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Probing Electrochemical Behaviour of Lignocellulosic, Orange Peel

Derived Hard Carbon as Anode for Sodium Ion Battery
To cite this article: Arka Saha et al 2020 J. Electrochem. Soc. 167 090505

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 Journal of The Electrochemical Society, 2020 167 090505

Probing Electrochemical Behaviour of Lignocellulosic, Orange

Peel Derived Hard Carbon as Anode for Sodium Ion Battery
Arka Saha,1,2,=,z Tali Sharabani,1,2 Eliran Evenstein,1,2 Gilbert Daniel Nessim,1,2,z
Malachi Noked,1,2,z and Rosy Sharma1,2,=,z
1
Department of Chemistry, Bar-Ilan University, Ramat Gan 529002, Israel
2
Bar-Ilan Institute of Nanotechnology and Advanced Materials, Ramat Gan 529002, Israel

Hard carbon (HC) has emerged as potential anode material for sodium-ion batteries (SIB). However, it is plagued with several
issues like low capacity, poor cyclability, significant electrolyte degradation on interface. Realization of HC as anode requires
fundamental understanding of the effect of its porous structure/composition on electrochemical performance. Herein, we report the
use of lignocellulosic orange peel precursor for HC synthesis with tuneable surface area (SA), controlled porosity using phosphoric
acid treatment. Physicochemical properties of HC were further tailored using N-doping. The electrochemical response of various
HCs was tested with careful attention to the effect of HC SA and nitrogen content on the performances as anode. We show that
optimized bio-waste based HC exhibits Na+ specific capacity of 125 mAhg−1 at 70 mAg−1 with significantly suppressed CO2
evolution during cycling, indicating mitigated electrolyte degradation and superior performance. We believe that this study sheds
light on design rules for bio-waste low-cost precursors for synthesizing HC with tailored physical and electrochemical properties.
Using such design guidelines, is crucial for developing HC based anode materials for SIB’s.
© 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ab7c55]

Manuscript submitted January 27, 2020; revised manuscript received February 23, 2020. Published March 13, 2020. This paper is
part of the JES Focus Issue on Battery Safety, Reliability and Mitigation.

Rechargeable sodium-ion (SIB) batteries are emerging as a low-
cost alternative to lithium-ion technology for largescale applications.
In contrast to lithium, the terrestrial reserves of sodium are plentiful
in the Earth’s crust and thus offers a sustainable solution.1–6
Nevertheless, even after a decade of research, the anode for
sodium-ion remains the biggest challenge towards its practical
implementation. The inability of graphite to host Na attributed to
the lower energetic stability of sodium graphite intercalation
compound (Na-GICs) and formation potentials below the sodium
metal resulted in a serious delay of the SIB technology.7,8 In an
attempt to revive the interest in SIB, a number of research groups
have investigated various possible anode materials acquiring higher
energy density, superior power performances, and meaningfully
prolonged stability.
A quite large number of metals and non-metals such as tin,
antimony, bismuth, lead, germanium, phosphorus etc. were reported
to exhibit reversible alloying with sodium thereby demonstrating
moderately high theoretical capacity.9–17 Similarly, transition metal
(M = Fe, Co, Cu, Mn, Ni, Mo) oxides, chalcogenides, nitrides,
phosphides, and selenides were also rigorously investigated as
conversion type anodes for hosting Na+. Nevertheless, despite the
promising properties of such materials (alloying, conversion and
conversion alloying), their electrochemical performance in Na cells
is strongly affected by large volumetric and structural changes, poor
cycling stability, and low energy efficiency governed by the high
voltage hysteresis. In addition, cost and toxicity signify two
additional factors to be considered for transition metal-based
electrodes.9,18
In comparison to all the aforementioned options, carbon-based
materials were found to be superior in terms of price, accessibility
and tuneable electronic and physical properties, and thus considered
as one of the most important negative electrodes in alkali ion battery
systems.19–26 Non- graphitic carbon-based materials generally called
“HC” have been considered as a potential candidate for the SIB
anode materials.27–33 When we consider commercial HC as an
anode, high temperature synthesis, production cost and poor rate
capability have been considered as major drawback in their
implementation.19,34 Furthermore, the large surface area and com-
plex porous nature of HC also leads to detrimental parasitic reactions
on the interface as well as results in interference from non-faradaic
processes. It is now well-known that if the structure and physical
properties of HC can be modulated, a controlled charge storage
mechanism can be observed.35,36 Consequently, during past few
years major research interest for suitable Na anode has been
concentrated for designing low cost HC-based anode materials
because of their positive aspects of reversible Na-ion de-(intercala-
tion) attributed to the multiple host sites.20,37,38 Lignocellulosic
biomass derived from fruit waste is one of the cheap and available
sources for producing HC, however only few studies are available
for lignocellulosic biomass-derived carbons for Na-anode.39–42 It
was shown that structural modification of these bio mass materials,
could modulate the physical properties and performances by dissol-
ving the lignocellulosic part from the starting materials.39,40 A large
amount of orange peel is generated as a waste product of citrus
processing industries which represents about 50%–60% of the
processed fruit.43–45 The traditional waste management of orange-
peel is either not economically attractive or mature enough to be
fully implemented and have environmental concerns thus most of it
is used as a fodder or for landfilling of sites.Since, orange peel is
very rich in lignocellulosic content, herein, we report the use of
orange-peels as lignocellulosic precursor for fabricating HC by
carefully tuning their physical properties using acid treatment. In this
report, we have carefully investigated the impact of phosphoric acid
(H3PO4) leaching on the structure, surface area and electrochemical
performance of the derived carbon as anode material for SIBs.
Further stabilization and surface passivation of the fabricated carbon
was achieved using optimized doping with nitrogen. In operando
online electrochemical mass spectrometry was also employed to
probe the CO2 evolution during cell performance in order to study
the efficacy of doping in mitigating electrolyte degradation. We
believe that our reported methodology and results will enlighten
the readers to pursue greener, environmental friendly and simple
synthesis protocols for fine-tuned carbon materials utilizing the
lignin-rich bio-waste.

Experimental
=
These authors contributed equally to this work.
z
E-mail: arkasahacsmcri.edu@gmail.com; Gilbert.Nessim@biu.ac.il; Synthesis of orange peel based HC.—The sun-dried orange
malachi.noked@biu.ac.il; rrosysharma@gmail.com peels were grinded and subjected to acid treatment (Phosphoric acid,
 Journal of The Electrochemical Society, 2020 167 090505

Sigma Aldrich, 85%) for 1, 7, and 14 d respectively. After the acid

treatment, samples were washed vigorously with deionised water to
remove excess phosphoric acid and then dried at 100 °C for 48 h.
The resulting powder was then carbonized at 900 °C for 1 h in an
argon atmosphere at a heating rate of 1 °C min−1. Depending on the
duration of acid treatment, the obtained materials were referred to as
C-1D, C-7D and, C-14D respectively throughout the manuscript.
The synthesis procedure is described in Fig. 1.
For further optimization, C-14D was doped with nitrogen using
melamine as the nitrogen source. The doping was carried out by
mixing melamine and C-14D in desired weight proportion followed
by carbonisation at 800 °C for 1 h in argon atmosphere at a heating
rate of 5 °C min−1. The obtained material was labelled as C-14D-XN
where X is the wt. percent of melamine used for doping. (X = 5%,
7%, 10%).
The synthesized HC were characterized using SEM, XRD, BET,
TEM and Raman spectroscopy. The instrument specification and
other details related to the characterization are given in section S1 of
the supporting information.
Figure 1. Schematic diagram representing synthesis of HC using orange
Fabrication of electrode and cell assembly.—Composite elec- peel biomass.
trodes were prepared by mixing 87% HC, 8% KS 6 graphite and 5%
PVDF in NMP. The mixing was carried out using a Thinky mixer
To probe the crystallographic properties of the fabricated HC
(ARV-310/ARV-310LED) at 2000 rpm, 40 kPa for 3 min 60-micron
materials, XRD measurements were carried out. XRD patterns
thick layer of the prepared slurry was then coated on a clean and
observed for C-1D, C-7D and C-14D are presented in Fig. 3. All
polished Cu foil using “Dr. blade” and dried overnight at 100 °C.
the three HC materials exhibited two broad peaks corresponding to
After rolling, the anodes of 12 mm diameter (∼1.6 mg loading) were
(002) and (101) planes of graphitic carbon around 23.1 and 43.8°
punched and dried overnight under vacuum at 100 °C.
respectively indicating the effective formation of layered HC
The HC half cells were assembled using coin-type cells (2032,
materials using the orange peel precursor. The prominent (002)
NRC, Canada) with sodium metal as anode, 1 M NaPF6 in EC: FEC
peak at 2Ѳ = 23.1 reflects the degree of graphitization in all carbon
(9:1 wt%) as the electrolyte and Celgard 3501 as the separator.
materials. From Fig. 3, it can be seen that C-1D and C-7D exhibits a
Galvanostatic charge/discharge was carried out using BCS-805
relatively sharp, intense (002) peak whereas a suppressed, broad
battery cycler (Bio-logic Science instruments) in a potential window
peak was observed for C-14D. In addition, for C-14D, (002) plane
of 0.01−3 V.
was slightly shifted towards lower diffraction angle which indicates
a decrease in graphitic nature leading to an increase in the inter-layer
Online electrochemical mass spectroscopy.—Cells were as-
distance. These denatured graphitic domains are expected to have
sembled inside the Ar filled glovebox with different HC (ø 12 mm)
random orientations leading to X-ray scattering in different direction
against Na (ø 10 mm) in 1 M NaPF6 in EC: FEC electrolyte. Two
ultimately resulting in a broader peak. This indicate that the duration
glass fiber separators (ø 29 mm) were placed between the cathode and
of phosphoric acid treatment has a profound influence on the
anode. The cell was then taken out of the glove box and was
crystallinity of the carbon material. Furthermore, the broadening
connected to the OEMS capillary using one of the Swagelok valves
of the (002) plane with prolong acid treatment also reflects
attached to the head space of the cell. The electrochemical measure-
the amorphization of the HC as well as increased porosity of the
ments were carried out using VSP-potentiostat (Bio-logic Science
material.48 The generation of pores are expected to enhance
instruments) in a potential window of 0.01−3 V.
the ion adsorption and render the surface of carbon more accessible
for Na-intercalation which can effectively increase the capacity and
Result and Discussion the rate performance of the system. It is previously reported that
Characterization.—In order to investigate the effect of acid
leaching on the material structure and porosity, different batches of
HC were extensively characterized using microscopy, spectroscopic
and electrochemical tools.
Figure 2 shows SEM images of the synthesized carbon materials
obtained after annealing in Ar atmosphere. From the SEM images it
can be clearly seen that duration of acid treatment resulted in slight
variation in the morphology of the particles. However, the careful
comparison of SEM images indeed pointed out certain changes in
the particle size primarily dominated by the dissolution of ligno-
cellulosic part as a function of acid treatment time. Presence of big
flake like structures can be clearly seen in Fig. 2a which found to be
significantly reduced with prolonged H3PO4 acid treatment. Instead,
appearance of small particles were observed which tend to be
clustered together in the C-14D. The slight decrease in the particle
size with short term acid treatment can be attributed to the dissolution
of less stable minor components of the biomass (2b). While the
prolong acid treatment results in the dissolution of more stable
component such as cellulose, hemicellulose and lignocellulose.39 As
a result of the aforementioned dissolution of polymer framework, a
decrease in particle size is observed with the increasing duration of Figure 2. SEM images of (a) as prepared HC, (b) C-1D, (c) C-7D and
acid treatment Figs. 2c and 2d.39,46,47 (d) C-14D.
 Journal of The Electrochemical Society, 2020 167 090505
Figure 3. XRD pattern of Orange Peel derived HC through H3PO4 acid
treatment.
Figure 4. Comparative voltage profile of the 3rd cycle corresponding to
C-1D, C-7D and C-14D cycled at a current of 40 mA g−1.
non-metals (N, S) prefers doping in the interlayer and pores of HC
leading to larger inter layer distances.49–51 So nitrogen doping is
attempted to further optimize the physical properties of C-14 D and
the results are shown in Fig. S1a is (available online at stacks.iop.
org/JES/167/090505/mmedia). A comparative XRD analysis was
also carried out demonstrating the difference in the XRD patterns of
C-14D, double annealing in absence (C-14D-0N) and presence of
melamine (C-14D-5N) (Fig. S1b). Both the double annealed samples
demonstrated enhanced peak intensity corresponding to (002) plane
in comparison to the C-14D sample. The increased intensity of (002)
plane indicated better graphitic nature of the double annealed
samples irrespective of the presence and absence of melamine.
Nevertheless, the shift of (002) peak to higher diffraction angles for
the C-14D-0N indicated a significant decrease in the interlayer
distance which make the material less efficient for the intercalation
process. However, an optimization between the preserved graphitic
nature with a balanced interlayer distance was achieved in presence
of melamine and as a result the N-doped sample (C-14D-N) was
used for further electrochemical characterizations.
Nitrogen adsorption-desorption isotherms and pore size distribu-
tion were next recorded to further ensure the nature of porosity in the
materials with prolong acid treatment time. Brunauer–Emmett–Teller
(BET) surface area of C-14D was found to be 530 m2/g which was
much higher in comparison to the 5 m2/g for C-1D, 40 m2/g for C-6D
indicating the substantial enhancement in the surface area upon
prolonged acid treatment. The porous structure of these materials
was also studied by assigning the nature of the isotherms to the
IUPAC classification. The isotherm corresponding to C-14D is
assignable to type IV indicating its mesoporous nature with varying
pore size from 10 to 20 nm (Figs. S2a, S2e), whereas, C-6D exhibits
Type-II isotherm, indicating the mesoporous nature with bigger pore
size distribution (25 nm or above) (Figs. S2b, S2f). However, the low
porosity was reflected by C-1D through its type VI isotherm and pore
size distribution (Figs. S2c, S2g). Nitrogen doping to the C-14D HC
material (C-14D-N), decrease it overall surface area from 530 m2/g to
75 m2/g but exhibits well organised mesopores (Fig. S2d, S2h). The
BET results are in good agreement with XRD analysis as it can be
concluded that the duration of phosphoric acid treatment has a strong
impact on both the porous structure and surface area of the carbon
material. Both characterizations, indicate that short time acid treat-
ment (1 d) results in carbon material with low porosity and low
surface area, whereas, prolong acid treatment (7 d) result in generation
of mesopores that increase on further exposure to H3PO4 (14 d). The
difference in the porous structure of carbon material resulting from
the different duration of acid treatment can be explained on the basis
of increased dissolution of more stable lignocellulosic part with
prolong exposure to acid that results in different distribution of the
micro and meso pores in the carbon material.39,52,53 The lower surface
area of the nitrogen doped (C-14D-N) is quite expected and can be
explained on the basis of an additional heat treatment step and non-
metal doping of the C-14D which might induce pore closure. This
synthesis approach enabled us to farther study the effect of carbon
porosity, and nitrogen doping on the electrochemical response as
described below.
Electrochemical performance.—The effect of acid treatment on
the sodium-ion storage ability of the fabricated carbon was inves-
tigated by employing galvanostatic charge-discharge cycling. The
comparative voltage profile corresponding to the 3rd cycle of C-1D,
C-7D and C-14D is presented in Fig. 4. The voltage profiles clearly
reveal the direct dependence of electrochemical performance over
the acid treatment time and demonstrates the superior behaviour of
C-14D which is the sample prepared using long acid treatment. The
improved performance of C-14D can be explained on the basis of
high meso-porosity achieved after long acid treatment which is
known to be beneficial for sodium ion storage.54 The increased
contribution of both the high voltage and low voltage sloping regions
in the voltage profile corresponding to C-14D suggests its enhanced
ability to store Na+ both by intercalation into layers as well as filling
of mesopores.
The possibility of higher contribution from the capacitive
accumulation and double layer adsorption of Na+ in C-14D cannot
be completely ruled out, however based on the surface area with
careful assumption of 25μF/cm2 (BET), the EDL over 2 V of
discharge should not exceed 25 mAh g−1 therefore it is not the
major cause for the difference.55–57 In fact, when the surface area of
the C-14D is significantly decreased by nitrogen doping, only a
slight effect on the overall capacity is obtained, strongly support the
claim that the capacity of C-14D is mostly through Na+ insertion.58
As, C-14D clearly out-performed in comparison to all other samples,
it was used for further investigations.
The charge, discharge capacities and associated coulombic
efficiencies of C-14D over the long-term cycling is depicted on
Fig. 5. It can be clearly inferred from the data presented in the figure
that C-14D exhibited stable performance over more than 150 cycles
with a coulombic efficiency of ∼99%. It is well known that, HC with
low surface areas and an optimized balance between open and closed
pores, are well-suited for sodium ion insertion in order to minimize
electrolyte decomposition during the first cycle.35 Thus, it is crucial
to optimize the disordered carbons with sufficiently minimum
surface areas in order to achieve the maximum electrochemical
 Journal of The Electrochemical Society, 2020 167 090505
Figure 5. long-term cycling performance and associated coulombic effi-
ciency of C-14D cycled at a current of 70 mA g−1.
Figure 6. Discharge capacity of C-14D and C-14D-7N (a) as a function of
different current density, and, (b) as a function of cycles at 70 mA g−1.
activity. Consequently, to further stabilize C-14D, and optimize its
surface area, nitrogen doping with 5, 7 and 10% melamine was
attempted. Amongst, all the three concentration, sample doped with
7% melamine showed the best performance (Fig. S3) and thus used
for further studies.
Figure 7. In operando online electrochemical mass spectrometry investiga-
tion of CO2 evolution during cycling of C-14D and C-14D-7N as a function
of applied potential.
The rate performance of the C-14D and C-14D-7N doped sample
is presented in Fig. 6a. A clear stabilization of the electrochemical
response can be witnessed from the rate performance of C-14D-7N
in comparison to the C-14D. Although the capacity delivered by C-
14D at low-rates are slightly higher than the doped sample, a clear
enhancement in the response of C-14D-7N in comparison to C-14D
were observed at higher currents. The superior behavior demon-
strated by the N-doping was further confirmed during long-term
cycling performance, where, the doped sample exhibited improved
stability as well as higher capacity after the 10th cycle (Fig. 6b). The
improved performance of the N-doped sample can be ascribed to the
presence of doping‐induced defects which facilitates the Na+
diffusion kinetics and resulted in better rate performance.
Furthermore, we suggest that the optimized surface area and pore-
structure achieved upon N-doping resulted in suppressed electro-
chemical degradation and is the reason behind superior performance
of C-14D-7N.
The evolution of CO2 during electrochemical performance is
known to arise as a byproduct of alkyl carbonates chemical and
electrochemical degradation on the surface of electrodes subjected to
voltages beyond the anodic\cathodic stability of the electrolyte.59
Thus, to confirm the suppressed electrolytic degradation, in oper-
ando evolution of CO2 in response to the applied potential was
investigated using online electrochemical mass spectroscopy.
The comparative plot demonstrating the evolution of CO2 from
doped and undoped sample is presented in Fig. 7. A substantial
decrease in the CO2 evolution corresponding to the doped sample
was witnessed which indicated suppressed electrolyte degradation
on the C-14D-7N electrode/electrolyte interface in comparison to the
undoped C-14D sample and thus explains the better performance.
The lower CO2 evolution in the doped sample can be ascribed to the
lower surface area and closed pores due to the additional carboniza-
tion steps and thus further indicates the importance of optimized
pore structure and surface area of the carbon anode materials in
achieving stable battery cycling.
Conclusions
In this study, we reported the use of a lignocellulose rich, orange
peel biomass as a precursor for synthesizing HC using acid treatment
and carbonization procedures. In-depth investigations were carried
out to study the effect of acid treatment duration on the size and type
of pores and surface area of the generated material. It was concluded
that prolonged acid treatment leads to development of mesoporous
characteristic and increased surface area that leads to improved Na+
storing ability by increasing both the intercalation in layers as well
as filling of microporous. In addition to control over the surface area
 Journal of The Electrochemical Society, 2020 167 090505
we optimized the HC using N-doping that resulted in significantly
improved electrochemical performance and suppressed electrolyte
degradation which was confirmed by in operando investigations of
CO2 generation using online electrochemical mass spectrometry
measurements. We believe that this study provide synthesis guide-
lines for optimization of HC’s parameters based on bio-waste as
low-cost precursors for synthesizing carbon materials with tailored
physical and electrochemical properties. This is an important step
toward realization of Bio-mass based HCs anode materials for SIB’s.
Acknowledgments
A.S. and Rosy are thankful to the planning and budgeting
committee of the council of higher education for awarding post-
doctoral research fellowship. M.N. and D.N. are thankful to the
Israeli council of higher education for Alon Fellowship. The project
was conducted through the support of INREP, and through the
support of IMOE.
ORCID
Malachi Noked https://orcid.org/0000-0001-8995-0632
References
1. M. D. Slater, D. Kim, E. Lee, and C. S. Johnson, Adv. Funct. Mater., 23, 947
(2013).
2. E. D. l. Llave, V. Borgel, K. J. Park, J. Y. Hwang, Y. K. Sun, P. Hartmann,
F. F. Chesneau, and D. Aurbach, ACS Appl. Mater. Interfaces, 8, 1867 (2016).
3. C. X. Zu and H. Li, Energy Environ. Sci., 4, 2614 (2011).
4. H. Pan, Y. S. Hu, and L. Chen, Energy Environ. Sci., 6, 2338 (2013).
5. J.-Y. Hwang, S.-T. Myung, and Y.-K. Sun, Chem. Soc. Rev., 46, 3529 (2017).
6. K. Kubota and S. Komaba, J. Electrochem. Soc., 162, A2538 (2015).
7. W. Wan and H. Wang, Int. J. Electrochem. Sci., 10, 3177 (2015).
8. K. Nobuhara, H. Nakayama, M. Nose, S. Nakanishi, and H. Iba, J. Power Sources,
243, 585 (2013).
9. H. Zhang, I. Hasa, and S. Passerini, Adv. Energy Mater., 8, 1702582 (2018).
10. A. Darwiche et al., J. Am. Chem. Soc., 134, 20805 (2012).
11. D. Su, S. Dou, and G. Wang, Nano Energy, 12, 88 (2015).
12. H. Che, H. Che, S. Chen, Y. Xie, H. Wang, K. Amine, X.-Z. Liaoa, and Z.-F. Ma,
Energy Environ. Sci., 10, 1075 (2017).
13. L. D. Ellis, B. N. Wilkes, T. D. Hatchard, and M. N. Obrovac, J. Electrochem. Soc.,
161, 416 (2014).
14. J. W. Wang, X. H. Liu, S. X. Mao, and J. Y. Huang, Nano Lett., 12, 5897 (2012).
15. P. R. Abel, Y.-M. Lin, T. D. Souza, C.-Y. Chou, A. Gupta, J. B. Goodenough,
G. S. Hwang, A. Heller, and C. B. Mullins, J. Phys. Chem. C, 117, 18885 (2013).
16. N. Yabuuchi, Y. Matsuura, T. Ishikawa, S. Kuze, J.-Y. Son, Y.-T. Cui, H. Oji, and
S. Komaba, Chem. Electro. Chem, 1, 580 (2014).
17. L. D. Ellis, T. D. Hatchard, and M. N. Obrovac, J. Electrochem. Soc., 159, 1801
(2012).
18. F. Klein, B. Jache, A. Bhide, and P. Adelhelm, Phys. Chem. Chem. Phys., 15, 15876
(2013).
19. X. Dou, I. Hasa, D. Saurel, C. Vaalma, L. Wu, D. Buchholz, D. Bresser, S. Komaba,
and S. Passerini, Mater. Today, 23, 87 (2019).
20. M. Anji Reddy, M. Helen, A. Groß, M. Fichtner, and H. Euchner, ACS Energy Lett.,
3, 2851 (2018).
21. J. Hu, M. Noked, E. Gillette, Z. Gui, and S. B. Lee, Carbon N. Y., 93, 903 (2015).
22. H. Song et al., Adv. Energy Mater., 8, 1701203 (2018).
23. Y. Kuang et al., Adv. Energy Mater., 8, 1802398 (2018).
24. F. Jiang, T. Li, Y. Li, Y. Zhang, A. Gong, J. Dai, E. Hitz, W. Luo, and L. Hu, Adv.
Mater., 30, 1703453 (2018).
25. J. Hu, M. Noked, E. Gillette, F. Han, Zhe Gui, C. Wangc, and S. B. Lee, J. Mater.
Chem. A, 3, 21501 (2015).
26. J. Hu, C.-F. Sun, E. Gillette, Z. Gui, Y. Wang, and S. B. Lee, Nanoscale, 8, 12958
(2016).
27. H. Zhua et al., Nano Energy, 33, 37 (2017).
28. F. Shen, H. Zhu, W. Luo, J. Wan, L. Zhou, J. Dai, B. Zhao, X. Han, K. Fu, and
L. Hu, ACS Appl. Mater. Interfaces, 7, 23291 (2015).
29. H. Li et al., ACS Appl. Mater. Interfaces, 8, 2204 (2016).
30. F. Zhang, Y. Yao, J. Wan, D. Henderson, X. Zhang, and L. Hu, ACS Appl. Mater.
Interfaces, 9, 391 (2017).
31. A. Saha, A. Paul, D. N. Srivastava, and A. B. Panda, Int. J. Hydrogen Energy, 43,
21655 (2018).
32. A. Saha, P. Bharmoria, A. Mondal, S. C. Ghosh, S. Mahanty, and A. B. Panda,
J. Mater. Chem. A, 3, 20297 (2015).
33. S. Nandi, A. Saha, P. Patel, N. H. Khan, R. I. Kureshy, and A. B. Panda, ACS Appl.
Mater. Interfaces, 10, 24480 (2018).
34. S. Bublil, T. Sharabani, M. Turgeman, J. Grinblat, Y. Elias, M. Noked,
M. F. Greenstein, and D. Aurbach, Langmuir, 35, 11670 (2019).
35. B. Xiao, T. Rojo, and X. Li, Chem. Sus. Chem, 12, 133 (2019).
36. B. Zhang, C. M. Ghimbeu, C. Laberty, C. Vix-Guterl, and J.-M. Tarascon, Adv.
Energy Mater., 6, 1501588 (2016).
37. L. Xiao, H. Lu, Y. Fang, M. L. Sushko, Y. Cao, X. Ai, H. Yang, and J. Liu, Adv.
Energy Mater., 8, 1703238 (2018).
38. S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama,
A. Ogata, K. Gotoh, and K. Fujiwara, Adv. Funct. Mater., 21, 3859 (2011).
39. X. Dou, I. Hasa, D. Saure, M. Jauregui, D. Buchholz, T. Rojo, and S. Passerini,
Chem. Sus. Chem, 11, 3276 (2018).
40. K. Subramani, N. Sudhan, M. Karnan, and M. Sathish, ChemistrySelect, 2, 11384
(2017).
41. V. Simone, A. Boulineau, A. de Geyer, D. Rouchon, L. Simonin, and S. Martinet,
J. Energy Chem., 25, 761 (2016).
42. L. Wu, D. Buchholz, C. Vaalma, G. A. Giffin, and S. Passerini, ChemElectroChem,
3, 292 (2016).
43. R. S. Orozco, P. B. Hernández, G. R. Morales, F. U. Núñez, J. O. Villafuerte,
V. L. Lugo, N. F. Ramírez, C. E. B. Díaz, and P. C. Vázquez, Bio. Resources, 9,
1873 (2014).
44. M. A. Martín, J. A. Siles, A. F. Chica, and A. Martín, Bioresour. Technol., 101,
8993 (2010).
45. D. Mamma and P. Christakopoulos, Waste Biomass Valorization, 5, 529 (2014).
46. M. Lara-Serrano, S. Morales-delaRosa, J. M. Campos-Martín, and J. L. G. Fierro,
Appl. Sci., 9, 1862 (2019).
47. J. van Spronsen, M. A. T. Cardoso, G.-J. Witkamp, W. de Jong, and M. C. Kroon,
Chem. Eng. Process. Process Intensif., 50, 196 (2011).
48. E. R. Buiel, A. E. George, and J. R. Dahn, Carbon N. Y., 37, 1399 (1999).
49. Z. Hong, Y. Zhen, Y. Ruan, M. Kang, K. Zhou, J. M. Zhang, Z. Huang, and
M. Wei, Adv. Mater., 30, 1802035 (2018).
50. Z. Li et al., Adv. Energy Mater., 7, 1 (2017).
51. L. Qie, W. Chen, X. Xiong, C. Hu, F. Zou, P. Hu, and Y. Huang, Adv. Sci., 2
(2015).
52. X. Dou, I. Hasa, M. Hekmatfar, T. Diemant, R. J. Behm, D. Buchholz, and
S. Passerini, Chem. Sus. Chem, 10, 2668 (2017).
53. M. C. Baquero, L. Giraldo, J. C. Moreno, F. Suárez-Garcı, A. Martinez-Alonso, and
J. M. D. Tascon, J. Anal. Appl. Pyrolysis, 70, 779 (2003).
54. E. Buiel, A. E. George, and J. R. Dahn, J. Electrochem. Soc., 145, 2252 (1998).
55. M. Noked, A. Soffer, and D. Aurbach, J. Solid State Electrochem., 15, 1563 (2011).
56. G. Salitra, A. Soffer, L. Eliad, Y. Cohen, and D. Aurbach, J. Electrochem. Soc.,
147, 2486 (2000).
57. C. Lin, J. Electrochem. Soc., 146, 3639 (1999).
58. N. Sun, Z. Guan, Y. Liu, Y. Cao, Q. Zhu, H. Liu, Z. Wang, P. Zhang, and B. Xu,
Adv. Energy Mater., 9, 1901351 (2019).
59. K. Uta Schwenke, S. Solchenbach, J. Demeaux, B. L. Lucht, and H. A. Gasteiger,
J. Electrochem. Soc., 166, A2035 (2019).