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Title: A Minireview on Hard Carbon as Na-ion Battery Anodes: Progresses and Chal-
lenges

Authors: Biwei Xiao; Teófilo Rojo; Xiaolin Li

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To be cited as: 10.1002/cssc.201801879

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MINIREVIEW

A Minireview on Hard Carbon as Na-ion Battery Anodes:

Progresses and Challenges
Biwei Xiao,[a] Teófilo Rojo,[b,c]* and Xiaolin Li[a]*

Abstract: Hard carbon (HC) is the state-of-the-art anode material for
Na-ion batteries due to its excellent overall performance, wide
availability and relatively low cost. Recently, tremendous effort has
been carried out to elucidate the Na storage mechanism in HC and
to explore synthesis approaches that can enhance the performance
and lower the cost. However, disputations remain in the fields,
particularly on the fundamental questions of ion transfer and storage
and the ideal HC structure for high performance. This mini-review
aims to give an analysis and summary of the theoretical limitations of
HC, discrepancies of the storage mechanism, and methods to
improve the performance. In the end, future research on developing
ideal structured HC, advanced electrolyte and optimized electrolyte-
electrode interphase are proposed on the basis of recent progress.
1. Introduction
Na-ion batteries (SIBs), with similar mechanism to Li-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 provides rich
experience for SIB development. Many of the SIB cathode
materials were developed benefiting from the LIB counterparts.
However, the intrinsic dissimilarities between Li and Na, such as
ionic radius (0.71 Å for Li+ and 1.03 Å for Na+) and
electrochemical potential (2.71 V vs standard hydrogen
electrode (SHE) for Na/Na+ and 3.04 V vs SHE for Li/Li+), lead to
some inconsistencies and sometimes even misguidance in
research practices.[1, 3, 4] Efforts have been made in sorting out
the discrepancies in the development of SIBs [5] and great
progress has been achieved within the last a couple of years.[6]
Long life SIBs with over 100Wh•Kg-1 energy density,[7] close to
LiFePO4 and LiMn2O4 cells, have been demonstrated in large
format cells. While there are numerous reports on SIB cathode
materials with equivalent performance to some of the LIB
cathode materials, the anode material has been a hassle of the
full cell performance.[8]
Hard carbon (HC) is the state-of-the-art anode material for SIBs.
Ion transfer and storage in HC almost were reported at the same
time as the intercalation into graphite and other kinds of carbon
materials for LIBs.[9] It was known to have higher capacity and
better compatibility with ether electrolyte compared to graphite,
which was found to experience exfoliation because of solvent
intercalation.[10, 11] The competition between HC and graphite
continued until ethylene carbonate (EC)-based electrolyte was
introduced. The stable solid electrolyte interphase (SEI)
generated by EC enabled 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 the knowledge of the similarity and
difference of Na and Li-ions, scientists start to carefully re-
consider the electrolyte systems, the role of the SEI and other
properties required for high performance HC anodes for SIBs.[13-
19]
Fundamental understanding of the HC structure, ion-transfer
and storage mechanism, interaction with different electrolytes is
essential for improving HC performance and has attracted
unprecedented attention.[4, 13, 14, 20] In this review, we try to focus
on the recent progress and future challenges in understanding
these three scientific problems related to HC as SIB anodes: 1)
HC structure and the capacity limit; 2) the ion storage
mechanism in HC; 3) the SEI and electrolyte system.
Figure 1. Schematic illustrations of the ion storage in graphite
and HC.

[a] Dr. Biwei Xiao, Dr. Xiaolin Li

Energy & Environment Directorate
Pacific Northwest National Laboratory
Richland, Washington, 99352, United States
E-mail: xiaolin.li@pnnl.gov
[b] Dr. Teófilo Rojo
CIC energiGUNE
Parque Tecnológico de Álava
C/ Albert Einstein 48, 01510 Miñano, Spain
E-mail: teo.rojo@ehu.eus
[c] Dr. Teófilo Rojo
Departamento de Química Inorgánica
Universidad del País Vasco
UPV/EHU, P.O.Box.664, 48080 - Leioa, Spain

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MINIREVIEW
2. HC structure and Na-ion storage
mechanism
HC is non-graphitizable and the structure at the molecular level
is much more complicated than the long range ordered layer
structure of graphite. The unique structure intrinsically
determines that: 1) HC has multiple types of storage sites for the
reversible accommodation of Na-ions. 2) The capacity limit of
HC, unlike graphite, remains elusive. Understanding the above
two fundamental questions is critical to guide the development of
high performance HC materials.
2.1. Na-ion storage sites in the “House of cards” structure
and estimation of the capacity limit
Among the proposed structures of HC, the “house of cards”
model currently is widely adopted as the model structure to
study the ion storage mechanism by battery material
scientists.[21] It is believed that HC differs from graphite that it is
not formed by the periodic stacking of graphene layers with well-
defined spacing (3.3 Å) (Figure 1). Instead, it consists of
randomly distributed turbostratic domains with curved graphene
nanosheets and expanded interlayer spacing, as well as
micropores formed between these microstructures (Figure 1). [21]
Such a structure requires the carbon precursor to be
thermosetting and contain highly branched and crosslinked
structures. During pyrolysis at above 1000 °C, the branches
prevent the occurrence of long range-ordered graphitization.
Even with higher pyrolysis temperature (above 3000 °C), the
final product is non-graphitizable glassy carbon with lots of
closed pores.[22]
The intrinsic difference of the structure between graphite and HC
renders different ion-storage sites for the two types of carbon
anodes. For graphite, the ions are stored mainly between the
graphitic layers. The theoretical capacity for the ion storage of
graphite is largely based on the intercalation compound of alkali
metal ions and graphite. Using Li-ion storage in graphite as an
example, a theoretical capacity of 372 mAh•g-1 can be concluded
by simply assuming that every 6 carbon atoms capture 1 Li-ion
and forms a stage-I graphite intercalation compound (GIC)
LiC6.[23]
There are several different ion storage sites for HC materials
including 1) intercalation between graphene sheets in the
turbostratic graphitic structures; 2) storage in the closed
micropores; 3) surface and defect absorption (there are much
more defects in HC than that of graphite). Figure 1 shows the
schematic of the ion storage at the sites and the dictating
parameters. Although the complication from the structure
variation with material synthesis makes it almost impossible to
get a specific number as the “theoretical capacity” for a certain
ion storage type in HC, it is very important to have an
established estimation on the capacity limit. Such an estimation
will provide guidance for the structure design of HC for high
performance anodes.
The capacity limit of Na-ion storage at each kind of storage site
in HC was considered one by one. First, considering the Na-ion
intercalation between the graphene sheets of the turbostratic
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graphitic structures, graphene/graphene oxide sheets with large
interlayer spacing have been used as the model systems to
estimate the maximum contribution from Na intercalation.
Theoretical calculation showed that the intercalation of Na-ions
into pristine graphite has positive formation energy for NaC 6 or
NaC8 (Figure 2a)[24] and negative sodiation potential at low Na
contents (Figure 2b).[25] Both indicate that Na intercalation into
graphite is thermodynamically unstable compared to Na plating
(0 V) and it cannot form stage-I structures of NaC6 or NaC8.[24, 26-
28]
The results are consistent with the experimental low specific
capacity of Na electrochemical/vapor intercalation into graphite,
which is generally only able to form a NaC70 compound with 31
mAh•g-1 capacity.[28] However, the sodiation potential has good
correlation to the interlayer spacing and the percentage of NaC 8
formation (Figure 2b). It increases with the increase of NaC 8
percentage and tops at ~40% NaC8 formation, then oscillates at
~0 V with a spread of about ±0.1 V and the interlayer spacing is
Biwei Xiao is currently a postdoctoral
research associate at Pacific Northwest
National Laboratory. He obtained his Ph.D.
degree from Prof. Xueliang Sun’s group in
University of Western Ontario in 2017 and
received his Bachelor degree in Materials
Science and Engineering from Sichuan
University, China in 2011. His research has
been focusing on cathode materials for both
lithium-ion batteries and sodium-ion
batteries, carbon materials, and synchrotron
radiation techniques.
Teófilo Rojo received his Ph.D. in
chemistry from the University of the Basque
Country in 1981. He became a full ‐ time
professor of inorganic chemistry at the
UPV/EHU in 1992. His research has been
focused on solid state chemistry and
materials science. Since 2010 he is the
Scientific Director of the Electrochemical
Energy Storage Area at CIC Energigune,
leading research on batteries and
supercapacitors. Appointed in 2015 as an
academic member of the Royal Spanish
Academy of Exacts, Physical and Natural Sciences, in 2016 he was named
member of the Working Party on Chemistry and Energy of EuCheMS
(European Chemical Science).
Xiaolin Li is a senior scientist at Pacific
Northwest National Laboratory. He received
his B.S. and Ph.D. in chemistry from
Tsinghua University and conducted his
postdoctoral research in Prof. Hongjie Dai's
group at Stanford. His current research
interest is on materials design and
fundamental electrochemistry for
rechargeable batteries and fuel cells.
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MINIREVIEW

always >4.2 Å. Further calculation shows that the sodiation

potential increases with the initial interlayer distance between
two graphene sheets and the defects. Figure 2c shows that the
sodiation potential is >0 V when the interlayer distance is >3.94
Å or with one point defect of mono-vacancy (MV) or di-vacancy
(DV) in the 6×6×2 model and interlayer distance of 3.4 Å. [25]
Practical HC materials usually have the interlayer spacing of
~3.8 Å and many defects in the disordered structure. Hence, the
intercalation may form 100% NaC8, which delivers a theoretical
capacity of 279 mAh•g-1 at close to 0 V.[29] Recently, expanded
graphite with an interlayer spacing of 4.3 Å was prepared
experimentally. It realized ~284 mAh•g-1 reversible capacity for
Na storage, corroborating the above theoretical calculation. [30]. It
is reasonable to assume that the intercalation contributes a
maximum capacity of ~279 mAh•g-1 for Na-ion storage in HC.
Second, the capacity limit of absorption/clustering of Na-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”, assuming that the Na-ions adsorb
on the surface of the porosities and fully fill them and turn into
Na metal, the specific capacity would follow the following
equation:
Q = ρFV/3.6A
Where ρ is the density of Na metal (0.97 g•cm -3), F is the
Faraday constant (~96500 C•mol-1), V is the volume of closed
pores (unit: cm3•g-1) and A is the molar mass of Na (23 g•mol -
1 [29]
). This empirical equation provides a rough estimation of the
capacity derived from porosity. Because the Na-ions will only
turn into quasi-metal (see Section 2.2) and do not fill 100% of
the porosity and the process is not completely reversible, the
value calculated using the above equation slightly overestimates
the maximum capacity contribution from the pores. But it will
give us some information of the upper boundary.
The estimation of the volume of closed pores also introduces
inaccuracy because of the technical limitation in porosity
measurement. The pore volume from regular N2 absorption and
the closed pore volume are not the same. N2 Gas adsorption
methods are only able to provide open porosity information,
which usually contributes to irreversible capacity and low first
cycle Coulombic efficiency. The closed pores and the open
pores that fall behind the detecting limit will not be accounted for.
The closed pore volume can be estimated from true density
measurement using the liquid (Butanol etc.) and gas phase (He
gas) displacement experiments.[31] Commercial HC usually has Third, surface absorption storage of Na-ions is associated with
the true density of 1.52 g•cm-3 and small surface area and open the surface directly in contact with the electrolyte, but the
pore volume from N2 absorption.[31] Assuming the turbostratic surface area varies largely between different HC products. And
graphitic domain in HC has similar density of ~2.2 g•cm -3 to practically,
graphite, a rough volume of 0.22 cm3•g-1 can be estimated for Figure 2. Simulation results of the intercalation of Na-ion into
the closed pores, which would result in ~248 mAh•g-1 capacity graphene layers. (a) Calculated formation energies of alkali
derived from pore-filling in theory. metal (M)-graphite compounds (Reproduced with permission [15],
The above capacity calculated for the closed pore filling also Copyright PNAS 2016). (b) Simulation of the sodiation potential
includes the contribution from vacancy defects that are not in and interlayer spacing for a NaC8 ordering. (c) The sodiation
contact to the electrolyte. These vacancies are also tiny closed potential at low Na contents as a function of the initial interlayer
pores that contributes to the low true density of HC. The effects distances c0 for two pristine graphene layers and layers with
of doped heteroatoms and defects on the surface are not mono-vacancy (MV), di-vancy (DV), and Stone-Wales (SW)
included. defects. (Reproduced with permission[16], Copyright Royal
Society of Chemistry 2015).

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cycle Coulombic efficiency. The capacitive storage will become

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marginal in this regard.
reducing the surface area is an important approach to reduce
the electrolyte decomposition (Section 4.1) and to improve the
MINIREVIEW

first
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MINIREVIEW

Based on the sole combination of the contribution from intercalation and pore-filling, HC could possibly deliver a
Table 1 Summary of representative publications with over 280 mAh•g -1 reversible
capacity.
Electrolyte
Electrochemical performance Pyrolysis method Structure Ref.

298 mAh•g-1 at 50 mA•g-1 1M NaClO4 Peat moss Delated interlayer spacing with [32]
203 mAh•g-1 at 500 mAg-1 EC+DEC 1100 oC open macropores
1M NaClO4 Banana peels
355 mAh•g-1 at 50 mA•g-1 Delated interlayer spacing [33]
EC+DEC 1100 oC
335 mAh•g-1 at 40 mA•g-1 1M NaClO4 Sucrose Absence of pores detectable [34]
200 mAh•g-1 at 300 mAg-1 EC+PC 1100 oC through N2 adsorption
288 mAh•g-1 at 50 mA•g-1 1M NaClO4 Pomelo peels H3PO4 activation creates 3D- [35]
71 mAh•g-1 at 5000 mAg-1 EC+PC 700 oC connected porous structure
315 mAh•g-1 at 100 mA•g-1 1M NaClO4 Peanut shells Highly interdilated graphene [36]
107 mAh•g-1 at 2500 mAg-1 EC+DEC 1200 oC layers
1M NaClO4 Gelatin Mesoporous carbon assisted by
360 mAh•g-1 at 50 mA•g-1 [37]
EC+DEC 700 oC magnesium citrate
Resorcinol–
1M NaClO4
360 mAh•g-1 at 20 mA•g-1 formaldehyde Enlargement of macropore size [20]
EC+DEC
1600 oC
Disordered structure,
338 mAh•g-1 at 30 mA•g-1 1M NaClO4 PANi [38]
interconnected porosity and
111 mAh•g-1 at 600 mAg-1 EC+DEC 700 oC
nitrogen doping
1M NaPF6 Sucrose/GO Graphite oxide reduces the
280 mAh•g-1 at 20 mA•g-1 [39]
EC+DEC 1100 oC surface area to only 5.4 m2/g
1M NaClO4 PEDOT/PPy Sulfur doping expanded the
303 mAh•g-1 at 500 mA•g-1 [40]
EC+PC 700 oC interlayer spacing
1M NaClO4 Shaddock peel Honeycomb-like structure with
430.5 mAh•g-1 at 30 mA•g-1 [41]
EC+DEC 700 oC large interlayer spacing
1M NaClO4 Dry oak leaves
360 mAh•g-1 at 10 mA•g-1 Freestanding carbon membranes [42]
EC+DEC 1000 oC
1M NaPF6 Cotton
315 mAh•g-1 at 30 mA•g-1 Uniform microtubular structure [43]
EC+DMC 1300 oC
Sucrose/GO POx doping increases the
1M NaPF6
359 mAh•g-1 at 20 mA•g-1 /H3PO4 spacing and causes more [44]
EC+DEC
1100 oC defective structure
438 mAh•g-1 at 0.05 mA•per unit 1M NaPF6 α-cellulose [45]
52.5% closed pore
area EC+DEC 2400 oC
Large micropores and large
1M NaPF6 Argan shells
333 mAh•g-1 at 25 mA•g-1 number of active sites with HCl- [46]
EC+DEC 1200 oC
pretreatment
1M NaPF6 Carbon dot Ultrathin sheet with large area,
328 mAh•g-1 at 100 mA•g-1 [47]
PC+FEC 1200 oC expanded layer and P doping
Urea
1M NaClO4 Expanded layer spacing and
350 mAh•g-1 at 50 mA•g-1 Sol gel [48]
EC+PC enlarged surface area
650 oC
“Honeycomb briquette” shaped
1M NaClO4 PVP
394 mAh•g-1 at 20 mA•g-1 microstructure with macropores [49]
PC+FEC 1000 oC
with P doping
Sucrose
1M NaClO4 Few in-plane defect and non-
361 mAh•g-1 at 20 mA•g-1 Hydrothermal [50]
EC+DEC detectable porosity
1300 oC
Paper
1M NaPF6 Highly defective induced by
308 mAh•g-1 at 20 mA•g-1 650 oC [51]
EC+DEC microwave treatment.
Microwave
1M NaClO4 Apple pomace
297 mAh•g-1 at 20 mA•g-1 Non-detectable closed pores [52]
EC+PC 1100 oC

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MINIREVIEW
capacity of >530 mAh•g-1 if the structure is 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 the
works 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, defect amount and pore size to
improve the capacity of HC.
2.2. Disputation on sodiation pathways: Intercalation-pore
filling vs. adsorption-intercalation-pore filling
Figure 3. Disputation on 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 pristine, 0.4 V, 0.2 V, 0.1 V, 0 V and
charged to 2 V respectively. (d) Dependence of the interlayer
spacing estimated from the XRD result vs the discharge capacity
in both SIB and LIB. (Reproduced with permission from [45],
Copyright John Wiley & Sons Ltd. 2011) (e) Sodiation
potentiograms for different carbons. (f) Plot of the sloping
capacity vs the ID/IG ratio from Raman spectra. (Reproduced
with permission[47], Copyright American Chemical Society 2015).
(g) Operando 23Na ss-NMR spectra for an electrochemical cell
with Na metal and HC electrodes. (Reproduced with
permission[50], Copyright Royal Society of Chemistry 2016). (h)
23
Na magic angle spinning (MAS) NMR of HC at various
discharge points. (i) EPR spectra of HC at various discharge
points. (Reproduced with permission[51], Copyright John Wiley &
Sons Ltd. 2018)
An anode material not only needs to have a high specific
capacity but also a relatively low voltage potential in order to
enable high energy density for full cells. In this regard, it is
essential to understand the correlation between the sodiation
potential and the storage sites, in another word, the sodiation or
Na-ion storage/transfer pathways. It is the foundation for
appropriate tuning of the HC structure.
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The typical discharge curve of HC vs. Na metal is composed of
a slope region (Region I) and a plateau region (Region II). There
is a major debate recently on the assignment of these two
regions to the different Na-ion storage mechanisms.[22] Figures
3a and 3b show the schematic of the intercalation-pore filling
mechanism and the adsorption-intercalation-pore filling
mechanism, respectively. In the model (Figure 3a) proposed
early by Dahn et al., Region I was assigned to the intercalation
of Na-ions into the parallel graphitic layers and Region II was
assigned to the filling of nanoporosity between randomly stacked
layers. The intercalation of Na-ions follows a slope trend
because the potential for further insertion of Na-ions can be
changed when there are more Na-ions in the graphene layer.[21]
The mechanism has been supported by many other studies.
Komaba et al. observed a negative shift using ex-situ X-ray
diffraction (XRD) when HC was discharged to 0.1 V, indicating
that the interlayer spacing was expanded because of Na-ion
insertion (Figures 3c-3d). Small angle X-ray scattering (SAXS)
analysis on the sample discharged below 0.2 V showed
decreased intensity corresponding to the nanopores with size of
ca. 14 Å reversibly. It indicated that within this voltage range, the
Na-ions inserted into the nanopores.[53] Bai et al.[54] also believes
the low plateau is associated with the pore-filling mechanism
from the fact that they found the low-voltage plateau
disappeared after filling the HC micropores with sulfur.
The debate originally was raised when highly porous HC was
studied for Na-ion storage. Ding et al. found that the low voltage
plateau capacity was not positively proportional to the porosity of
the HC material.[32] The d-spacing of the graphene layers
expanded from 3.96 Å to 4.16 Å within the voltage window of
0.1-0.2V, indicating that Na intercalation took place. This leads
to the speculation that the low voltage region II is not due to pore
filling and Dahn’s model may be subject to amendments.
Many other studies side with amending the sodiation mechanism.
Figure 3b shows the representative model of the sodiation
sequence of HC. Bommier et al. tuned the microstructure of HC
through the pyrolysis of sucrose under 1100, 1400 and 1600 °C
so that the resultant HCs displayed decreasing d-spacing
between the graphene sheets and increasing size of turbostratic
nanodomains with temperature increase. [55] As shown in Figure
3e-f, they observed decreased capacity from the slope region
while increased capacity from the plateau region with the
increasing of the turbostratic nanodomains, completely opposite
trend to the conventional “intercalation-pore filling” model.
Because larger turbostratic nanodomains is unambiguously
more favorable for Na-ion intercalation, it indicates that the
plateau region instead of the sloping region is associated with
the Na-ion intercalation. Inspired by the theoretical calculation of
the effect of defect on improving the sodiation potential,
speculation was made that the slope region is more likely to be
linked with the defect of the HC.[29] Following the work,
experimental studies on the defect effect on HC performance
have been conducted including introducing defect to the HC
structure by heteroatom doping. Li et al. used both boron and
phosphorus to dope HC and found that the interlayer spacing
was expanded after doping, which in turn contributed to higher
capacity of the plateau region. By increasing the doping level of

MINIREVIEW
boron and phosphorus, the slope region capacity was also
increased accordingly. The wide range of binding energy
explains why the adsorption proceeds in the slope region. The
study revealed that the slope region is related to binding of Na-
ions to defects and the plateau region is due to Na
intercalation.[56]
All the studies provided comprehensive characterizations of the
sodiation of HC and caution has been taken in claiming the
conclusion. However, the measurement of surface area, pore
volume, and pore size distribution was mainly achieved by
collecting N2 gas adsorption on surface/open pores, the closed
pores or pores that fall beyond the detecting limit may not be
accounted for. Hence, the change of the closed pores with the
experimental condition and the effect to the capacity contribution
has not yet been fully assured. It is essential to adopt methods
such as SAXS to fully unveil the possible contribution from
closed pores.[22] Also, in gas absorption measurements, gasses
with greater accuracy such as Kr adsorption, which provides
details of ultramicropores (< 0.7 nm) and small surface area that
are generally not taken into consideration, should be adopted to
avoid the discrepancy caused by the detection limit of N 2 or
CO2.[57]
Another debate lies on the Na clustering in the nanopores at the
end of discharge. Stratford et al. used operando 23Na solid-state
nuclear magnetic resonance (ss-NMR) to examine the behavior
of Na during discharge and charge.[58] As shown in Figure 3g,
the colored peak shows a shift to higher frequency close to Na
metal at the end of discharge revealing that these Na-ions are
quasi-metallic clusters. The process is highly reversible,
corresponding to Region III in Figure 3b. However, in Qiu et al.’s
study using ex-situ NMR and electron paramagnetic resonance
(EPR) as shown in Figure 3h-i, no such evidence was observed
at the end of discharge to 0 V. Instead, only a sharp peak
corresponding to Na metal was observed when the HC was
discharged to -0.03 V.[29] Such a discrepancy has been
explained by Stratford et al. by assuming the Na cluster formed
at the end of discharge was meta-stable and ex-situ studies tend
to show misleading result since the Na metal could have
disappeared before the HC electrode was collected for
characterizations.[58]
3. Solid electrolyte interphase (SEI) and
electrolyte systems for SIB HC anodes
The performance of HC as SIB anodes does not solely depend
on its structure, 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 proven impractical in
graphite for LIBs start to be seriously reconsidered. An ideal
electrolyte for SIBs should be stable enough in the voltage range
and does not hamper the Na-ion transfer kinetics. In the
meantime, it should not deteriorate the structure of the anode
material.
3.1. The role of SEI: Ternary intercalation in graphite vs.
binary intercalation in HC
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Electrolyte with cyclic carbonate including propylene carbonate
(PC) and ethylene carbonate (EC), linear carbonate including
dimethyl carbonate (DMC), diethylene carbonate (DEC), ethyl
methyl carbonate (EMC) and ethers have been thoroughly
investigated in LIBs.[60] Electrolyte decomposes on carbon
anodes under low voltage and the decomposition product forms
a layer termed as SEI that 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 generally
associated with the co-intercalation mechanism.[61] As shown in
Figure 4a, the intercalation of alkali metal ions into graphite may
undergo three separate scenarios. First, if the alkali ion is very
large and has weak solvation effect, no intercalation will take
place. Second, if the alkali ion solvates strongly, it may induce a
co-intercalation mechanism by forming a ternary-graphite
intercalation compound (t-GIC). This process expands the
graphite layers and leads to two consequences. If the t-GIC is
stable against oxidation, the co-intercalation becomes 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 for the performance. The original
application of graphite in LIBs was strongly impeded by the
exfoliation problem with PC or ether electrolyte, making it
impractical until EC was introduced. The decomposition product
from EC is able to form very stable SEI and prevents the co-
intercalation and exfoliation effectively. [11] With regard to these,
the SEI is generally required to be ionically conductive and
stable.
In SIBs, however, different behavior was observed when using
graphite and HC as the anode materials. As mentioned in
Section 2.1, the intercalation of Na-ions into graphite is
thermodynamically unfavorable because extra energy is needed
to overcome the van der Waals interactions between adjacent
graphene layers. However, when using ether-based electrolyte,
highly reversible and fast intercalation/de-intercalation was
observed.[62, 63] 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 (Figure 4b).
Furthermore, the reversible co-intercalation of the t-GIC has long
term stability for SIBs while fast fade for LIBs due to the
structure difference of the t-GIC.[64] The fact that t-GIC can
transport across the HC surface at fast rate raised concerns of
the actual role of SEI for HC, the thickness of which should be
controlled to a certain degree that it prohibits the electrolyte
decomposition while does not affect the cation and even t-GIC
transport.[65, 66]
Along the same line, it is natural to understand HC with the
structure of highly disordered graphitic domains randomly
stacked together, is unfavorable for the ternary co-intercalation.
Indeed, Li et al. compared the voltage profiles of HC cycled in
carbonate and ether electrolyte.[17] As shown in Figure 4c,
similar charge-discharge curves were obtained and no co-
intercalation plateau was observed in HC. This is consistent with
the simulation result that ether intercalation only happens at the
edge of the graphene layers.[17] It is binary interaction in HC no
matter carbonate or ether electrolyte was used.
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MINIREVIEW

dissolve into the electrolyte since there is a lack of cross-linked

organic species.[69]
The outstanding performance of HC in ether-based electrolyte
together with the ternary intercalation with graphite challenges
the universality of creating a “good” SEI layer. At least, the
question of what is a “good” SEI has been raised. Unlike Li
intercalation into graphite, Na intercalation into HC does not
involve much exfoliation trouble. The SEI is not a significant
component from this regard. The inherently higher voltage of Na
against Li promises increased electrochemical potential (vs.
SHE) for the electrolyte decomposition and different SEI
properties in SIBs,[53] hence the requirement of SEI for stable
performance is much lower than that of LIBs.

Figure 4. Ternary intercalation in graphite and binary

intercalation in HC. (a) Schematic figures showing different co-
intercalation and exfoliation scenarios of alkali metal ions
intercalation into graphite (Reproduced with permission [57],
Copyright John Wiley & Sons Ltd. 2017). (b) Charge/discharge
curves of graphite in diglyme (DEGDME) with different
electrolyte salts. (Reproduced with permission [55], Copyright
John Wiley & Sons Ltd. 2015) (c) Typical charge/discharge
curves of HC in TEGDME and carbonate. (Reproduced with
permission[56], Copyright John Wiley & Sons Ltd. 2018)
Figure 5. Comparison of the electrochemical performance of HC
in carbonate and ether electrolyte. (a) Long term cycling
3.2. Ether vs. carbonate: SEI formation and ion transfer
performance of HC in carbonate. (b) Long term cycling
kinetics
performance in TEGDME. (c) In-situ EIS measurement of HC
cycled in carbonate. (d) In-situ EIS measurement of HC cycled
Recent researches have revealed that HC shows much better
in TEGDME. (Reproduced with permission[56], Copyright John
performance in ether-based electrolytes than carbonate
Wiley & Sons Ltd. 2018)
electrolytes. Figure 5a-b shows that the performance of HC in
both electrolytes was close at low current density (50 mA•g -1).
While HC in TEGDME showed dramatically better performance
than in carbonate when the rate was elevated to 500 and 1000 4. From fundamental understanding to
mA•g-1.[17] It is consistent with the results reported by Yang et practical material design
al.[68] X-ray photoelectron spectroscopy (XPS) analysis of the
cycled HC electrolyte surface showed that the SEI formed in In order for HC to be practically used for SIB full cells, both high
TEGDME was much thinner compared to that in carbonate. reversible capacity and high initial Coulombic efficiency (ICE)
Similar conclusion was also drawn in Zhang et al.’s work using are desired from the performance wise. It is dictated by the HC
diglyme as the electrolyte solvent.[68] structure and the efficiency of the electrolyte. Hence
Na-ion transfer kinetic difference in the two systems has been modifications on both sides can elevate the capacity and ICE.
investigated using an in-situ three-electrode electrochemical
impedance spectroscopy (EIS) measurement (Figure 5c-d). It 4.1. Structural modification
was found that the impedance of the HC electrode vs reference
electrode did not drop significantly until reaching the plateau Enlarging the interlayer spacing, defect control and porosity
region in carbonate electrolyte. However, when sodiated in control have been well-documented to improve the HC
TEGDME, the impedance dropped at the slope region and the performance as SIB anodes. Enlarging the interlayer spacing is
overall value was consistently lower than that of carbonate, an unambiguous approach to improve the capacity in all of the
indicating that the Na-ion transfer through the SEI in carbonate reports as has been discussed in previous sections. A good
was much more sluggish compared to that in TEGDME. In example is the use of expanded graphite, which delivered 283
addition to the poor ionic conductivity of the SEI formed in mAh•g-1 capacity at 20 mA•g-1, close to the theoretical
carbonate, it was also found to be unstable and tends to intercalation capacity.[30]

This article is protected by copyright. All rights reserved


MINIREVIEW
There are various approaches for defect engineering. Usually it
is through controlling the annealing temperature or elemental
doping. The hetero atom doped to the graphitic planes are
reactive sites where Na-ions adsorb to and hence can improve
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 of N/S-co-doped HC using
cellulose/polyaniline microspheres as the precursors. The final
product achieved a high capacity of 280 mAh•g-1 at 30 mA•g-1
along with superior rate capability (130 mAh•g-1 at 10 Ah•g-1).
The outstanding performance was ascribed to the easy
adsorption due to expanded interlayer and doping-induced
defects. The defects enable decreased diffusion barrier and
enhanced electronic conductivity.[70] However, discrepancies
exist in the role of the defects. Recently, Xiao et al. was able to
obtain outstanding performance of 361 mAh•g-1 capacity and
86.1% ICE with HC of low in-plane defect (Figure 6a). The
simulation results revealed that the Na distribution is highly
uniform within defect-free carbon layers while the Na distribution
becomes sparse when there are defects in the carbon structure.
It was proposed that Na-ions get trapped at the defect sites due
to strong adsorption energy, which are 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
restricted performance.[50] The discrepancy between these
studies implies that it is essential to classify the particular defect
type and amount, which may affect the contribution degree to
the capacity.
Figure 6. HC structure engineering to improve the ICE. (a) ICEs
of HC with different ramping rate, lower ramping rate resulted in
lower defect amount and porosity. (Reproduced with
permission,[42] Copyright ) (b) Photo 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
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mixed with GO. (Reproduced with permission,[31] Copyright
American Chemical Society 2015)
Increasing the porosity is also believed to be beneficial to the
HC performance. High capacity was achieved based on
macropores/mesopores/micropores or open 3D structures that
allow for efficient electrolyte utilization and Na-ion diffusion
rate.[38] However, both Bommier et al.[34] and Xiao et al.[50]
reported that the reversible capacity was inversely proportional
to the amount of measurable porosity (≥ 0.4 nm), that is, low
measurable porosity results in high reversible capacity. These
works, however, cannot rule out the importance of closed pores,
since most of the pore-filling capacity is contributed by closed
pores.[22] In the patent of Kano et al., a high initial discharge
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
α-cellulose at 2400 oC at a heat ramp of 10 oC/min.[45]
It has to be noted that large surface area allows for more
abundant Na-ion intercalation pathways but accelerates the
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 when HC was synthesized through the pyrolysis of
pomelo peels activation by H3PO4, the surface area was
measured to be over 1272 m2•g-1, which resulted in only 21%
ICE.[35] A good approach is the improvement of the performance
with HC of low surface area. Luo et al. added graphite oxide
(GO) into 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% (Figure 6b-d).[39]
4.2. Pre-treatment of HC anodes
Although the higher voltage potential of Na/Na+ than Li/Li+ leads
to increased electrochemical potential for the electrochemical
reduction of electrolyte in SIBs than in LIBs, there is still a large
amount of capacity loss during the first cycle. As shown in
Figure 4c, even though TEGDME was found to form very little
SEI, it is still only able to achieve an ICE of 72%. The
irreversible defect binding, pore-filling and so forth are
responsible for this loss and hence a method to compensate it is
essential for full cell tests.[13, 60] Pre-cycling of the HC electrode
for several cycles prior to full-cell assembly has been proven to
be able to boost the full cell performance. [71] The irreversible
consumption of Na-ions due to SEI formation and ion trapping
can be effectively compensated through the pre-cycling process.
Li et al. found that the HC-Na0.44MnO2 full cell was only able to
deliver less than 30 mAh•g-1 capacity with only less than 20%
ICE and it faded to almost 0 mAh•g-1 after 100 cycles. However,
after pre-cycling the HC against Na metal for several times, the
full cell showed over 60% ICE and over 60 mAh•g-1 capacity
after 500 cycles (Figure 6a-b).[71] This method involves the
collection of HC after pre-cycling by disassembly the HC/Na
metal cell, hence is not convenient for practical purposes. In
regard of this, a pre-treatment using stabilized Li metal powder
(SLMP) was employed recently. The approach is based on a
“local short-circuit” mechanism, through which the local potential

MINIREVIEW
was brought down by the SLMP and the SEI formation and pre-
intercalation happened after immersing the electrode in the
electrolyte.[72] For HC tested in SIBs, Na metal powder is
commercially unavailable and unstable in air, hence SLMP was
explored as a pre-treatment agent.[17] Figures 7c-7d show the
performance of the pre-treated HC in both TEGDME and
carbonate electrolyte (1M 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 pre-treated HC
delivers stable cycling and high capacity in TEGDME. When
tested in full cell against Na3V2(PO4)3, the pre-treated HC was
able to achieve over 80% ICE with much higher capacity and
stability in TEGDME. The study revealed that while SLMP is a
good pre-treatment agent for HC in SIBs, it is not compatible
with carbonate electrolyte, since the Li-containing SEI formed in
carbonate electrolyte is detrimental for the transport of Na-
ions.[17, 19]
Figure 7. Pre-treatment to improve the HC performance. (a) Full
cell performance of HC vs Na0.44MnO2 without any pre-cycling.
(b) Full cell performance of HC vs Na0.44MnO2 with pre-cycled
HC. (Reproduced with permission[61], Copyright Elsevier 2016).
(c) Pre-treated HC cycled in TEGDME against Na metal. (d) Pre-
treated HC cycled in carbonate against Na metal. (Reproduced
with permission[56], Copyright John Wiley & Sons Ltd 2018)
5. Conclusions and perspectives
SIBs have attracted tremendous attention and the technology
soon will be ready for deployment on grid scale energy storage
or low speed electrical vehicles. With the broad adoption of LIBs
in various applications and the limited Li resources, the
prevalence of SIBs can be foreseen. It is essential to develop
high performance HC anode materials for SIBs and that relies
on thorough understanding of the structure, ion transfer and
storage mechanisms. This mini-review has covered the
fundamental understandings of the ion-storage mechanisms and
progress in tuning the material structure and electrolyte for
better performance. “Theoretical capacity” of HC has been
roughly estimated and supplemented by reported experimental
results. There is still plenty of room to improve the HC
performance before hitting the ceiling. Several discrepancies
between different studies in the community have been discussed
and potential solutions provided. In terms of Na storage
mechanisms, debates remain in the assignment of the Na
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storage behaviors of the slope region and plateau region during
discharge. The discrepancy roots in the complicated nature of
HC and limitations of the characterization techniques. Defect
and porosity were considered to be important to further improve
the capacity and ICE of HC by some researchers, but others
believe that they are not as profound. While these debates
continue, consensus has been reached that delating the
interlayer spacing of HC is an unequivocal approach to fully
exploit the Na storage capability.
Recent progress of the fundamental understanding has paved
the way to propose the directions of designing ideal HC structure
for high performance. When used as anode material in a full cell,
the capacity of HC is expected to derive from relatively low
voltage ranges. Regarding this, one should consider to improve
the plateau capacity and rate performance as a priority when
designing the structure. Several methods can be considered to
achieve the goal together with high ICE. First, the surface and
open porosity of HC needs to be low to avoid harsh parasitic
reactions with the electrolyte, surface capacitive storage that
happens during the slope range. The closed pores should be
appropriate to have high capacity and balanced energy density.
Second, the turbostratic domains should be dilated enough to
allow for easier Na intercalation/de-intercalation and high
capacity while not too large to enable exfoliation. Third, the
defects require appropriate engineering because it accounts for
the increase of sodiation of potential, expand the interlayer
spacing and trapping of ions flow the flux and generating
repulsive electric field, which makes their effect on the capacity
controversial. At last, it has to be noted that the porosity among
all the HC material parameters may require re-assessment. In
most of the researches, porosity was measured based on N2
adsorption/desorption, which has a low pore volume detection
limit and poor characterization on the closed pores.
Developing advanced electrolyte and optimized SEI are also
important for HC to have high performance as SIB anodes. The
development of LIBs has provided tremendous knowledge for
SIBs to leverage, while the dissimilarity of Na and Li also
indicate that SIBs may in the end have the unique optimized
electrolyte of their own. The electrolyte not only needs to have
good interaction at the HC anode side but also the cathode side,
which has more requirement for high voltage stability than in
LIBs. In regard of this, it is crucial to develop high performance
electrolytes of high voltage stability.
Acknowledgements
The authors would like to acknowledge the financial support
from the U.S. Department of Energy’s (DOE’s) Office of
Electricity Delivery & Energy Reliability (OE) under Contract No.
70247A.
Keywords: sodium-ion batteries • anode • hard carbon • ion
storage

MINIREVIEW
[1] P. K. Nayak, L. Yang, W. Brehm, P. Adelhelm, Angew
Chem Int Ed Engl 2018, 57, 102.
[2] J. Deng, W.-B. Luo, S.-L. Chou, H.-K. Liu, S.-X. Dou,
Advanced Energy Materials 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 Engl 2015, 54, 3431.
[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 Materials 2016, 5, 191.
[8] C. Fang, Y. Huang, W. Zhang, J. Han, Z. Deng, Y. Cao, H.
Yang, Advanced Energy Materials 2016, 6, 1501727.
[9] Y. Liu, J. S. Xue, T. Zheng, J. R. Dahn, Carbon 1996, 34,
193.
[10] W. Xing, Journal of The Electrochemical Society 1996, 143.
[11] K. Xu, Chem Rev 2004, 104, 4303.
[12] D. Aurbach, Journal of The Electrochemical Society 1996,
143.
[13] H. Hou, X. Qiu, W. Wei, Y. Zhang, X. Ji, Advanced Energy
Materials 2017, 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 Environ. 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, Advanced Energy Materials
2018, 1801441.
[18] F. A. Soto, A. Marzouk, F. El-Mellouhi, P. B. Balbuena,
Chemistry of Materials 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, Journal of The Electrochemical
Society 2000, 147, 1271.
[22] D. Saurel, B. Orayech, B. Xiao, D. Carriazo, X. Li, T. Rojo,
Advanced Energy Materials 2018, 8, 1703268.
[23] M. Winter, J. O. Besenhard, M. E. Spahr, P. Novák,
Advanced Materials 1998, 10, 725.
[24] Y. Liu, B. V. Merinov, W. A. Goddard, 3rd, Proc Natl Acad
Sci U S A 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, The Journal of Physical Chemistry C 2013,
118, 16.
[27] K. Nobuhara, H. Nakayama, M. Nose, S. Nakanishi, H. Iba,
Journal of Power Sources 2013, 243, 585.
[28] P. Ge, Solid State Ionics 1988, 28-30, 1172.
This article is protected by copyright. All rights reserved
1864564x, 2019, 1, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.201801879 by Readcube (Labtiva Inc.), Wiley Online Library on [23/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
[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,
Advanced Energy Materials 2017, 7, 1700403.
[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] M. Yoshio, J. R. Brodd, A. Kozawa, Lithium-Ion Batteries
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. Hazelton, 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, Journal of
Materials Chemistry 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 (Weinh) 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, Advanced
Energy Materials 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
Letters 2016, 1, 395.
[45] A. Kano, N. Hojo, M. Fujimoto, United States Patent
Application Publication 2016, 20160104889.
[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
(Weinh) 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, Advanced Energy Materials 2018, 8,
1702781.
[50] L. Xiao, H. Lu, Y. Fang, M. L. Sushko, Y. Cao, X. Ai, H.
Yang, J. Liu, Advanced Energy Materials 2018.
[51] Z. Li, Y. Chen, Z. Jian, H. Jiang, J. J. Razink, W. F. Stickle,
J. C. Neuefeind, X. Ji, Chemistry of Materials 2018.
[52] X. Dou, C. Geng, D. Buchholz, S. Passerini, APL Materials
2018, 6, 047501.
[53] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki,
T. Nakayama, A. Ogata, K. Gotoh, K. Fujiwara, Advanced
Functional Materials 2011, 21, 3859.

MINIREVIEW
[54] P. Bai, Y. He, X. Zou, X. Zhao, P. Xiong, Y. Xu, Advanced
Energy Materials 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, Advanced Energy Materials 2017, 1602894.
[57] C. Matei Ghimbeu, J. Górka, 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 (Camb) 2016, 52, 12430.
[59] 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,
Advanced Energy Materials 2017, 1700403.
[60] J. Song, B. Xiao, Y. Lin, K. Xu, X. Li, Advanced Energy
Materials 2018, 8, 1703082.
[61] T. Abe, N. Kawabata, Y. Mizutani, M. Inaba, Z. Ogumi,
Journal of The Electrochemical Society 2003, 150.
[62] B. Jache, P. Adelhelm, Angew Chem Int Ed Engl 2014, 53,
10169.
[63] H. Kim, J. Hong, Y.-U. Park, J. Kim, I. Hwang, K. Kang,
Advanced Functional Materials 2015, 25, 534.
This article is protected by copyright. All rights reserved
1864564x, 2019, 1, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.201801879 by Readcube (Labtiva Inc.), Wiley Online Library on [23/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
[64] S. C. Jung, Y.-J. Kang, Y.-K. Han, Nano Energy 2017, 34,
456.
[65] J. Xu, Y. Dou, Z. Wei, J. Ma, Y. Deng, Y. Li, H. Liu, S. Dou,
Adv Sci 2017, 4, 1700146.
[66] J. Maibach, F. Jeschull, D. Brandell, K. Edstrom, M. Valvo,
ACS Appl Mater Interfaces 2017, 9, 12373.
[67] G. Yoon, H. Kim, I. Park, K. Kang, Advanced Energy
Materials 2017, 7, 1601519.
[68] J. Zhang, D.-W. Wang, W. Lv, S. Zhang, Q. Liang, D.
Zheng, F. Kang, Q.-H. Yang, Energy Environ. Sci. 2017, 10, 370.
[69] R. Mogensen, D. Brandell, R. Younesi, ACS Energy
Letters 2016, 1, 1173.
[70] D. Xu, C. Chen, J. Xie, B. Zhang, L. Miao, J. Cai, Y. Huang,
L. Zhang, Advanced Energy Materials 2016, 6, 1501929.
[71] 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.
[72] M. W. Forney, M. J. Ganter, J. W. Staub, R. D. Ridgley, B.
J. Landi, Nano Lett 2013, 13, 4158.
 1864564x, 2019, 1, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.201801879 by Readcube (Labtiva Inc.), Wiley Online Library on [23/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
MINIREVIEW
MINIREVIEW
HC is currently the most suitable Biwei Xiao, Teófilo Rojo,* and Xiaolin Li*
anode material for the nascent Na-ion
battery technology. This mini-review Page No. – Page No.
focuses on elucidating the full
potential of HC materials and future
directions to exploit the performance A Minireview on Hard Carbon as Na-
through the discussion of recent ion Battery Anodes: Progresses and
progresses and clarifying some of the Challenges
discrepancies in the ion storage
mechanisms.

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