DOI: 10.1002/cssc.
201801879 Minireviews
Hard Carbon as Sodium-Ion Battery Anodes: Progress and
Challenges
Biwei Xiao,[a] Tejfilo Rojo,*[b, c] and Xiaolin Li*[a]
Hard carbon (HC) is the state-of-the-art anode material for
sodium-ion batteries due to its excellent overall performance,
wide availability, and relatively low cost. Recently, tremendous
effort has been invested to elucidate the sodium storage
mechanism in HC, and to explore synthetic approaches that
can enhance the performance and lower the cost. However,
disagreements remain in the field, particularly on the funda-
mental questions of ion transfer and storage and the ideal HC
1. Introduction
Sodium-ion batteries (SIBs), with a similar mechanism to that
of lithium-ion batteries (LIBs) and potentially lower cost, are
emerging as the most close-to-market beyond-LIB technology
for grid-scale energy storage.[1, 2] The development of LIBs pro-
vides rich experience for the development of SIBs. Many SIB
cathode materials were developed by benefiting from the LIB
counterparts. However, the intrinsic dissimilarities between lith-
ium and sodium, such as ionic radius (0.71 a for Li + and 1.03 a
for Na + ) and electrochemical potential (2.71 V vs. standard hy-
drogen electrode (SHE) for Na/Na + and 3.04 V vs. SHE for Li/
Li + ), lead to some inconsistencies and sometimes even mis-
guidance in research practices.[1, 3, 4] Efforts have been made to
overcome the discrepancies in the development of SIBs,[5] and
great progress has been achieved in recent years.[6] Long-life
SIBs with an energy density of over 100 Wh kg@1,[7] which is
close to those of LiFePO4 and LiMn2O4 cells, have been demon-
strated in large-format cells. Although there are numerous re-
ports on SIB cathode materials with equivalent performance to
that of some of the LIB cathode materials, the anode material
has been detrimental to the performance of the full cell.[8]
[a] Dr. B. Xiao, Dr. X. Li
Energy & Environment Directorate
Pacific Northwest National Laboratory
Richland, WA, 99352 (USA)
E-mail: xiaolin.li@pnnl.gov
[b] Dr. T. Rojo
CIC energiGUNE, Parque Tecnoljgico de ]lava
C/ Albert Einstein 48, 01510 MiÇano (Spain)
E-mail: teo.rojo@ehu.eus
[c] Dr. T. Rojo
Departamento de Qu&mica Inorg#nica, Universidad del Pa&s Vasco
UPV/EHU, P.O. Box 664, 48080 Leioa (Spain)
The ORCID identification number(s) for the author(s) of this article can
be found under:
https://doi.org/10.1002/cssc.201801879.
ChemSusChem 2019, 12, 133 – 144
structure for high performance. This Minireview aims to pro-
vide an analysis and summary of the theoretical limitations of
HC, discrepancies in the storage mechanism, and methods to
improve the performance. Finally, future research on develop-
ing ideal structured HCs, advanced electrolytes, and optimized
electrolyte–electrode interphases are proposed on the basis of
recent progress.
Hard carbon (HC) is a state-of-the-art anode material for
SIBs. Ion transfer and storage in HC were reported at almost
the same time as that of intercalation into graphite and other
kinds of carbon materials for LIBs.[9] HC was known to have a
higher capacity and better compatibility with ether electro-
lytes, relative to graphite, which was found to experience exfo-
liation because of solvent intercalation.[10, 11] Competition be-
tween HC and graphite continued until ethylene carbonate
(EC)-based electrolyte was introduced. The stable solid–electro-
lyte interphase (SEI) generated by EC enabled a wide voltage
window, high specific capacity, and long cycling stability of
graphite without exfoliation concerns, and it finally became
the state-of-the-art anode for LIBs.[12] Recently, with knowledge
of the similarities and differences between sodium and lithium
ions, scientists started to carefully reconsider the electrolyte
systems, the role of the SEI, and other properties required for
high-performance HC anodes for SIBs.[13–19] A fundamental un-
derstanding of the HC structure, ion-transfer and storage
mechanisms, and interaction with different electrolytes is es-
sential for improving the performance of HC and has attracted
unprecedented attention.[4, 13, 14, 20] Herein, we focus on recent
progress and future challenges in understanding three scientif-
ic problems related to HC as SIB anodes: 1) HC structure and
the limit in capacity; 2) the ion-storage mechanism in HC; and
3) the SEI and electrolyte system.
2. HC Structure and Sodium-Ion-Storage
Mechanism
HC is non-graphitizable and the structure at the molecular
level is much more complicated than that of the long-range
ordered layered structure of graphite. The unique structure in-
trinsically determines that 1) HC has multiple types of storage
sites for the reversible accommodation of sodium ions, and
2) the limit f capacity of HC, unlike graphite, remains elusive.
133 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Minireviews
Understanding these two fundamental questions is critical to sheets and expanded interlayer spacing, as well as micropores
guide the development of high-performance HC materials. formed between these microstructures (Figure 1).[21] Such a
structure requires the carbon precursor to be thermosetting
and contain highly branched and cross-linked structures.
2.1. Sodium-ion-storage sites in the “house of cards” struc- During pyrolysis at above 1000 8C, the branches prevent the
ture and estimation of the limit of capacity occurrence of long-range ordered graphitization. Even with a
higher pyrolysis temperature (above 3000 8C), the final product
Among the proposed structures of HC, the house of cards
is non-graphitizable glassy carbon with lots of closed pores.[22]
model currently is widely adopted as the model structure to
The intrinsic difference of the structure between graphite
study the ion-storage mechanism by battery material scien-
and HC results in different ion-storage sites for the two types
tists.[21] It is believed that HC differs from graphite in that it is
of carbon anodes. For graphite, the ions are stored mainly be-
not formed by the periodic stacking of graphene layers with
tween the graphitic layers. The theoretical capacity for the ion
well-defined spacing (3.3 a); instead, it consists of randomly
storage of graphite is largely based on the intercalation com-
distributed turbostratic domains with curved graphene nano-
pound of alkali-metal ions and graphite. By using lithium-ion
storage in graphite as an example, a theoretical capacity of
Biwei Xiao is currently a postdoctoral
372 mAh g@1 can be concluded by simply assuming that every
research associate at Pacific Northwest
six carbon atoms capture one lithium ion to form a stage I
National Laboratory. He received his
graphite intercalation compound (GIC): LiC6.[23]
Bachelor degree in materials science
There are several different ion-storage sites for HC materials,
and engineering from Sichuan Univer-
including 1) intercalation between graphene sheets in turbos-
sity, P.R. China, in 2011, and obtained
tratic graphitic structures; 2) storage in closed micropores; and
his Ph.D. degree from Prof. Xueliang
3) surface and defect absorption (there are many more defects
Sun’s group at the University of West-
in HC than those in graphite). Figure 1 shows a schematic de-
ern Ontario in 2017. His research focus-
scription of ion storage at different sites and the dictating pa-
es on cathode materials for both lithi-
rameters. Although complications of structure variations
um- and sodium-ion batteries, carbon
during synthesis of the materials make it almost impossible to
materials, and synchrotron radiation
get a specific value as the “theoretical capacity” for a certain
techniques.
ion-storage type in HC, it is very important to have an estab-
lished estimation of the capacity limit. Such an estimation will
Tejfilo Rojo received his Ph.D. in
provide guidance for the structural design of HCs for high-per-
chemistry from the University of the
formance anodes.
Basque Country in 1981. He became a
The capacity limits of sodium-ion storage at each kind of
full-time professor of inorganic chemis-
storage site in HC were considered individually. First, consider-
try at UPV/EHU in 1992. His research
ing sodium-ion intercalation between the graphene sheets of
has been focused on solid-state
the turbostratic graphitic structures, graphene/graphene oxide
chemistry and materials science. Since
sheets with a large interlayer spacing have been used as
2010, he has been Scientific Director of
model systems to estimate the maximum contribution from
the Electrochemical Energy Storage
sodium intercalation. Theoretical calculations showed that the
Area at CIC energiGUNE, leading re-
intercalation of Na ions into pristine graphite had a positive
search on batteries and supercapaci-
formation energy for NaC6 or NaC8 (Figure 2 a)[24] and negative
tors. Appointed in 2015 as an academ-
sodiation potential at low Na contents (Figure 2 b).[25] Both indi-
ic member of the Royal Spanish Academy of Exact, Physical, and
cate that Na intercalation into graphite is thermodynamically
Natural Sciences, in 2016 he was named a member of the Working
unstable compared with Na plating (0 V), and it cannot form
Party on Chemistry and Energy of EuCheMS (European Chemical
stage I structures of NaC6 or NaC8.[24, 26–28] The results are consis-
Science).
tent with the experimental low specific capacity of Na electro-
chemical/vapor intercalation into graphite, which is generally
Xiaolin Li is a senior scientist at Pacific
only able to form a NaC70 compound with a capacity of
Northwest National Laboratory. He re-
31 mAh g@1.[28] However, the sodiation potential has good cor-
ceived his B.S. and Ph.D. in chemistry
relation to the interlayer spacing and percentage of NaC8 for-
from Tsinghua University and conduct-
mation (Figure 2 b). It increases with the increasing percentage
ed his postdoctoral research in Prof.
of NaC8 and reaches a maximum of about 40 % NaC8 forma-
Hongjie Dai’s group at Stanford. His
tion, then oscillates at about 0 V, with a spread of about
current research interest is on the
: 0.1 V, and an interlayer spacing always > 4.2 a. Further calcu-
design of materials and fundamental
lations show that the sodiation potential increases with the ini-
electrochemistry for rechargeable bat-
tial interlayer distance between two graphene sheets and the
teries and fuel cells.
defects. Figure 2 c shows that the sodiation potential is > 0 V if
the interlayer distance is > 3.94 a, or with one point defect of

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Figure 1. Schematic illustration of the differences in ion storage between graphite and HC.
MV or DV in the 6 V 6 V 2 model and an interlayer distance of
3.4 a.[25] Practical HC materials usually have an interlayer spac-
ing of about 3.8 a and many defects in the disordered struc-
ture. Hence, intercalation may form 100 % NaC8, which delivers
a theoretical capacity of 279 mAh g@1 at close to 0 V.[29] Recent-
ly, expanded graphite with an interlayer spacing of 4.3 a was
prepared experimentally, and realized a reversible capacity for
Na storage of about 284 mAh g@1, which corroborated results
of the above theoretical calculations.[30] It is reasonable to
assume that intercalation contributes a maximum capacity of
about 279 mAh g@1 for sodium-ion storage in HC.
Second, the capacity limit of absorption/clustering of
sodium ions in pores is estimated from the pore-filling model,
which is dependent on the amount and size of the closed
pores. Based on the space-filling model, which assumes that
the sodium ions adsorb on the surface of the porosities and
fully fill them to form sodium metal, the specific capacity, Q,
would be given by Equation (1):
Q ¼ 1FV=3:6A
in which 1 is the density of sodium metal (0.97 g cm@3), F is the
Faraday constant ( & 96 500 C mol@1), V (cm3 g@1) is the volume
of closed pores, and A is the molar mass of sodium
(23 g mol@1).[29] This empirical equation provides a rough esti-
mation of the capacity derived from porosity. Because sodium
ions will only turn into a quasi-metal (see Section 2.2), do not
fill 100 % of the porosity, and the process is not completely re-
versible, the value calculated from Equation (1) slightly overes-
timates the maximum capacity contribution from the pores,
but it will give us some information on the upper boundary.
The estimation of the volume of closed pores also introdu-
ces inaccuracy because of the technical limitation in porosity
measurements. The pore volume from regular N2 absorption
and the closed pore volume are not the same. Nitrogen gas
adsorption methods are only able to provide open porosity in-
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Minireviews
formation, which usually contributes to irreversible capacity
and a low first cycle Coulombic efficiency. The closed and
open pores that fall below the limit of detect will not be ac-
counted for. The closed pore volume can be estimated from
true density measurements by means of liquid- (butanol etc.)
and gas-phase (He gas) displacement experiments.[31] Commer-
cial HC usually has a true density of 1.52 g cm@3, a small surface
area, and open pore volume determined by means of N2 ab-
sorption.[31] Assuming that the turbostratic graphitic domain in
HC has a similar density to that of graphite of about
2.2 g cm@3, a rough volume of 0.22 cm3·g@1 can be estimated
for the closed pores, which would result in a capacity of about
248 mAh g@1 derived from pore-filling theory.
The above capacity calculated for closed-pore filling also in-
cludes the contribution from vacancy defects that are not in
contact with the electrolyte. These vacancies are also tiny
closed pores that contribute to the low true density of HC. The
effects of doped heteroatoms and defects on the surface are
not included.
ð1Þ Third, surface absorption storage of sodium ions is associat-
ed with the surface directly in contact with the electrolyte, but
the surface area varies greatly between different HC products.
Practically, reducing the surface area is an important approach
for reducing decomposition of the electrolyte (Section 4.1) and
to improve the first cycle Coulombic efficiency. The capacitive
storage will become marginal in this regard.
Based on the sole combination of the contribution from in-
tercalation and pore filling, HC could possibly deliver a capaci-
ty of > 530 mAh g@1 if the structure were ideal enough to fulfill
all of these extreme conditions. Admittedly, it is very difficult
to reach the maximum capacity; the number is still well above
results published on HC (Table 1). Such a big gap indicates
that there is still plenty of room for achieving high capacity for
HC. Particularly, more attempts are expected beyond tuning
the surface area, interlayer spacing, amount of defects, and
pore size to improve the capacity of HC.
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Figure 2. Simulation results of the intercalation of sodium ions into gra-
phene layers. a) Calculated formation energies of alkali metal (M)–graphite
compounds (Reproduced with permission,[24] Copyright National Academy of
Sciences, 2016.) b) Simulation of the sodiation potential and interlayer spac-
ing for NaC8 ordering. c) Sodiation potential at low sodium contents as a
function of the initial interlayer distances, c0, for two pristine graphene
layers and layers with monovacancies (MVs), divacancies (DVs), and Stone–
Wales (SW) defects. (Reproduced with permission,[25] Copyright Royal Society
of Chemistry, 2015.)
2.2. Debate on sodiation pathways: Intercalation–pore filling
versus adsorption–intercalation–pore filling
An anode material not only needs to have a high specific ca-
pacity, but also a relatively low voltage potential to enable a
high energy density in full cells. In this regard, it is essential to
understand the correlation between the sodiation potential
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Minireviews
and storage sites; in other words, the sodiation or sodium-ion
storage/transfer pathways. This is the foundation for appropri-
ate tuning of the structure of HC.
The typical discharge curve of HC versus sodium metal is
composed of a slope region (region I) and a plateau region (re-
gion II). Recently, there has been a major debate on the assign-
ment of these two regions to different sodium-ion-storage
mechanisms.[22] Figure 3 a and b shows a schematic illustration
of the intercalation–pore filling mechanism and the adsorp-
tion–intercalation–pore filling mechanism, respectively. In the
early model proposed by Dahn and Stevens (Figure 3 a), re-
gion I was assigned to the intercalation of sodium ions into
the parallel graphitic layers, and region II was assigned to the
filling of nanoporosity between randomly stacked layers.[21] The
intercalation of sodium ions follows a sloping trend because
the potential for further insertion of sodium ions can be al-
tered if there are more sodium ions in the graphene layer. The
mechanism has been supported by many other studies.
Komaba et al. observed a negative shift by using ex situ XRD,
if HC was discharged to 0.1 V, which indicated that the interlay-
er spacing was expanded because of Na-ion insertion (Fig-
ure 3 c and d).[53] Small-angle X-ray scattering (SAXS) analysis
on the sample discharged below 0.2 V showed a reversible de-
crease in intensity, corresponding to nanopores with sizes of
about 14 a. These results indicated that, within this voltage
range, sodium ions inserted into the nanopores. Bai et al. also
believed that the low plateau was associated with the pore-fill-
ing mechanism because they found that the low-voltage pla-
teau disappeared after filling the HC micropores with sulfur.[54]
The debate originally began when highly porous HC was
studied for Na-ion storage. Ding et al. found that the low-volt-
age plateau capacity was not positively proportional to the po-
rosity of the HC material.[32] The d spacing of the graphene
layers expanded from 3.96 to 4.16 a, within the voltage
window of 0.1–0.2 V, which indicated that Na intercalation
took place. This leads to the speculation that low-voltage re-
gion II is not due to pore filling and the Dahn model may be
subject to amendments.
Many other studies are in agreement with amending the so-
diation mechanism. Figure 3 b shows a representative model of
the sodiation sequence of HC. Bommier et al. tuned the micro-
structure of HC through the pyrolysis of sucrose at 1100, 1400,
and 1600 8C, so that the resultant HCs displayed decreasing d
spacing between the graphene sheets and an increasing size
of turbostratic nanodomains with increasing temperature.[55] As
shown in Figure 3 e and f, they observed a decreased capacity
from the slope region, whereas an increased capacity from the
plateau region was observed with an increase in the turbos-
tratic nanodomains; this is completely opposite to the trend
observed in the conventional intercalation pore filling model.
Because larger turbostratic nanodomains are unambiguously
more favorable for Na-ion intercalation, this indicates that the
plateau region, instead of the sloping region, is associated
with Na-ion intercalation. Inspired by theoretical calculations
on the effect of defects on improving the sodiation potential,
speculation was made that the slope region was more likely to
be linked with defects in the HC.[29] Following this work, experi-
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 Minireviews

Table 1. A summary of representative publications on materials with a reversible capacity of over 280 mAh g@1.[a]

Electrochemical performance Electrolyte Pyrolysis method Structure Ref.

298 mAh g@1 at 50 mA g@1,
203 mAh g@1 at 500 mA g@1
355 mAh g@1 at 50 mA g@1
335 mAh g@1 at 40 mA g@1,
200 mAh g@1 at 300 mA g@1
288 mAh g@1 at 50 mA g@1,
71 mAh g@1 at 5000 mA g@1
315 mAh g@1 at 100 mA g@1,
107 mAh g@1 at 2500 mA g@1
360 mAh g@1 at 50 mA g@1
360 mAh g@1 at 20 mA g@1
338 mA g@1 at 30 mA g@1,
111 mAh g@1 at 600 mA g@1
280 mAh g@1 at 20 mA g@1
303 mAh g@1 at 500 mA g@1
430.5 mAh g@1 at 30 mA g@1
360 mAh g@1 at 10 mA g@1
315 mAh g@1 at 30 mA g@1
359 mAh g@1 at 20 mA g@1
438 mAh g@1 at 0.05 mA
per unit area
333 mAh g@1 at 25 mA g@1
328 mAh g@1 at 100 mA g@1
350 mAh g@1 at 50 mA g@1
394 mAh g@1 at 20 mA g@1
361 mAh g@1 at 20 mA g@1
308 mAh g@1 at 20 mA g@1
297 mAh g@1 at 20 mA g@1
1 m NaClO4 EC + DEC peat moss, 1100 8C expanded interlayer spacing with open macropores [32]
1 m NaClO4 EC + DEC banana peel, 1100 8C expanded interlayer spacing [33]
1 m NaClO4 EC + PC sucrose, 1100 8C absence of pores detectable through N2 adsorption [34]
1 m NaClO4 EC + PC pomelo peel, 700 8C H3PO4 activation creates a 3D-connected porous [35]
structure
1 m NaClO4 EC + DEC peanut shell, 1200 8C highly interdilated graphene layers [36]
1 m NaClO4 EC + DEC gelatin, 700 8C mesoporous carbon assisted by magnesium citrate [37]
1 m NaClO4 EC + DEC resorcinol–formaldehyde, 1600 8C enlargement of macropore size [20]
1 m NaClO4 EC + DEC PANi, 700 8C disordered structure, interconnected porosity and [38]
nitrogen doping
1 m NaPF6 EC + DEC sucrose/GO, 1100 8C graphite oxide reduces the surface area to only [39]
5.4 m2 g@1
1 m NaClO4 EC + PC PEDOT/Ppy, 700 8C sulfur doping expanded the interlayer spacing [40]
1 m NaClO4 EC + DEC shaddock peel, 700 8C honeycomb-like structure with large interlayer spacing [41]
1 m NaClO4 EC + DEC dry oak leaves, 1000 8C freestanding carbon membranes [42]
1 m NaPF6 EC + DMC cotton, 1300 8C uniform microtubular structure [43]
1 m NaPF6 EC + DEC sucrose/GO/H3PO4, 1100 8C POx doping increases the spacing and causes a more [44]
defective structure
1 m NaPF6 EC + DEC a-cellulose, 2400 8C 52.5 % closed pore [45]
1 m NaPF6 EC + DEC argan shell, 1200 8C large micropores and a large number of active sites [46]
with HCl pretreatment
1 m NaPF6 PC + FEC carbon dot, 1200 8C ultrathin sheets with a large area, expanded layers, [47]
and P doping
1 m NaClO4 EC + PC urea, sol–gel, 650 8C expanded layer spacing and enlarged surface area [48]
1 m NaClO4 PC + FEC PVP, 1000 8C “honeycomb briquette” shaped microstructure with [49]
macropores with P doping
1 m NaClO4 EC + DEC sucrose, hydrothermal, 1300 8C few in-plane defects and undetectable porosity [50]
1 m NaPF6 EC + DEC paper, 650 8C, microwave highly defective structure induced by microwave treatment [51]
1 m NaClO4 EC + PC apple pomace, 1100 8C undetectable closed pores [52]

[a] DEC = diethylene carbonate, PC = propylene carbonate, DMC = dimethyl carbonate, FEC = fluoroethylene carbonate, GO = graphite oxide, PEDOT =
poly(3,4-ethylenedioxythiophene), Ppy = polypyridine, PVP = polyvinylpyrrolidone.

mental studies on the effects of defects on HC performance
have been conducted, including introducing defects into the
HC structure through heteroatom doping. Li et al. used both
boron and phosphorus to dope HC and found that the inter-
layer spacing was expanded after doping, which in turn con-
tributed to higher capacity of the plateau region.[56] By increas-
ing the doping level of boron and phosphorus, the slope
region capacity was also increased accordingly. The wide range
of binding energy explains why adsorption proceeds in the
slope region. The study revealed that the slope region was re-
lated to binding of Na ions to defects and the plateau region
was due to Na intercalation.
All studies provided comprehensive characterization of the
sodiation of HC and caution has been taken in forming conclu-
sions. However, measurements of surface area, pore volume,
and pore size distribution were mainly achieved by determin-
ing N2 gas adsorption on surface/open pores; the closed pores
or pores that fall outside the limit of detection may not be ac-
counted for. Hence, the change in the closed pores with exper-
imental conditions and the effect on the capacity contribution
have not yet been fully assured. It is essential to adopt meth-
ods such as SAXS to fully unveil possible contributions from
closed pores.[22] Also, in gas absorption measurements, gasses
with greater accuracy, such as Kr adsorption, which provides
details of ultra-micropores (< 0.7 nm) and small surface area
that are generally not taken into consideration, should be
adopted to avoid discrepancies caused by the limits of detec-
tion of N2 or CO2.[57]
Another debate lies in sodium clustering in the nanopores
at the end of discharging. Stratford et al. used operando 23Na
ss-NMR spectroscopy to examine the behavior of Na during
discharging and charging.[58] As shown in Figure 3 g, the col-
ored peak shows a shift to higher frequency close to Na metal
at the end of discharging, which reveals that these Na ions are
quasi-metallic clusters. The process is highly reversible, corre-
sponding to region III in Figure 3 b. However, in a study by Qiu
et al., who used ex situ NMR and EPR spectroscopy, as shown
in Figure 3 h and i, no such evidence was observed at the end
of discharging to 0 V. Instead, only a sharp peak corresponding
to Na metal was observed if the HC was discharged to
@0.03 V.[29] Such a discrepancy has been explained by Stratford
et al. by assuming that the Na cluster formed at the end of dis-
charging was metastable, and ex situ studies tend to show
misleading results because the Na metal could have disap-
peared before the HC electrode was collected for characteriza-
tion.[58]

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 Minireviews

Figure 3. Differences in the HC sodiation mechanism. a) Schematic illustration of HC with an intercalation–adsorption mechanism. b) Schematic illustration of
HC with an adsorption–intercalation–pore filling mechanism. c) Ex situ XRD patterns for HC corresponding to the pristine sample (A), and those discharged to
0.4 (B), 0.2 (C), 0.1 (D), and 0 V (E), and charged to 2 V (F). d) Dependence of the interlayer spacing estimated from the XRD results versus the discharge ca-
pacity in a SIB and LIB. (Reproduced with permission,[53] Copyright Wiley, 2011.) e) Sodiation potentiograms for different types of carbon. f) A plot of the slop-
ing capacity versus the ratio of the intensity of the D and G bands (ID/IG) obtained from Raman spectra. (Reproduced with permission,[55] Copyright American
Chemical Society, 2015.) g) Operando 23Na solid-state (ss) NMR spectra for an electrochemical cell with Na metal and HC electrodes. (Reproduced with permis-
sion,[58] Copyright Royal Society of Chemistry, 2016.) h) 23Na magic angle spinning (MAS) NMR spectra of HC at various discharge points. i) EPR spectra of HC
at various discharge points. (Reproduced with permission,[29] Copyright Wiley, 2018.)

3. SEI and Electrolyte Systems for SIB HC

Anodes
The performance of HC as SIB anodes does not solely depend
on the structure of HC, but is also highly affected by the SEI
and electrolyte. Because of the special structure of HC and
unique properties of Na ions, many electrolytes have proven
to be impractical with graphite for LIBs to be seriously recon-
sidered. An ideal electrolyte for SIBs should be stable enough
over the voltage range used and not hamper the Na-ion-trans-
fer kinetics. It should also not deteriorate the structure of the
anode material.
3.1. Role of the SEI: Ternary intercalation in graphite versus
binary intercalation in HC
Electrolyte with cyclic carbonate, including propylene carbon-
ate (PC) and ethylene carbonate (EC); linear carbonate, includ-
ing dimethyl carbonate (DMC), diethylene carbonate (DEC),
ethyl methyl carbonate (EMC); and ethers have been thor-
oughly investigated in LIBs.[59] The electrolyte decomposes on
carbon anodes at low voltage and the decomposition product
forms a layer termed the SEI, which is a critical prerequisite for
high performance in LIBs. On one hand, it prevents continuous
decomposition of the electrolyte;[11] on the other hand, it is
critical for stabilizing the structure of graphite, which is gener-
ally associated with the cointercalation mechanism.[60]
As shown in Figure 4 a, the intercalation of alkali-metal ions
into graphite may undergo three separate scenarios. First, if
the alkali ion is very large and has a weak solvation effect, no
intercalation will take place. Second, if the alkali ion solvates
strongly, it may induce a cointercalation mechanism by form-
ing a ternary-graphite intercalation compound (t-GIC). This pro-
cess expands the graphite layers and leads to two consequen-
ces. If the t-GIC is stable against oxidation, cointercalation be-

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Figure 4. Ternary intercalation in graphite and binary intercalation in HC. a) Schematic illustrations of different cointercalation and exfoliation scenarios of
alkali-metal-ion intercalation into graphite (Reproduced with permission,[66] Copyright Wiley, 2017.) b) Charge/discharge curves of graphite in diethylene
glycol dimethyl ether (DEGDME) with different electrolyte salts. (Reproduced with permission,[63 Copyright Wiley, 2015.) c) Typical charge/discharge curves of
HC in tetraethylene glycol dimethyl ether (TEGDME) and carbonate. (Reproduced with permission,[17] Copyright Wiley, 2018.)

comes reversible and contributes to the capacity; however, if
the t-GIC is unstable against oxidation, it may decompose and
exfoliate the graphite structure, which is detrimental to the
performance. The original application of graphite in LIBs was
strongly impeded by exfoliation problems with PC or ether
electrolyte, making it impractical until EC was introduced. The
decomposition product from EC is able to form a very stable
SEI and prevents cointercalation and exfoliation effectively.[11]
With regard to these factors, the SEI is generally required to be
ionically conductive and stable.
In SIBs, however, different behavior was observed with
graphite and HC as the anode materials. As mentioned in Sec-
tion 2.1, the intercalation of Na ions into graphite is thermody-
namically unfavorable because extra energy is needed to over-
come the van der Waals interactions between adjacent gra-
phene layers. However, with an ether-based electrolyte, highly
reversible and fast intercalation/deintercalation was ob-
served.[61, 62] The process results in a reversible capacity of
about 150 mAh g@1, regardless of the types of electrolyte salts
used, and a voltage plateau emerged at around 1 V (Fig-
ure 4 b). Furthermore, the reversible cointercalation of the t-
GIC has long-term stability in SIBs, but fast fading in LIBs due
to structural differences of the t-GIC.[63] Because t-GIC can
transport across the HC surface at a fast rate, concerns were
raised about the actual role of the SEI for HC, the thickness of
which should be controlled to a certain degree to prohibit
electrolyte decomposition, but not affect the cation or t-GIC
transport.[64, 65]
Along the same lines, it is natural to understand that HC,
with the structure of highly disordered graphitic domains ran-
domly stacked together, is unfavorable for ternary cointercala-
tion. Indeed, Li et al. compared the voltage profiles of HC
cycled in carbonate and ether electrolytes.[17] As shown in Fig-
ure 4 c, similar charge–discharge curves were obtained and no
cointercalation plateau was observed in HC. This is consistent
with the simulation results that ether intercalation only occurs
at the edge of the graphene layers.[17] It is a binary interaction
in HC, regardless of whether carbonate or ether electrolytes
are used.
3.2. Ether versus carbonate: SEI formation and ion-transfer
kinetics
Recent research has revealed that HC performs much better in
ether-based electrolytes than that in carbonate electrolytes.
Figure 5 a and b shows that the performance of HC in both
electrolytes is similar at a low current density (50 mA g@1), but
HC in TEGDME showed a dramatically better performance than
that in carbonate if the rate was elevated to 500 and
1000 mA g@1.[67] This is consistent with the results reported by

ChemSusChem 2019, 12, 133 – 144 www.chemsuschem.org 139 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 5. Comparison of the electrochemical performance of HC in carbonate and ether electrolytes. a) Long-term cycling performance of HC in carbonate.
b) Long-term cycling performance in TEGDME. c) In situ electrochemical impedance spectroscopy (EIS) measurements of HC cycled in carbonate. d) In situ EIS
measurements of HC cycled in TEGDME. (Reproduced with permission,[17] Copyright Wiley, 2018.)
Yang et al.[68] X-ray photoelectron spectroscopy (XPS) analysis
of the cycled HC electrolyte surface showed that the SEI
formed in TEGDME was much thinner than that in carbonate.
A similar conclusion was also drawn by Zhang et al., who used
DEGDME as the electrolyte.[67]
Sodium-ion-transfer kinetic differences in the two systems
have been investigated by means of in situ three-electrode EIS
measurements (Figure 5 c and d). The impedance of the HC
electrode versus a reference electrode did not drop significant-
ly until reaching the plateau region in carbonate electrolyte.
However, upon sodiation in TEGDME, the impedance dropped
in the slope region and the overall value was consistently
lower than that in carbonate, which indicated that Na-ion
transfer through the SEI in carbonate was much more sluggish
than that in TEGDME. In addition to the poor ionic conductivity
of the SEI formed in carbonate, it was also found to be unsta-
ble and tended to dissolve into the electrolyte because there
was a lack of cross-linked organic species.[68]
The outstanding performance of HC in ether-based electro-
lyte, together with ternary intercalation with graphite, chal-
lenges the universality of creating a “good” SEI layer. At least,
the question has been raised of what is a good SEI. Unlike Li
intercalation into graphite, Na intercalation into HC does not
cause many exfoliation problems. The SEI is not a significant
component from this regard. The inherently higher voltage of
Na versus Li promises increased the electrochemical potential
(vs. SHE) for electrolyte decomposition and different SEI prop-
erties in SIBs;[53] hence, the requirement for a SEI for stable per-
formance is much lower than that of LIBs.
ChemSusChem 2019, 12, 133 – 144 www.chemsuschem.org
Minireviews
4. From a Fundamental Understanding to
Practical Design of Materials
For HC to be practically used for SIB full cells, both a high re-
versible capacity and high initial Coulombic efficiency (ICE) are
desired from the performance perspective. This is dictated by
the HC structure and efficiency of the electrolyte; hence modi-
fications to both sides can elevate the capacity and ICE.
4.1. Structural modification
Enlarging the interlayer spacing and controlling defects and
porosity have been well documented to improve the HC per-
formance as SIB anodes. Enlarging the interlayer spacing is an
unambiguous approach to improve the capacity in all studies,
as discussed in previous sections. A good example is the use
of expanded graphite, which delivers a capacity of
283 mAh g@1 at 20 mA g@1; this is close to the theoretical inter-
calation capacity.[30]
There are various approaches for defect engineering. Usually,
it is through controlling the annealing temperature or elemen-
tal doping. The heteroatoms doped into the graphitic planes
are reactive sites at which Na ions adsorb, and hence, can im-
prove the capacity. In the meantime, these dopants are able to
expand the graphene layers to enable more Na intercalation.[48]
Zhang et al. reported a method for preparing N/S codoped
HCs by using cellulose/polyaniline microspheres as the precur-
sors. The final product achieved a high capacity of
280 mAh g@1 at 30 mA g@1, along with a superior rate capability
140 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

(130 mAh g@1 at 10 Ah g@1). The outstanding performance was
ascribed to easy adsorption due to expanded interlayers and
doping-induced defects. The defects enable a decreased diffu-
sion barrier and enhanced electronic conductivity.[69] However,
discrepancies exist in the role of the defects. Recently, Xiao
et al. were able to obtain an outstanding performance of a ca-
pacity of 361 mAh g@1 and 86.1 % ICE with a HC containing low
in-plane defects (Figure 6 a).[50] The simulation results revealed
Figure 6. HC structure engineering to improve the ICE. a) ICEs of HC at dif-
ferent ramping rates; a lower ramping rate resulted in a lower amount of
defects and porosity. (Reproduced with permission,[50] Copyright American
Chemical Society, 2016.) b) Photographs of the HC produced from sucrose
and sucrose mixed with GO. c) Initial charge/discharge curves of the pristine
HC from the pyrolysis of sucrose. d) Initial charge/discharge curves of HC
from the pyrolysis of sucrose mixed with GO. (Reproduced with permis-
sion,[39] Copyright American Chemical Society, 2015.)
that the Na distribution was highly uniform within defect-free
carbon layers, whereas the Na distribution became sparse if
there were defects in the carbon structure. It was proposed
that Na ions became trapped at the defect sites due to strong
adsorption energy, which was excluded from the total ion flux.
A repulsive electric field is generated with these fixed Na ions
and it prevents other ions from approaching, leading to re-
stricted performance. The discrepancy between these studies
implies that it is essential to classify the particular defect types
and amounts, which may affect the degree of contribution to
the capacity.
Increasing the porosity is also believed to be beneficial for
the HC performance. A high capacity was achieved based on
macro-/meso-/micropores or open 3D structures that allowed
for efficient electrolyte utilization and Na-ion diffusion rates.[38]
However, the groups of Bommier[34] and Xiao[50] reported that
the reversible capacity was inversely proportional to the
amount of measurable porosity (+ 0.4 nm), that is, low measur-
able porosity resulted in high reversible capacity. These stud-
ies, however, cannot rule out the importance of closed pores
because most of the pore-filling capacity is contributed to by
closed pores.[22] In the patent of Kano et al., a high initial dis-
ChemSusChem 2019, 12, 133 – 144 www.chemsuschem.org
Minireviews
charge capacity of 438 m2 g@1 was obtained by creating a
closed pore ratio of 52.5 %; the HC was synthesized through
the pyrolysis of a-cellulose at 2400 8C at a heat ramp of
10 8C min@1.[45]
It should to be noted that a large surface area allows for
more abundant Na-ion intercalation pathways, but accelerates
parasitic reactions between HC and the electrolyte, which are
the major source of first cycle irreversible capacity. It is not
suitable for application in practical full cells. For example, it
was reported that, if HC was synthesized through the pyrolysis
of pomelo peel activated by H3PO4, the surface area was mea-
sured to be over 1272 m2 g@1, which resulted in only 21 %
ICE.[35] A good approach is to improve the performance of HC
by using a low surface area. Luo et al. added GO to sucrose
before pyrolysis to prevent foaming during caramelization or
dehydration. The resultant HC showed a surface area of only
5.4 m2 g@1, which improved the ICE from 74 to 83 % (Fig-
ure 6 b–d).[39]
4.2. Pretreatment of HC anodes
Although the higher voltage potential of Na/Na + than that of
Li/Li + leads to an increased electrochemical potential for the
electrochemical reduction of the electrolyte in SIBs than that in
LIBs, there is still a large amount of capacity lost during the
first cycle. As shown in Figure 4 c, although TEGDME was
found to form very little SEI, it was still only able to achieve an
ICE of 72 %. Irreversible defect binding, pore filling, and so
forth are responsible for this loss, and hence, a method of
compensation it is essential for full-cell tests.[13, 59] Precycling of
the HC electrode for several cycles prior to full-cell assembly is
proven to boost the full-cell performance.[70] The irreversible
consumption of Na ions due to SEI formation and ion trapping
can be effectively compensated for through the precycling
process. Li et al. found that the HC–Na0.44MnO2 full cell was
only able to deliver a capacity of less than 30 mAh g@1, with
less than 20 % ICE, and it faded to almost 0 mAh g@1 after 100
cycles.[70] However, after precycling the HC against Na metal
several times, the full cell showed over 60 % ICE and a capacity
of over 60 mAh g@1 after 500 cycles (Figure 6 a and b). This
method involves the collection of HC after precycling by disas-
sembly the HC/Na metal cell; hence it is not convenient for
practical purposes. In regard of this, pretreatment with stabi-
lized Li metal powder (SLMP) was employed recently. The ap-
proach is based on a “local short-circuit” mechanism, through
which the local potential was brought down by the SLMP and
SEI formation and preintercalation occurred after immersing
the electrode in the electrolyte.[71] For HC tested in SIBs, Na
metal powder is commercially unavailable and unstable in air;
hence SLMP has been explored as a pretreatment agent.[17] Fig-
ure 7 c and d shows the performance of the pretreated HC in
both TEGDME and carbonate electrolyte (1 m NaClO4 in EC +
DMC); in both cases, the ICE was increased to above 92 % (the
ICEs of untreated HC were about 70 % in both electrolytes).
The pretreated HC delivers stable cycling and a high capacity
in TEGDME. Upon testing in a full cell against Na3V2(PO4)3, the
pretreated HC was able to achieve over 80 % ICE with a much
141 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 7. Pretreatment to improve the performance of HC. a) Full-cell performance of HC versus Na0.44MnO2 without any precycling. b) Full-cell performance
of HC versus Na0.44MnO2 with precycled HC. (Reproduced with permission,[70] Copyright Elsevier, 2016.) c) Pretreated HC cycled in TEGDME versus Na metal.
d) Pretreated HC cycled in carbonate versus Na metal. (Reproduced with permission,[17] Copyright Wiley, 2018.)
higher capacity and stability in TEGDME. The study revealed
that, although SLMP is a good pretreatment agent for HC in
SIBs, it is not compatible with carbonate electrolyte because
the Li-containing SEI formed in carbonate electrolyte is detri-
mental for the transport of Na ions.[17, 19]
5. Summary and Outlook
SIBs have attracted tremendous attention and the technology
will soon be ready for deployment in grid-scale energy storage
or low-speed electrical vehicles. With the broad adoption of
LIBs in various applications and limited Li resources, the preva-
lence of SIBs can be foreseen. It is essential to develop high-
performance HC anode materials for SIBs and this relies on a
thorough understanding of the structure, ion transfer, and stor-
age mechanisms. Herein, we have reviewed fundamental un-
derstandings of the ion-storage mechanisms and progress in
tuning the structure of the material and electrolyte for better
performance. The theoretical capacity of HC has been roughly
estimated and supplemented by reported experimental results.
There is still much room to improve the HC performance. Sev-
eral discrepancies between different studies in the community
have been discussed and potential solutions provided. In
terms of sodium storage mechanisms, debates remain in the
assignment of the sodium storage behavior of the slope and
plateau regions during discharge. The discrepancy lies in the
complicated nature of HC and limitations of the characteriza-
tion techniques. Defects and porosity were considered to be
important to further improve the capacity and ICE of HC by
some researchers, but others believed that they were not as
profound. Although these debates continue, a consensus has
been reached that expanding the interlayer spacing of HC is
an unequivocal approach to fully exploit the Na storage capa-
bility.
ChemSusChem 2019, 12, 133 – 144 www.chemsuschem.org
Minireviews
Recent progress in the fundamental understanding has
paved the way to propose directions for designing an ideal HC
structure for high performance. If it is used as an anode mate-
rial in a full cell, the capacity of HC is expected to be derived
from relatively low voltage ranges. In this regard, one should
consider improving the plateau capacity and rate performance
as a priority when designing the structure. Several methods
can be considered to achieve this goal, together with a high
ICE. First, the surface and open porosity of HC needs to be low
to avoid harsh parasitic reactions with the electrolyte and sur-
face capacitive storage, which occurs in the slope region. The
closed pores should be appropriate for a high capacity and
balanced energy density. Second, the turbostratic domains
should be dilated enough to allow for easier Na intercalation/
deintercalation and a high capacity, but not too large to
enable exfoliation. Third, defects require appropriate engineer-
ing because they account for the increase in the potential for
sodiation, expand the interlayer spacing, and trap ion flows in
a flux to generate a repulsive electric field; thus their effect on
the capacity is detrimental. Finally, it should be noted that the
porosity, of all parameters of the HC material, may require reas-
sessment. In most research, porosity has been measured based
on N2 adsorption/desorption, which has a low detection limit
for the pore volume and poor characterization of closed pores.
The development of an advanced electrolyte and optimized
SEI are also important for a high performance of the HC as SIB
anodes. The development of LIBs has provided tremendous
knowledge for research into SIBs, although the dissimilarity of
Na and Li also indicate that SIBs may, in the end, require their
own unique, optimized electrolyte. The electrolyte not only
needs to interact well at the HC anode side, but also the cath-
ode side, which has a greater requirement for high-voltage sta-
bility than that in LIBs. In this regard, it is crucial to develop
high-performance electrolytes with high-voltage stability.
142 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Acknowledgements
We would like to acknowledge financial support from the U.S.
Department of Energy’s (DOE’s) Office of Electricity Delivery and
Energy Reliability (OE) under contract no. 70247A.
Conflict of interest
The authors declare no conflict of interest.
Keywords: carbon · electrochemistry · ion storage · materials
science · sodium
[1] P. K. Nayak, L. Yang, W. Brehm, P. Adelhelm, Angew. Chem. Int. Ed. 2018,
57, 102 – 120; Angew. Chem. 2018, 130, 106 – 126.
[2] J. Deng, W.-B. Luo, S.-L. Chou, H.-K. Liu, S.-X. Dou, Adv. Energy Mater.
2018, 8, 1701428.
[3] J. Y. Hwang, S. T. Myung, Y. K. Sun, Chem. Soc. Rev. 2017, 46, 3529.
[4] W. Luo, F. Shen, C. Bommier, H. Zhu, X. Ji, L. Hu, Acc. Chem. Res. 2016,
49, 231.
[5] D. Kundu, E. Talaie, V. Duffort, L. F. Nazar, Angew. Chem. Int. Ed. 2015, 54,
3431; Angew. Chem. 2015, 127, 3495.
[6] N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba, Chem. Rev. 2014, 114,
11636.
[7] Y. Li, Y.-S. Hu, X. Qi, X. Rong, H. Li, X. Huang, L. Chen, Energy Storage
Mater. 2016, 5, 191.
[8] C. Fang, Y. Huang, W. Zhang, J. Han, Z. Deng, Y. Cao, H. Yang, Adv.
Energy Mater. 2016, 6, 1501727.
[9] Y. Liu, J. S. Xue, T. Zheng, J. R. Dahn, Carbon 1996, 34, 193.
[10] W. Xing, J. Electrochem. Soc. 1996, 143, 3482.
[11] K. Xu, Chem. Rev. 2004, 104, 4303.
[12] D. Aurbach, J. Electrochem. Soc. 1996, 143, 3809.
[13] H. Hou, X. Qiu, W. Wei, Y. Zhang, X. Ji, Adv. Energy Mater. 2017, 7,
1602898.
[14] M. Wahid, D. Puthusseri, Y. Gawli, N. Sharma, S. Ogale, ChemSusChem
2018, 11, 506.
[15] G. G. Eshetu, S. Grugeon, H. Kim, S. Jeong, L. Wu, G. Gachot, S. Laruelle,
M. Armand, S. Passerini, ChemSusChem 2016, 9, 462.
[16] H. Che, S. Chen, Y. Xie, H. Wang, K. Amine, X.-Z. Liao, Z.-F. Ma, Energy En-
viron. Sci. 2017, 10, 1075.
[17] B. Xiao, F. A. Soto, M. Gu, K. S. Han, J. Song, H. Wang, M. H. Engelhard, V.
Murugesan, K. T. Mueller, D. Reed, V. L. Sprenkle, P. B. Balbuena, X. Li,
Adv. Energy Mater. 2018, 8, 1801441.
[18] F. A. Soto, A. Marzouk, F. El-Mellouhi, P. B. Balbuena, Chem. Mater. 2018,
30, 3315.
[19] F. A. Soto, P. Yan, M. H. Engelhard, A. Marzouk, C. Wang, G. Xu, Z. Chen,
K. Amine, J. Liu, V. L. Sprenkle, F. El-Mellouhi, P. B. Balbuena, X. Li, Adv.
Mater. 2017, 29, 1606860.
[20] G. Hasegawa, K. Kanamori, N. Kannari, J.-i. Ozaki, K. Nakanishi, T. Abe,
ChemElectroChem 2015, 2, 1917.
[21] D. A. Stevens, J. R. Dahn, J. Electrochem. Soc. 2000, 147, 1271.
[22] D. Saurel, B. Orayech, B. Xiao, D. Carriazo, X. Li, T. Rojo, Adv. Energy
Mater. 2018, 8, 1703268.
[23] M. Winter, J. O. Besenhard, M. E. Spahr, P. Nov#k, Adv. Mater. 1998, 10,
725.
[24] Y. Liu, B. V. Merinov, W. A. Goddard, 3rd, Proc. Natl. Acad. Sci. USA 2016,
113, 3735.
[25] P.-c. Tsai, S.-C. Chung, S.-k. Lin, A. Yamada, J. Mater. Chem. A 2015, 3,
9763.
[26] Y. Okamoto, J. Phys. Chem. C 2014, 118, 16.
[27] K. Nobuhara, H. Nakayama, M. Nose, S. Nakanishi, H. Iba, J. Power Sour-
ces 2013, 243, 585.
[28] P. Ge, Solid State Ionics 1988, 28 – 30, 1172.
[29] S. Qiu, L. Xiao, M. L. Sushko, K. S. Han, Y. Shao, M. Yan, X. Liang, L. Mai,
J. Feng, Y. Cao, X. Ai, H. Yang, J. Liu, Adv. Energy Mater. 2017, 7,
1700403.
ChemSusChem 2019, 12, 133 – 144 www.chemsuschem.org
Minireviews
[30] Y. Wen, K. He, Y. Zhu, F. Han, Y. Xu, I. Matsuda, Y. Ishii, J. Cumings, C.
Wang, Nat. Commun. 2014, 5, 4033.
[31] Lithium-Ion Batteries (Eds.: M. Yoshio, J. R. Brodd, A. Kozawa), Springer,
New York, 2009.
[32] J. Ding, H. Wang, Z. Li, A. Kohandehghan, K. Cui, Z. Xu, B. Zahiri, X. Tan,
E. M. Lotfabad, B. C. Olsen, D. Mitlin, ACS Nano 2013, 7, 11004.
[33] E. M. Lotfabad, J. Ding, K. Cui, A. Kohandehghan, W. P. Kalisvaart, M. Ha-
zelton, D. Mitlin, ACS Nano 2014, 8, 7115.
[34] C. Bommier, W. Luo, W.-Y. Gao, A. Greaney, S. Ma, X. Ji, Carbon 2014, 76,
165.
[35] K.-l. Hong, L. Qie, R. Zeng, Z.-q. Yi, W. Zhang, D. Wang, W. Yin, C. Wu, Q.-
j. Fan, W.@x. Zhang, Y.-h. Huang, J. Mater. Chem. A 2014, 2, 12733.
[36] J. Ding, H. Wang, Z. Li, K. Cui, D. Karpuzov, X. Tan, A. Kohandehghan, D.
Mitlin, Energy Environ. Sci. 2015, 8, 941.
[37] Z. Guan, H. Liu, B. Xu, X. Hao, Z. Wang, L. Chen, J. Mater. Chem. A 2015,
3, 7849.
[38] H. Liu, M. Jia, N. Sun, B. Cao, R. Chen, Q. Zhu, F. Wu, N. Qiao, B. Xu, ACS
Appl. Mater. Interfaces 2015, 7, 27124.
[39] W. Luo, C. Bommier, Z. Jian, X. Li, R. Carter, S. Vail, Y. Lu, J. J. Lee, X. Ji,
ACS Appl. Mater. Interfaces 2015, 7, 2626.
[40] L. Qie, W. Chen, X. Xiong, C. Hu, F. Zou, P. Hu, Y. Huang, Adv. Sci. 2015,
2, 1500195.
[41] N. Sun, H. Liu, B. Xu, J. Mater. Chem. A 2015, 3, 20560.
[42] H. Li, F. Shen, W. Luo, J. Dai, X. Han, Y. Chen, Y. Yao, H. Zhu, K. Fu, E.
Hitz, L. Hu, ACS Appl. Mater. Interfaces 2016, 8, 2204.
[43] Y. Li, Y.-S. Hu, M.-M. Titirici, L. Chen, X. Huang, Adv. Energy Mater. 2016,
6, 1600659.
[44] Z. Li, L. Ma, T. W. Surta, C. Bommier, Z. Jian, Z. Xing, W. F. Stickle, M.
Dolgos, K. Amine, J. Lu, T. Wu, X. Ji, ACS Energy Lett. 2016, 1, 395.
[45] A. Kano, N. Hojo, M. Fujimoto, US 20160104889, 2016.
[46] M. Dahbi, M. Kiso, K. Kubota, T. Horiba, T. Chafik, K. Hida, T. Matsuyama,
S. Komaba, J. Mater. Chem. A 2017, 5, 9917.
[47] H. Hou, L. Shao, Y. Zhang, G. Zou, J. Chen, X. Ji, Adv. Sci. 2017, 4,
1600243.
[48] J. Yang, X. Zhou, D. Wu, X. Zhao, Z. Zhou, Adv. Mater. 2017, 29,
1604108.
[49] Y. Li, Y. Yuan, Y. Bai, Y. Liu, Z. Wang, L. Li, F. Wu, K. Amine, C. Wu, J. Lu,
Adv. Energy Mater. 2018, 8, 1702781.
[50] L. F. Xiao, H. Y. Lu, Y. J. Fang, M. L. Sushko, Y. L. Cao, X. P. Ai, H. X. Yang, J.
Liu, Adv. Energy Mater. 2018, 8, 1703238.
[51] Z. F. Li, Y. C. Chen, Z. L. Jian, H. Jiang, J. J. Razink, W. F. Stickle, J. C. Neue-
feind, X. L. Ji, Chem. Mater. 2018, 30, 4536.
[52] X. Dou, C. Geng, D. Buchholz, S. Passerini, APL Mater. 2018, 6, 047501.
[53] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama,
A. Ogata, K. Gotoh, K. Fujiwara, Adv. Funct. Mater. 2011, 21, 3859.
[54] P. Bai, Y. He, X. Zou, X. Zhao, P. Xiong, Y. Xu, Adv. Energy Mater. 2018, 8,
1703217.
[55] C. Bommier, T. W. Surta, M. Dolgos, X. Ji, Nano Lett. 2015, 15, 5888.
[56] Z. Li, C. Bommier, Z. S. Chong, Z. Jian, T. W. Surta, X. Wang, Z. Xing, J. C.
Neuefeind, W. F. Stickle, M. Dolgos, P. A. Greaney, X. Ji, Adv. Energy
Mater. 2017, 7, 1602894.
[57] C. Matei Ghimbeu, J. Gjrka, V. Simone, L. Simonin, S. Martinet, C. Vix-
Guterl, Nano Energy 2018, 44, 327.
[58] J. M. Stratford, P. K. Allan, O. Pecher, P. A. Chater, C. P. Grey, Chem.
Commun. 2016, 52, 12430.
[59] J. Song, B. Xiao, Y. Lin, K. Xu, X. Li, Adv. Energy Mater. 2018, 8, 1703082.
[60] T. Abe, N. Kawabata, Y. Mizutani, M. Inaba, Z. Ogumi, J. Electrochem. Soc.
2003, 150, A257.
[61] B. Jache, P. Adelhelm, Angew. Chem. Int. Ed. 2014, 53, 10169; Angew.
Chem. 2014, 126, 10333.
[62] H. Kim, J. Hong, Y.-U. Park, J. Kim, I. Hwang, K. Kang, Adv. Funct. Mater.
2015, 25, 534.
[63] S. C. Jung, Y.-J. Kang, Y.-K. Han, Nano Energy 2017, 34, 456.
[64] J. Xu, Y. Dou, Z. Wei, J. Ma, Y. Deng, Y. Li, H. Liu, S. Dou, Adv. Sci. 2017,
4, 1700146.
[65] J. Maibach, F. Jeschull, D. Brandell, K. Edstrom, M. Valvo, ACS Appl.
Mater. Interfaces 2017, 9, 12373.
[66] G. Yoon, H. Kim, I. Park, K. Kang, Adv. Energy Mater. 2017, 7, 1601519.
[67] J. Zhang, D.-W. Wang, W. Lv, S. Zhang, Q. Liang, D. Zheng, F. Kang, Q.-H.
Yang, Energy Environ. Sci. 2017, 10, 370.
[68] R. Mogensen, D. Brandell, R. Younesi, ACS Energy Lett. 2016, 1, 1173.
143 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Minireviews
[69] D. Xu, C. Chen, J. Xie, B. Zhang, L. Miao, J. Cai, Y. Huang, L. Zhang, Adv. [71] M. W. Forney, M. J. Ganter, J. W. Staub, R. D. Ridgley, B. J. Landi, Nano
Energy Mater. 2016, 6, 1501929. Lett. 2013, 13, 4158.
[70] X. Li, P. Yan, M. H. Engelhard, A. J. Crawford, V. V. Viswanathan, C. Wang,
J. Liu, V. L. Sprenkle, Nano Energy 2016, 27, 664. Manuscript received: August 16, 2018
Revised manuscript received: October 22, 2018
Accepted manuscript online: October 22, 2018
Version of record online: November 21, 2018

ChemSusChem 2019, 12, 133 – 144 www.chemsuschem.org 144 T 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim