial formance electrode binder and battery separator due to their versatile
value of this technology.[94] The positive electrode or counter functional groups and hydrophilic feature in electrolyte solutions. In gen-
electrode of a DSSC receives electrons from the external circuit eral, biomass has established itself as a pivotal resource to produce various
and reduces I 3 into I in electrolyte. Platinum is the state-of-the- key materials/components in electrochemical energy storage and conver-
art counter electrode because of its electrocatalytic behavior for I 3 sion technologies, not only because of its abundance and renewable nat-
reduction. Recent research shows that biomass-derived porous ure, but also because of the high performances and desired features they
carbon doped with multi-heteroatoms can be used as an effective display in recent and ongoing research.
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 Acknowledgements
8.24%.[96] This remarkable efficiency is attributed to the porosity, This work received financial support from the Science and Technology Bureau of
specific surface area, heteroatom doping, which facilitates cat- Shenzhen (Grant No. JCYJ20170306171540744) and the Science and Technology
-
alytic reduction of I3 . Bureau of Ningbo (Grant No. 201501CX-C01006). F.Y. and S.L. contributed equally
A lead–carbon battery uses blend of lead and carbon powder as to this work.
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 Conflict of Interest
and cycle performance, particularly at partial state of charge and
deep cycle operation mode. Recent research shows that biomass- The authors declare no conflict of interest.
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 Keywords
[97]
material. biomass, battery, energy storage, fuel cells, supercapacitor