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Exploring competitive features of stationary

sodium ion batteries for electrochemical
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Cite this: DOI: 10.1039/c8ee03727b

energy storage
Tiefeng Liu, ab Yaping Zhang,c Zhanguo Jiang,ab Xianqing Zeng,a Jiapeng Ji,a
Zeheng Li,a Xuehui Gao,a Minghao Sun,a Zhan Lin,b Min Ling, *a
Junchao Zheng *d and Chengdu Liang *a

Received 22nd December 2018,
Accepted 12th March 2019
DOI: 10.1039/c8ee03727b
rsc.li/ees
Owing to the excellent abundance and availability of sodium reserves, sodium ion batteries (NIBs) show
great promise for meeting the material supply and cost demands of large-scale energy storage systems
(ESSs) used for the application of renewable energy sources and smart grids. However, the cost
advantages of stationary NIBs alone are not enough to ensure their commercial success. In this review,
we summarize the emerging attractive characteristics of stationary NIBs, such as high-rate capability,
all-climate operation, and full-battery recyclability. Together with inherent cost advantages, these merits
have resulted in an excellent compatibility between stationary NIBs and large-scale ESSs that dictates their
validity in practical applications. Representative electrode materials are highlighted to illustrate advances in
corresponding features. The insights presented in this review can inspire further research interest into NIB
design and serve as a guide for the application of NIBs in large-scale stationary energy storage.

1 Introduction in both time and region. Therefore, large-scale energy storage

Innovations in energy access bring enormous opportunities
and challenges to the energy industry.1 Electrical power is the
backbone of modern industrial society, with versatile applications,
such as in heating, lighting, transport, and communication.2 Most
electrical power has traditionally been derived from the combustion
of non-renewable fossil fuels, which presents well-known problems,
including reserve depletion and global warming.3 Recently, electrical
generation has been altered by the emergence of renewable energy
technologies.4 Various renewable and clean energy sources, such as
solar and wind energy, have been developed as complementary or
alternative technologies to prevailing fossil fuels in modern society.5
However, renewable energy is generated intermittently, leading to
an irregular electricity supply to the grid.6–8 However, electricity
utilization in offices, industry, transportation, and homes is periodic
a
Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering
Manufacture Technology, College of Chemical and Biological Engineering,
Zhejiang University, Hangzhou 310027, China. E-mail: minling@zju.edu.cn,
cdliang@zju.edu.cn
b
Electrochemical NanoEnergy Group, School of Chemical Engineering and Light
Industry, Guangdong University of Technology, Guangzhou 510006, China
c
State Key Laboratory of Environment-friendly Energy Materials, School of
Materials Science and Engineering, Southwest University of Science and
Technology, Mianyang 621010, China
d
School of Metallurgy and Environment, Central South University, Changsha,
410083, China. E-mail: jczheng@csu.edu.cn
systems (ESSs) are particularly important for the scaled-up
utilization of renewable energy technologies,9–11 as shown in Fig. 1.
Among energy storage technologies, rechargeable batteries
have attracted intensive research interest in ESS construction
owing to their intrinsic features of high round-trip efficiency,
long cycling, and ease of maintenance.12–14 Unlike energy
storage for mobile electronics (B4 W h) and electrified trans-
portation (B40 kW h), ESSs must offer the ability to store MW h
capacities that are large enough to meet renewable energy
and smart grid demands.15 Such large-scale electricity storage
requires the production of extremely large batteries, causing
material abundance, battery cost, and safety to become the
primary issues.16 In addition to the above issues, the commercial
success of ESSs generally relies on opportunities to generate
income.17 ESSs are desired to be utilized in the energy market
as load-levelling devices18 (Fig. 1). Examples include ancillary
services that facilitate the integration of wind and solar energy
into grids and enhance grid resilience through peak regulation
between day and night.19 Therefore, stationary batteries must be
well-suited to targeted ESS applications. In this context, the key
metrics of stationary batteries for ESS applications must first be
reviewed.
Firstly, applications that shift energy in a timely fashion and
harvest renewable energy are comparatively more energy intensive.
This requires stationary batteries with sufficient energy densities
and low self-discharge behavior.

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Fig. 1 Essential features of stationary NIBs for ESS applications. Inset, an example with actual data from the Kahuku Wind Plant wind-energy battery
storage system, illustrating enhanced flexibility resulting from batteries being charged or discharged to limit the rate of change of wind power. Source:
http://www.nrel.gov/docs/fy14osti/59003.pdf.
Secondly, frequent peak regulation within seconds or minutes is
a relatively short-duration process needed to conciliate momentary
differences between demand and supply. This favors a fast
response, requiring stationary batteries with alternate high-rate
charging and discharging in rapid succession.
Thirdly, battery charging/discharging operations must stable
in all climates. The electrochemical behavior of stationary
batteries must be independent of ambient temperature as much
as possible.
Finally, ESS applications inevitably produce massively end-
of-life batteries. The environmentally friendly disposal of waste
batteries to avoid incurring costs is a prescient product design
consideration.
To this end, several promising battery candidates, such as
lead–acid batteries (LABs), lithium-based batteries, and sodium-
based batteries, have been intensively investigated by the battery
community and research institutes to confirm their compatibility
with ESS applications.6,20 As a 100-year-old battery system, LABs
have already seen significant progress in low-cost and heavily
regulated operation. However, the key drawback of LABs is
insufficient energy density.21 In contrast, lithium-based batteries,
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such as lithium ion batteries22 (LIBs) and lithium–sulfur
batteries23 (LSBs), have high energy densities. However, the
large-scale application of MW h-class LIBs is challenged by
resource availability, because lithium is unevenly distributed
and of limited abundance in Earth’s mineral resources. Identified
lithium reserves are only 14.3 Mt according to United States
Geological Survey data for 2016. Furthermore, most accessible
global lithium reserves are in remote or politically sensitive areas,
such as Chile (52%) and Argentina (14%),24,25 resulting in high
risk and transport costs in the lithium supply. Remaining lithium
reserves, such as in China (22%) and Australia (11%), are unable to
meet the increased demand of ESS applications. If such a path was
pursued, Li recycling would be necessary.26–29 These adverse
factors make lithium-based batteries utilization in ESSs difficult
and costly. Furthermore, other chemical energy storage technolo-
gies, such as supercapacitors (SCs) and redox-flow batteries (RFBs)
have been fully evaluated. SCs have the evident advantage of high
power, having strong short-duration operation ability to help
regulate the grid peak. However, SCs suffer from low energy
density and high self-discharge loss.12 Unlike SCs, RFBs have
advantages of design and operational flexibility, very small
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self-discharge ratios, high safety, and long lifespans. However,
the whole RFB system is limited to low efficiency because
partial energy is required to drive liquid flow.20
Alternatively, sodium is well-known for its abundant reserves
and wide distribution.30–32 The elemental abundance of sodium is
1000 times that of lithium. Furthermore, sodium salt supplies are
readily available. The United States alone produces 23 billion tons
of soda ash, which far exceeds the global yield of lithium salts.
Consequently, the cost of sodium salts is much lower than that of
lithium analogues (for example, $0.50 kg1 Na2CO3 vs. $6.50 kg1
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Li2CO3).30 Therefore, the cost and resource advantages of sodium
encourage innovations in sodium-based batteries.33 A representative
sodium-based battery technology was successfully commercialized
in high-temperature Na/S batteries (HT-NSBs) in the 1980s.34 The
NGK Company has installed HT-NSBs at nearly 200 locations
worldwide to deliver a cumulative installation base of 3700 MW h.
However, HT-NSBs require relatively high temperatures (B300 1C)
to keep the electrolyte in a molten state, which represents a
chemical hazard to safe operations and causes severe corrosion
problems. Regrettably, in 2011, a fire accident at NGK Company
reduced confidence in HT-NSBs. Regardless, resources and
technological demonstrations of sodium-based batteries provide a
promising outlook.32 Compared with HT-NSBs, room-temperature
stationary sodium ion batteries (NIBs) are a safer alternative for ESS
applications,35–37 and have received increasing research interest in
the past decade.
Inspired by these factors, much effort has been devoted
toward developing cathodes, anodes, electrolytes, and other battery
accessories for NIBs. Corresponding reviews have significantly
aided the understanding of NIB fundamentals and reaction
mechanisms.38–49 However, the compatibility between NIBs
and ESSs, which dictates their validity in practical applications,
is unambiguous. In this review, we summarize NIB features for
ESS applications, as follows: (i) low-cost resource: precursor
materials for stationary NIBs are extremely abundant and highly
accessible, meeting material-supply and cost requirements;
(ii) high-power performance: high electric and ionic conductivity
of the electrode materials allows high-rate operation, endowing
stationary NIBs with a fast response to conciliate electricity
demand and supply; (iii) all-climate adaptability: NIBs can
operate under various climatic conditions, exhibiting excellent
flexibility and reliability, even with the failure of internal and
Fig. 2 Cost and resource analysis of sodium-ion batteries. Reproduced with permission from ref. 51 Copyright 2018, Nature Publishing Group.
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external heaters to maintain the battery temperature; (iv) full-
battery recyclability: NIBs are recyclable, not only avoiding environ-
mental pollution and the ecological impact of waste batteries, but
also minimizing the demand for critical raw resources through
closed-loop recycling of valuable electrode materials.
In this review, the compatibility between the NIBs and ESSs
is fully discussed. Representative electrode materials are intention-
ally extracted for mechanistic illustrations of the corresponding
features and advancements. We also provide a comprehensive
outlook and perspective on NIB recyclability and the major
opportunities and challenges in applying stationary NIBs in
ESSs. A prescient design principle for the electrode materials
and battery framework is proposed to improve the features of
NIBs and make them more competitive in the ESS market. Only
by understanding the decisive features and manipulating the
advantages of NIBs, practically viable ESSs based on NIBs can
certainly be achieved.
2 Cost advantages of stationary NIBs
ESS applications require large-scale battery installations.50
Battery cost is of vital importance in determining the economic
feasibility of ESS applications in renewable energy and smart
grids,31 with cost-effective battery technology a preferred choice.6
The cost proportion of a typical battery is shown in Fig. 2.51 The
battery cost is mainly dependent on the selected electrode
materials, organic electrolyte, and separator. Cathode materials
account for around one third of the total battery cost, which are
the most value battery component, regardless of LIBs and NIBs.
Therefore, the cathode cost plays a key role in the whole battery
cost. In general, the cathode consists of carrying ions, transition
metals, or organic electrode materials. In this respect, sodium
has several advantages compared with lithium because sodium
compounds are versatile and can be investigated as electrode
materials. Furthermore, cell accessories for NIBs are likely to use
more economical materials than LIBs.
2.1 Sodium resource abundance
Sodium salts, such as NaCl, Na2CO3, and Na2SO4, are available
and accessible from brine, seawater, and minerals.32 The
utilization of sodium instead of lithium should apparently lead
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to a pronounced cost saving. However, this conclusion is based
on sole electrode materials rather than the whole battery.
Vaalma et al. established a model for battery performance
and cost to break down the battery cost and evaluate the
influence of different electrode ingredients on cost (Fig. 2).51
For a capacity of 11.5 kW h, the LIB cathode requires 6734 g of
Li2CO3 as lithium source. According to an average price of
US$6.5 kg1 in 2015, the total lithium cost is $44. If the LIB is
also designed using a LiMn2O4 cathode and graphite anode, the
material cost of $1022, with lithium accounting for B4.3% of
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This conclusion is in agreement with the cost analysis of NIBs
by Kim et al.53
2.2 Cheap transition metals
Transition metals are key in constructing electrode materials,54–56
facilitating reducible/oxidizable processes along with Na ion
insertion/extraction, respectively. The abundance and accessibility
of transition metals favors the low cost of electrode materials.
Encouragingly, Na ions have a bigger size gap to transition metals
than Li ions with respect to ionic radii.57 For example, the Na+

the total material cost. For NIBs using a Mn-based cathode, the
cost of sodium is only $4.57, corresponding to a cost saving of
$38.95. Therefore, a B4% cost reduction in the cathode can be
achieved by replacing Li with Na.
In addition to cathode materials, the electrolyte salts also
contain carrying ions that allow ionic conductivity between the
cathode and anode.52 As for the cathode, substituting Na with
Li indicates a cost reduction in the electrolyte. However, the
electrolyte often consists of 1.0–1.2 M electrolyte salts (such as
LiPF6 or NaPF6) and mixed organic solvents (such as ethylene
carbonate and propylene carbonate). Normally, electrolyte salt
accounts for 10–20 wt% of the total electrolyte.26 The mixed
organic solvents are identical for LIBs and NIBs. Consequently,
using the Na alternative to Li in the electrolyte results in a
negligible cost saving. As shown in Fig. 2, the electrolytes
in LIBs and NIBs have similar costs, indicating less than a
1% cost decrease. In total, the cumulative saving is around
5% of battery cost when lithium is replaces with sodium.
cation (1.02 Å) is much larger than the Fe3+ cation (0.645 Å),
compared with the Li+ cation (0.76 Å). This feature is advantageous
for the fabrication of electrode materials. Iron, manganese, and
vanadium are abundant transition metals for electrode materials,
especially iron, which is the fourth most common element in the
Earth’s crust. However, owing to the similar size of Fe3+ (0.645 Å)
and Li+ (0.76 Å) cations, cation mixing occurs readily in layered
LiFeO2, resulting in a cation-disordered rock-salt phase and elec-
trochemically inert properties.46 Therefore, alternative phosphate
structures have been developed for these budget transition metals,
such as LiFePO4, LiMnPO4, and Li3V2(PO4)3. The key drawback
of these materials is the synthesis process, which requires an
inert atmosphere, resulting in relatively high costs and material
inconsistency.
In contrast to lithium ion compounds, sodium iron compounds
with layered structures are stable. The sodium storage performance
of NaFeO2 was first reported by Okada et al.58 NaFeO2 is an
O3-phase layered oxide, with the resultant electrode delivering

Fig. 3 (a) Charge/discharge profiles of a-NaFeO2 cathode against Na anode over the initial. Reproduced with permission from ref. 58 Copyright 2013
The Electrochemical Society; (b) rate capability of a Na/Na2/3[Fe1/2Mn1/2]O2 cell. Reproduced with permission from ref. 60 Copyright 2012 Nature
Publishing Group; (c) charge/discharge curves of a Na7/9Cu2/9Fe1/9Mn2/3O2 electrode at a rate of 0.1C. Reproduced with permission from ref. 62
Copyright 2015 Wiley-VCH; (d) galvanostatic charge–discharge curves of a Na3V2(PO4)2O2F3 nanocomposite between 2.0 and 4.3 V at a current density
of 64 mA h g1. Reproduced with permission from ref. 68 Copyright 2015 Royal Society of Chemistry; (e) first cycle galvanostatic data for Na4MnV(PO4)3
at 1Na+/20 h cycled between 2.5 and 4.3 V vs. Na+/Na. Reproduced with permission from ref. 69 Copyright 2018 Wiley-VCH; (f) calculated Na voltage vs.
calculated Li voltage for different structures. Reproduced with permission from ref. 70 Copyright 2011 Royal Society of Chemistry.

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a reversible capacity of 85 mA h g1 at a stable voltage plateau of
3.3 V. The electrochemical activity is derived from the Fe3+/Fe4+ redox
couple. Similarly, Na0.44MnO2 also exhibits outstanding electro-
chemical capability and cycling stability.59 Furthermore, iron-based
binary compounds, such as P2-Na2/3[Fe1/2Mn1/2]O2,60,61 and ternary
systems, such as P2-Na7/9Cu2/9Fe1/9Mn2/3O2,62 have been widely
reported to have excellent electrochemical behaviors.63 Therefore,
NaxMO2 (M = Mn and Fe) has been demonstrated to have electro-
chemical activities. These NaxMO2 materials can be prepared under
the air conditions, which provides cost advantages and simple
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synthetic processes for NIB electrode materials (Fig. 3).
Other than layered metal oxides, phosphate compounds
with open three-dimensional (3D) structures, such as Na super
ionic conductor (NASICON), are also more likely to accommodate
large Na+ cations than small Li+ cations.64 Fe2(MoO4)3 or Fe2(WO4)3
have been inserted with sodium to yield two new compounds,
Na2Fe2(MoO4)3 or Na2Fe2(WO4)3, respectively.65 Bruce et al. identi-
fied reversible sodium insertion/desertion with retention of the
monoclinic symmetry. Both electrodes showed voltages of 2.7 V
vs. Na+/Na. Furthermore, vanadium-based compounds43,66 such as
Na3V2(PO4)3,67 Na3V2(PO4)2O2F3,68 and Na4MnV(PO4)369 have been
extensively explored as electrode materials in NIBs. Carbon-coated
Na3V2(PO4)3 nanowalls, constructed by Li et al. through a facile
hydrothermal method, exhibited an excellent rate performance with
a small decrease in specific capacity from 114.8 to 94.9 mA h g1
when the current density was increased from 0.1 to 5C.67 Notably,
for Na and Li versions of the same compound, the phosphate
compounds were easily prepared under thermodynamic equili-
brium conditions,70 allowing the simple and low-cost fabrication of
electrode materials. Therefore, these Fe-/Mn-/V-based electrode
materials substantially contribute to decreasing NIB costs, regard-
less of the material cost and fabrication process.
2.3 Sustainable organic materials
Organic materials have recently been explored as electrode
materials for NIBs.71,72 Their redox reactions are mainly enabled
by a charge state change of the electroactive organic groups or
moieties.73 Organic electrode materials for NIBs are largely
classified as aromatic carbonyl compounds, pteridine derivatives,
polymer sulfates, and doped or porous polymers. Compared with
inorganic materials, organic materials have several natural merits
for NIB electrodes.74 Firstly, their material sustainability and
environmental benignity are improved compared with inorganic
counterparts.75 Organic materials are often derived from natural
materials through simple chemical or thermal treatments.
Furthermore, most biomolecules in organic formulas are based
on Na cations, offering a variety of electrode material candidates.
The carbonyl group is by far the most applied organic functional
moiety in organic materials. Wang et al. reported that carbonyl-
based organic salt Na2C6O6 was synthesized through a facile
antisolvent method.76 Na2C6O6 nanorods exhibited a reversible
capacity of B190 mA h g1 at 0.1C with over 90% capacity
retention after 100 cycles. This result demonstrates the accessi-
bility of biomass-derived organic electrode materials to sustainable
energy storage devices with low cost, high electrochemical
performance, and thermal stability (Fig. 4).
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Secondly, organic electrode materials have an obvious cost
saving in materials modification. Organic materials that are
mainly composed of naturally abundant elements (C, H, O, N, S)
have tunable functional groups, making tailoring of their redox
properties and electrochemical performances easier. Furthermore,
organic materials can be readily bonded to conductive carbon-
based materials, such as carbon nanotubes and graphene,
through conjugated systems, achieving improved rate performance,
reduced compound solubility, and extended cycling lifespan.77,78 Gu
et al. prepared a sandwich-like Na4C6O6–graphene composite using
commercial Na2C6O6 through a simple hydrothermal approach.79
This architecture exhibited a high reversible capacity of 488 mA h
g1, good cycling performance, and high-rate properties for sodium
storage (151 and 95 mA h g1 at 744 and 3720 mA g1, respectively).
A similar attempt was made by Kim et al.80 Organic active materials
were encapsulated into carbon nanotubes (CNTs) to form an
electrode with high active polymer content. These CNTs retain the
active polymer within the electrode structure, providing an effective
electronic conduction path. Furthermore, the CNTs can contain
large amounts of active polymer and, therefore, exhibit superior
electrochemical properties without self-discharge, making them
well-suited for use as cathode materials in NIBs. Zhao et al. also
reported using sodium terephthalate to stepwise replace oxygen
atoms in carboxylate groups with sulfur atoms, which improved the
electron delocalization, electrical conductivity, and sodium uptake
capacity.81 The carboxylate scaffold with two sulfur atoms
introduced reached a reversible capacity of 466 mA h g1 at a
current density of 50 mA g1. When four sulfur atoms were
introduced, the capacity increased to 567 mA h g1 at a current
density of 50 mA g1. Therefore, the utilization of organic
electrode materials greatly benefits function-oriented NIB design
without requiring complicated modifications.
2.4 Economical cell components
NIB components, such as separators and current collectors, are
cheaper than their LIB counterparts.45 The separator functions
as electronic insulation between the cathode and anode. Owing
to the larger atomic radius of Na compared with that of Li, the
traditional polypropylene (PP) separator in LIBs cannot provide
sufficient space for Na+ ions to pass through. As an alternative
separator, glass fiber has a larger spacing and is commonly
used in NIBs. The cost of glass fiber is only $0.3 m2, which is
much cheaper than that of PP in LIBs ($1 m2). Therefore, the
separator cost is approx. 10% lower for NIBs compared with
LIBs. Furthermore, aluminum does not alloy with sodium, so
aluminum can be used as an anode current collector instead of
copper. The price of 15 mm-thick aluminum foil is only one-
quarter that of 10 mm-thick copper foil ($0.3 m2 and $1.2 m2,
respectively). Therefore, replacing copper with aluminum
theoretically achieves a cost reduction of approx. 4.3%.
Electrode materials recycled from spent LIBs are much
cheaper than the fresh electrode materials. Using cathodes
(LiCoO2, LiNixCoyMnzO2, and LiFePO4) from recycled LIBs in
new LIBs has been widely performed.82–84 Recycled cathodes
showed performances similar to fresh materials. Similarly,
anodes, such as graphite, have been successfully recycled and
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Fig. 4 Proposed working principles of organic electrodes in NIBs with three types of reaction. Type 1 is CQO reactions: (a) quinone compounds with
benzoquinone (BQ); (b) carboxylates with disodium terephthalate (Na2TP); (c) anhydrides with 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA);
and (d) imides with 1,4,5,8-naphthalenetetracarboxylicdiimide (HNDI). Type 2 is doping reactions: (e) organic radical compounds of poly(2,2,6,6-
tetramethylpiperidinyloxy-4-vinylmethacrylate); (f) conductive polymers of polypyrrole; (g) a microporous polymer active site; (h) organometallic
ferrocene-based polymer. Type 3 is CQN reactions: (i) Schiff-based compound and (j) pteridine derivatives. Reproduced with permission from ref. 73
Copyright 2017, Wiley-VCH.

remanufactured.85 In particular, the direct regeneration of cheap transition metals and organic materials. Furthermore,
electrode materials uses less energy and raw materials without NIBs can use more economical cell components compared with
a complex preparation process, resulting in less emissions and LIBs. Table 1 shows an illustrative example of battery component
waste, and cost savings from compliance with air-pollution changes from LIB to NIBs. According to data from the London
regulations and disposal fees.86 Therefore, battery recycling is Metal Exchange in February 2018, the price of iron is only 1%
promising for reducing battery costs. We provide more information
on the potential for NIB recycling in Section 5.
Section summary. We have briefly reviewed the cost advantages Table 1 Different cell components in LIBs to NIBs
of NIBs compared with LIBs with respect to current electrode
materials and technologies. The substitution of Li with Na is not Items LIBs NIBs
solely capable of significantly decreasing battery cost. Furthermore, Cathode LiCoO2 NaFeO2
this advantage can, to some extent, be neutralized by the relatively Anode Graphite Hard carbon
Electrolyte salts LiPF6 NaClO4
low energy density of NIBs. In contrast, the potential cost savings Separator Polypropylene Glass fiber
associated with NIBs are greatly facilitated by the utilization of Current collector Cu/Al foils Al foils

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that of cobalt ($340 vs. $33 000 by ton). Therefore, NaFeO2 is
expected to be lower in cost than LiCoO2. According to Fig. 2,
the cathode accounts for one third of the total materials cost.
Therefore, substituting LiCoO2 with NaFeO2 represents an
approx. 30% cost saving. Furthermore, battery recycling can
contribute substantially to reducing materials costs. The anode
often accounts for around 20% of materials costs. If such a path
is pursued, the cost reduction from LIBs to NIBs could be up to
50%. Therefore, the insightful design of stationary NIBs will
become increasingly attractive.
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3 Power advantages of stationary NIBs
Both electricity demand and supply in power grids vary by time
and region, as shown in Fig. 1. Such frequent fluctuations not
only cause safety concerns on grids, but also result in electricity
loss. To avoid this scenario, large-scale ESSs can be deployed to
perform two key functions, namely, modulate intermittent renew-
able sources and regulate grids through peak shifting. Fig. 5 shows
the discharge time and power rating for various energy storage
technologies. Traditional pumped hydro and compressed air energy
storage technologies have a long response process. In addition,
high-power SCs enable fast responses within seconds while suffer-
ing from low energy densities. Therefore, stationary batteries are the
most suitable for ESSs, with such speculation having been strongly
validated. Recently, NIBs with high-power performance with long
cycling were reported. The highest rate for NIBs was recorded at
500C according to Yang et al.,87 and was close to that of commonly
used SCs. Therefore, NIBs can be fully charged or discharged within
7.2 s, enabling a quick response to voltage fluctuations in the
grid. Such high-power operation is of critical importance for ESS
applications to renewable energy sources and smart grids.
In this section, we summarize recent high-rate processes in
electrode materials involving layered metal oxides, NASICON-
type compounds, carbon-based composites, and alloy-type materials.
High-rate operation in battery systems requires a unique electrode
Fig. 5 Comparison of discharge time and power rating for various energy
storage technologies. Comparisons are generalized because several of
these technologies have broader power ratings and longer discharge times
than illustrated. Reproduced with permission from ref. 6. Copyright 2011
Reprinted with permission from AAAS.
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that combines a material with high ionic and electric conductivity
and an architecture with fast ionic and electric diffusion.88–91 The
former is often the focus for rational modifications of electrode
materials.92–94 The latter is critically required for creative electrode
architectures, such as 3D frameworks, high-performance binders,
and innovative electrode designs.95–97 We have also highlighted
the importance of advanced battery design in achieving high-
power NIB technologies.
3.1 Layered transition metal oxides with high rate behaviors
Using layered metal oxides as hosts is the most extensively studied
topic in NIB research. From LIB research, rational modifications of
layered electrode materials significantly enhances their electro-
chemical behavior in high-rate operation. For example, the reaction
kinetics can be boosted using a medium layer98 and by controlling
the morphology size.99 Among single-metal Na-intercalation oxides,
NaxMO2 (M = Co, Mn, Fe, Cr, and Ni), NaCrO2 modified with a
carbon coating by Yu et al. exhibited excellent capacity retention
with superior rate capability up to 150C, corresponding to a full
charge or discharge in 27 s.100 When assembled by NaCrO2 cathode
and hard carbon anode, full NIBs also enable a high current density
with a rate of 100C. Furthermore, Dong et al. applied the
topotactically synthetic method to obtain novel hierarchical
zigzag layered Na1.25V3O8 nanowires. Excellent electrochemical
performance was achieved with high capacity (158.7 mA h g1
at 200 mA g1) and cycling stability (capacity fading of
0.0138% per cycle at 1 A g1 for 1000 cycles).101
Binary or ternary transition metals in layered oxides based
on Ni, Fe, Mn, and Co have been also explored in recent years.
Hwang et al. focused on designing heterogeneous structures for
electrode materials. Spoke-like nanorods of Na[Ni0.61Co0.12Mn0.27]O2
were assembled in spherical secondary particles. Such cathode
nanorods featured a high discharge capacity of 130 mA h g1 at
10C.102 Similarly, a spherical particle consisting of a radially aligned
hierarchical columnar structure of O3-Na[Ni0.58Co0.06Mn0.36]O2
has also been reported. This cathode exhibited a rate capacity
of 132.6 mA h g1 at 10C and a capacity retention of 80% at
125 mA h g1 during 300 cycles in combination with a hard
carbon anode.103 These examples demonstrate the potential of
NIBs for meeting the high-rate requirements of ESS applications.
Table 2 summarizes reported layered metal oxides with high-rate
performance.
3.2 NASICON-type materials with high rate behaviors
Na Super Ionic Conductor (NASICON) materials have been
applied in NIB cathodes and anodes. The general formula of
NASICON materials is NaxMM 0 (XO4)3 (M/M 0 = V, Ti, Fe and Nb;
X = P, or S, x = 0–4). The NASICON-type framework is constructed of
corner-shared MO6 (M0 O6) and polyhedral XO4 groups. Such an
open framework provides sufficient space for Na ion diffusion
channels.114 To date, massive NASICON-type materials have been
investigated for sodium storage properties, such as Na3V2(PO4)3,115
Na3V2(PO4)2O2F3,116 NaTi2(PO4)3,117 NaZr2(PO4)3,118 NaSn2(PO4)3,119
Na3MnTi(PO4)3,120 and Fe2(MoO4)3,121 which exhibited superior
ionic conductivity and stable crystalline structures.122 These
high-rate materials have been summarized in Table 3. A family
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Table 2 Summary of current layered metal oxides with high rate behaviors

Material Phase transition Morphology Capacity (mA h g1) Highest rate (C) Cycle number and retention
NaCrO2100 O3-type Carbon coating 106, at 50C 150 90% at 300 cycles
NaNi1/4Co1/4Fe1/4Mn1/8Ti1/8O2104 O3-type Irregular particles 129, at 0.1C 120 91% at 300 cycles
NaFe0.5Co0.5O2106 O3-type Irregular particles 241, at 0.05C 30 85% at 50 cycles
NaNi1/3Co1/3Fe1/3O2107 O3-type Irregular particles 163, at 0.05C 30 98% at 20 cycles
Na3Ni2SbO6105 O3-type Sub-microparticles 117, at 0.1C 30 70% at 500 cycles
Na0.67Co0.5Mn0.5O2108 P2-type Irregular particles 147, at 0.1C 30 78% at 150 cycles
Na(NiCoFeTi)1/4O2109 O3-type Irregular particles 116, at 0.1C 20 75% at 400 cycles
Na0.66Ni0.17Co0.17Ti0.66O297 P2-type Irregular particles 92, at 0.2C 15 76% at 1000 cycles
Na[Ni0.58Co0.06Mn0.36]O2102 O3-type Spherical particle 141, at 1C 10 80% at 300 cycles
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Na[Ni0.61Co0.12Mn0.27]O2103 O3-type Spoke-like nanorod 160, at 0.1C 10 63% at 100 cycles

NaTi0.5Ni0.5O2110 O3-type Irregular particles 121, at 0.2C 10 75% at 300 cycles
Na[Fe1/3Ni1/3Ti1/3]O2111 O3-type Submicron particles 117, at 0.1C 10 57% at 1000 cycles
Na2/3Mn0.8Fe0.1Ti0.1O2112 P2-type Irregular particles 144, at 0.1C 10 95% at 50 cycles
Na[Ni0.25Fe0.5Mn0.25]O2113 O3-type Spherical particle 140, at 0.1C 10 76% at 150 cycle

Table 3 Summary of current NASICON-type materials with high rate behaviours

Material Morphology and structure Size (nm) Capacity (mA h g1) Highest rate (C) Cycle number and retention
Na3V2(PO4)3@C87 Hierarchical carbon 100–500 115, at 0.2C 500 54% at 20 000 cycles
Na3V2(PO4)3@C124 Layer-by-layer 20–40 104, at 1C 200 98% at 1000 cycles
C@Na3V2(PO4)3@pC131 Double-shell nanospheres 20–40 103, at 10C 200 80.5% at 1000 cycles
Na3V2(PO4)3@C@rGO135 3D porous composites 20 115, at 1C 100 64% at 10 000 cycles
Na3V2(PO4)3@CNT-G136 3D free-standing foam 50–100 109, at 30C 100 96% at 2000 cycles
Na3V2(PO4)3@C137 3D nanofibers 20–80 110, at 10C 100 99.6% at 50 cycles
B and N doped NVP@C134 2D nanosheet 200 114, at 1C 100 92%, at 2000 cycles
Na3V2(PO4)3@C126 3D skeleton 20–200 113, at 1C 50 87.5% at 8000 cycles
Na3V2(PO4)3@C–N-CNT138 Nanoparticles with CNT 100 94, at 0.2C 70 92.2% at 400 cycles
Na3V2(PO4)3@C/G139 3D porous composites 100 87, at 40C 40 80% at 1500 cycles
Na3V2(PO4)3@C@CMK-3140 3D CMK-3 3 115, at 1C 30 68% at 2000 cycles
Na3V2(PO4)2F3@AC68 Porous nanoparticles 50 130, at 0.5C 30 95% at 50 cycles
Na3V2(PO4)3@AC95 Nanoparticles 5 101, at 5C 10 96.4% at 200 cycles
Na3V2(PO4)3@MCNT141 MCNT nanocomposites 100 147, at 0.1C 10 94.3% at 50 cycles
NaTi2(PO4)3@graphene127 3D networks 100 112, at 1C 50 93% at 200 cycles
NaTi2(PO4)3@C117 Nanoparticles 100 117, at 1C 50 98% at 1000 cycles
NaTi2(PO4)3@graphene128 3D networks 30–40 129, at 0.1C 50 1000 (at 10C) 95.5%
NaTi2(PO4)3@C122 Carbon coating 100 212, at 0.1C 20 68% at 10 000 cycles
NaTi2(PO4)3@graphene142 2D structure 100–200 110, at 2C 20 95.5% at 1000 cycles
Na3MnTi(PO4)3120 Random particles 30 58.4, at 0.1C 10 98% at 100 cycles

of vanadium-based and titanium-based materials is of particular
interest, affording NIBs with high-rate performance surpassing
that of LIBs (Fig. 6).
Na3V2(PO4)3 is a representative NASICON-type material that
has attracted much attention in the modification of NIB
electrodes. Despite high ionic conductivity, Na3V2(PO4)3 has
low electronic conductivity owing to the separation of metal
polyhedra and strong electronegativity of anions in the polyanionic
structure.123 Modifications involving coating the electronically
conductive medium without affecting ion access and tailoring
the morphology size to the shorten ionic diffusion distance are
procedures of choice aimed at boosting rate performance. Mai
et al. have devoted much effort toward improving the rate
performance of Na3V2(PO4)3 in a series of important guiding
reports. Xu et al. synthesized layer-by-layer Na3V2(PO4)3 embedded
in reduced graphene oxide. Such a heterogeneous Na3V2(PO4)3-
based composite can afford rates of up to 200C with close to 50%
of the theoretical capacity.124 A novel 3D Na3V2(PO4)3 nanofiber
network was constructed by Ren et al. using a facile self-sacrificed
template method.125 Owing to the formation of a 3D nanofiber
network structure, which provides multi-channel ionic diffusion
pathway, continuous electronic conduction, and improved structural
integrity, as-prepared Na3V2(PO4)3 composite exhibited excellent
cyclability (95.9% capacity retention over 1000 cycles at 10C) and
high-rate performance (94 mA h g1 at 100C).
Other research groups have also performed excellent Na3V2(PO4)3
studies, confirming their potential in high-rate NIBs. Zhang et al.
prepared 3D-skeleton carbon-coated Na3V2(PO4)3 using a novel soft
template approach.126 This cathode material exhibited a discharge
capacity of 113 mA h g1 at 1C, which was very close to the
theoretical capacity (117 mA h g1). The capacity retention was
87.5% after 8000 cycles at 2C and the discharge capacity was
maintained at about 60 mA h g1 at 50C. Furthermore, Fang
et al. used chemical vapor deposition on pure Na3V2(PO4)3 particles.
The resulting hierarchical carbon-framework-wrapped Na3V2(PO4)3
composite delivered a close-to-theoretical reversible capacity at 0.2C
(115 mA h g1), superior high-rate capability (38 mA h g1 at 500C),
and ultra-long cycling stability (54% capacity retention after
20 000 cycles at 30C).87 NIBs with such high-power and long-
cycling performance similar to that of supercapacitors are of great
significance for addressing the urgent issues of intermittent supply
from renewable energy and power fluctuation in smart grids.

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Fig. 6 (a) Rate performance of 3.4 wt% C-NaCrO2. Reproduced with permission from ref. 95 Copyright 2015. Royal Society of Chemistry; (b) rate
capability of NaNi1/4Co1/4Fe1/4Mn1/8Ti1/8O2 at various current densities. Reproduced with permission from ref. 97 Copyright 2015. Royal Society of
Chemistry; (c) rate capability of cells at constant Na3Ni2SbO6 charge/discharge rates from 0.1 to 30C. Reproduced with permission from ref. 98 Copyright
2014. Wiley-VCH.

For NIB anodes, NaTi2(PO4)3 nanoparticles embedded in 3D
graphene networks have successfully been prepared using a
hydrothermal method.127 Porous NaTi2(PO4)3 nanoparticles (approx.
100 nm) were homogenously distributed within the graphene net-
work, resulting in a high rate capability (67 mA h g1 at 50C) and
long cycling life (80% capacity retention after 1000 cycles). Another
similar example was reported by Roh et al. using a microwave-
assisted one-pot method to prepare well-crystallized NaTi2(PO4)3
nanoparticles (30–40 nm) uniformly precipitated on rGO templates
through Ti–O–C bonds.128 Chemical interactions between the
NaTi2(PO4)3 nanoparticles and rGO immobilized the NaTi2(PO4)3
nanoparticles on the rGO sheets, which might be responsible for the
excellent electrochemical performance of the nanocomposite.
The NaTi2(PO4)3/rGO nanocomposite exhibited an excellent rate
capability (93.7 mA h g1 at 50C) and long cycling performance
(only 4.5% capacity loss after 1000 cycles at a high rate of 10C).
Furthermore, Wang et al. designed an architecture of NaTi2(PO4)3
nanoparticles embedded in the mesoporous carbon matrix that
was realized using a facile sol–gel method. The resulting anode
exhibited superior rate capability, with a capacity of up to
56 mA h g1 at 20C (4 A g1) and capacity retention of 68%
after 10 000 cycles. Furthermore, Guo et al. reported a facile
two-step strategy for constructing a flexible and binder-free
NaTi2(PO4)3/graphene film with a sandwich structure.129 The
NaTi2(PO4)3/graphene hybrid was embedded homogeneously
in an interconnected graphene nanosheet framework to form
a 3D flexible GN/NaTi2(PO4)3/GN film. The resultant film
exhibited outstanding cycling stability (91% capacity retention
over 1000 cycles at 500 mA g1). Furthermore, a polyanionic
Na3V2(PO4)2F3 cathode exhibited an excellent capacity of
75 mA h g1 at an ultrahigh rate of 70C (1C = 128 mA g1)
and a long lifespan of 3500 cycles at 30C while retaining 79% of
the initial capacity value.130
3.3 Carbon-based materials with high rate behaviors
Graphite, which is commonly applied in LIBs, is rarely used
in NIB anodes owing to the absence of stable Na–C binary
compounds.42 Experimental and theoretical studies also indi-
cated that the formation of sodium-rich binary graphite inter-
calation compounds (b-GIC) was thermodynamically disfavored.143

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Therefore, for the carbon–ester electrolyte, sodium ions were mainly
adsorbed in the interface between electrode materials, only
delivering a capacity of around 35 mA h g1. Recently, several
studies have demonstrated that Na ions can be inserted into the
graphite interlayer through the suitable selection of electrolyte
solvents.144 Adelhelm et al. observed a so-called cointercalation
reaction in a diglyme-based electrolyte, achieving a low-over-
potential sodium storage of about 100 mA h g1 with 41000 cycles
in the graphite anode.145,146 This was attributed to solvated ions that
can easily enter the graphite lattice and rapidly diffuse, simulta-
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investigated as alternative anodes in NIBs. Stevens and Dahn
compared the storage behavior of lithium and sodium in hard
carbon.148 In contrast to Li ion insertion/deinsertion to the
disordered graphene layers in LIBs, sodium ions were mainly
adsorbed on the surface of hard carbon with an organic
carbon–ester electrolyte. Therefore, the design of micro/nano-
structures in hard carbon materials is critical to achieve fast
reaction kinetics. Xiao et al. confirmed that nanosized hard
carbon nanoparticles (HCNP) exhibited a high specific capacity
(270 mA h g1 at the current density of 50 mA g1 in the voltage

neously leading to graphite exfoliation to form platelets. Another
strategy is to expand the interlayer spacing through a process of
oxidation and partial reduction on graphite. The expanded graphite
had an enlarged interlayer lattice distance of 4.3 Å, but retained
a long-range-ordered layered structure analogous to that of
graphite. The resultant anode delivered a high reversible capacity
of 284 mA h g1 at a current density of 20 mA g1 (Fig. 7).147
In addition to the incremental capacity of graphite, the rate
improvements attracted more attention to NIB anodes. Disordered
carbon materials, such as hard carbon, have been widely
range of 0–1.2 V), remarkable cycling lifespan (77% capacity
retention over 500 cycles), and high rate capability (45 mA h g1
at 2.5 A g1).149 A similar effort was reported by Lu et al. using
a facile NaCl-template-assisted method to obtain amorphous
carbon with high electronic conductivity and a high surface
area. Consequently, such 3D amorphous carbon (3DAC) with
controlled porosity and disordered structures exhibited an
excellent rate capability (66 mA h g1 at 9.6 A g1) and a high
reversible capacity (280 mA h g1 at a low current density of
30 mA g1).150

Fig. 7 (a) Schematic illustration of structure and rate capability of HCF-NVP. Reproduced with permission from ref. 87. Copyright 2015. Wiley-VCH. (b)
Rate performance and SEM image of NVP@C cathode materials. Reproduced with permission from ref. 131. Copyright 2014, Wiley-VCH. (c) Schematic
illustration of the crystal structure and synthesis of NaTi2(PO4)3@graphene nanosheets. Reproduced with permission from ref. 127 Copyright 2015,
American Chemical Society. (d) Schematic illustration of crystal structure and electrode reaction of Na3MnTi(PO4)3. Reproduced with permission from
ref. 120. Copyright 2016, Wiley-VCH. (e) Schematic of synthetic procedure for KTP@C nanocomposites. Reproduced with permission from ref. 132.
Copyright 2018, Wiley-VCH. (f) Schematic illustration of carbon-coated hierarchical NTP-NW/C nanowire clusters with stable framework, fast Na+
diffusion, and continuous e pathways. Reproduced with permission from ref. 133. Copyright 2019, Elsevier. (g) Schematic illustration of the structure of B
and N-doped Na3V2(PO4)3@C. Reproduced with permission from ref. 134. Copyright 2018. Wiley-VCH.

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Energy & Environmental Science
Table 4 Summary of current carbon-based materials with high rate behaviours
Material and morphology Capacity (mA h g1)
150 1
3D amorphous disordered carbon 205, at 0.3 A g
Nitrogen-doped carbon nanotube155 179.1, at 0.2 A g1
Nitrogen-doped carbon nanofiber156 315, at 0.5 A g1
Carbon nanosheets157 980, at 0.2 Ag1
N/S-Codoped carbon microspheres152 280, at 0.03 A g1
S-Doped N-rich carbon nanosheets158 350, at 0.05 A g1
Layered amorphous carbon/graphene151 230, at 0.1 A g1
Amorphous carbon nitride159 430, at 0.083 mA g1
Nitrogen-doped carbon sheets160 212, at 0.1 A g1
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Porous N-doped carbon nanosheets161 204.2, at 0.1 A g1
Nitrogen-doped carbon nanosheets162 329 at 50 mA g1,
Carbon quantum dots153 255.5 at 0.5 A g1
In addition to hard carbon, examples of high-rate NIB anodes
using high-surface-area graphene composites have been reported.
Defects in graphene can provide massive sites for sodium storage.
Li et al. demonstrated the surface capacitive contribution of
graphene-based materials to achieve high-rate NIB anodes.151
Surface-induced capacitive processes (SCP), such as capacitance
and pseudocapacitance, can provide fast charge/discharge capacity
in conjunction with the capacity provided by diffusion-controlled
intercalation processes (DIP). The resulting SCP-enhanced
NIB delivered an outstanding rate capacity of 120 mA h g1 at
10 A g1, and exceptional cycling stability, retaining 83.5%
capacity of 142 mA h g1 at 0.5 A g1 after 2500 cycles. To
further enhance the electric conductivity, Xu et al. used cellulose/
polyaniline composites as precursors to prepare N and S-codoped
carbon microspheres (NSC-SP). This NSC-SP anode exhibited a
high capacity (B280 mA h g1 at 30 mA g1), superior rate
capability (B130 mA h g1 at 10 A g1), and a long cycle life of
more than 3000 cycles.152 To date, disordered carbon materials as
NIB anodes have exhibited excellent properties, including high
rates and long cycling stability. Table 4 summarizes current
carbon-based materials with high rate behaviors.
3.4 Alloy- and conversion-type electrode materials with high
rate behaviors
As for carbon-based materials, alloy and conversion-type electrode
materials also exhibit excellent rate performance, favoring high-
power NIBs. Electrode materials have been based on alloy
reactions with metals (such as Sn, Pb, and Bi) and metalloids
(such as Si, Ge, and P).163 Duan et al. fabricated ultra-small
antimony (Sb) nanoparticles embedded in a 3D nitrogen-doped
porous carbon matrix through self-wrapping and controlled
growth processes using chitosan as a self-wrapping precursor. The
nanocomposite exhibited a reversible capacity of 138 mA h g1 at a
very high current density of 32 A g1 and a capacity of 372 mA h g1
after 100 cycles at 0.5 A g1.164 Similarly, Xie et al. developed a 3D
hierarchical Sn@CNT nanopillar array grown perpendicularly on
carbon paper as a free-standing electrode. The electrode achieved a
reversible capacity of 887 mA h cm2 in the first cycle and good
cyclability until 100 cycles.165 Chen et al. reported a bismuth-
intercalated graphite (Bi@graphite) anode material,166 where Bi
nanoparticles between graphite interlayers enhanced the capa-
city and the graphite sheath provided a robust fast electronic
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Highest rate (corresponding current density A g1) Cycle number
46C (9.6) 600
55C (10) 1000
47C (15) 7000
20C (20) 1200
35C (10) 3400
28C (10) 1000
43C (10) 2500
19C (8.33) 2000
47C (10)
49C (10) 2000
30C (10) 10 000
80C (20) 10 000
connection for long cycling stability. Bi@graphite possessed a
safe average storage potential of approximately 0.5 V vs. Na/Na+,
delivered a capacity of 160 mA h g1 at 1C, exhibited out-
standing cycling stability (approx. 90% capacity retention for
10 000 cycles at 20C), and maintain 70% capacity at 300C
(B110 mA h g1 at 48 A g1), which was equivalent to full
charge/discharge in 12 s. Conversion reactions for sodium
storage involve metal oxides (TiO2, Co3O4, SnO2, and Nb2O5),
sulfides (SnS, FeS, and MoS2), phosphides, and selenides.48
Chen et al. showed that intimate integration of graphene with
TiO2 enhanced the Na+ intercalation pseudocapacitive process
by reducing the diffusion energy barrier, affording a high-rate
capability and long cycle life.167 3D petal-like graphene-rich
wrapped rutile TiO2 (G/P-rTiO2) exhibited a reversible capacity
of 144.4 mA h g1 after 1100 cycles at a current density of 2.5C
and a capacity retention of 94.4% after 4000 cycles at 10C.168
A similar strategy was reported by Wang et al., who fabricated
partially single-crystalline mesoporous Nb2O5 nanosheet-wrapped
graphene. This composite exhibited a high reversible specific
capacity and outstanding high-rate performance.169 For metal
sulfides, Hu et al. used the intercalation reaction to modify FeS2
microspheres, together with selecting a compatible NaSO3CF3/
diglyme electrolyte and tuning the cut-off voltage to 0.8 V. A stable
electrically conductive layer-structured NaxFeS2 was formed and
exhibited a surprisingly high-rate capability (170 mA h g1
at 20 A g1) and unprecedented long-term cyclability (B90%
capacity retention for 20 000 cycles). Equally, a low-cost, high-
yield, and scalable two-step approach to obtain a new type of
hybrid material containing MoS2/graphene nanosheets through
ball-milling and exfoliation of commercial bulky MoS2 and graphite
was reported by Sun et al.170 MoS2/graphene nanosheets exhibited
remarkably high rate capabilities (284 mA h g1 at 20 A g1 and
201 mA h g1 at 50 A g1) (Fig. 8).
Table 5 summarizes alloy- and conversion-type electrode
materials with high rate behaviors. Regardless of whether metals
or metal oxides, sulfides, phosphides, and selenides were used,
these modifications were not only key for the high-rate capability
of the electrode materials, but also efficiently addressed the issue
of large volume variations during repeated cycling to improve the
cycling lifespan (Fig. 9).
Section summary. Fig. 10a and b summarize the high-rate
progress of NIB cathode and anodes, respectively. Clearly, NIBs
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Fig. 8 (a) Mechanism for the formation of carbon quantum dots. Reproduced with permission from ref. 153. Copyright 2015, Wiley-VCH. (b) Graphical
illustration of Na-storage mechanism for the NSC-SP product. Reproduced with permission from ref. 152. Copyright 2016, Wiley-VCH. (c) Synthesis of
porous carbons from longan shells. Reproduced with permission from ref. 154. Copyright 2018, Elsevier. (d) Schematic illustration of the formation and
structural characteristics of HCNP. Reproduced with permission from ref. 149. Copyright 2016, Elsevier. (e) Schematic diagram of Na ion storage
mechanisms of amorphous carbon/graphene nanocomposites. Reproduced with permission from ref. 151. Copyright 2015, Elsevier.

Table 5 Summary of current metals, metal oxides, and metal sulfides with high rate behaviors

Material Morphology Capacity (mA h g1) Highest rate Cycle number

166
Bi@graphite Mixing/thermal treatment 160, at 1C 300C 10 000
Sb171 Hydrothermal method 580, at 0.5C 20C 100
Germanium172 Thin film deposition 350, at 0.05C 170C 50
Black phosphorus173 Ball-milling method 770, 0.2 A g1 15C 70
Red phosphorus174 Carbothermic reduction 1027, at 0.2C 10C 160
MoS2/C nanofiber175 Electrospinning 484, at 1C 20C 1000
MoS2170 Ball-milling/exfoliation 403, at 0.9C 75C 250
SnS@graphene foam176 Hot bath and CVD 1010, at 0.1C 30C 200
FeS/C nanospheres177 Hydrothermal method 250, at 0.2 A g1 80C 20 000
MoS2/SWCNT178 Ultrasonic exfoliation 390, at 0.2C 20C 1000
FeSe2 microspheres179 Hydrothermal method 447, at 0.1 A g1 56C 2000
CoSe2180 Solvothermal method 573, at 1C 50C 1800
NiSe2181 Coprecipitation/selenization 311, at 1C 10C 100

have manifested remarkably high-rate capabilities, even with-
out modifications. The barriers for Na are lower than those of
Li in the transfer process due to the inherent advantage of the
electrode materials. Furthermore, the methods and strategies used
for material modification in LIBs can be applied to improve NIB
electrodes, accelerating the obtainment of high-rate capabilities.
Therefore, ultrahigh power NIBs can be achieved without com-
promising cost (Fig. 11).
4 Climate advantage of stationary NIBs
The reaction kinetics of electrode materials in most rechargeable
batteries are temperature-dependent. Specifically, the environmental
temperature plays a critical role in battery performance.182 Generally,
battery performance improves as the working temperature increases.
As NIBs use organic electrolytes, the working temperature must
be controlled under the threshold value of the organic solvents

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Fig. 9 (a) Schematic illustration of synthetic procedure for Sb4O5C12 and Sb/C. Reproduced with permission from ref. 164. Copyright 2015, Elsevier.
(b) Schematic illustration of the synthesis of Bi@graphite. Reproduced with permission from ref. 166. Copyright 2018, Royal Society of Chemistry.
(c) Schematic representation showing synthesis of MoS2/G nanosheet hybrids. Reproduced with permission from ref. 170. Copyright 2016, Wiley-VCH.

Fig. 10 Recent progress in rate performance of NIBs: (a) cathode and (b) anode.

to avoid fire risks or explosions. When operating under low-
temperature conditions, the batteries suffer electrochemical
decay. In particular, serious polarization of the battery reaction
leads to the fast arrival of cut-off voltages and, eventually,
battery failure, from which no capacity can be delivered or
restored in the battery. To avoid such failure, ESSs in the form
of rechargeable batteries must be paired with an additional
temperature management system to enable stable energy storage
and delivery. Traditionally, temperature-controlling accessories
have been widely used to address the climate concerns of
batteries. Wang et al. designed an internal self-heated nickel
foil accessory for the cell, which exhibited a superior temperature
management capability compared with traditional external tempera-
ture accessories. Notably, the internal heating system only
consumed 3.8% of battery capacity to achieve fast warming of
the battery system to 20 1C from a low-temperature environment
(20 1C).183,184 However, the additional accessories had negative
effects on the energy density and the cost of stationary ESSs, which
should be addressed before their wide application.
As an alternative, enhancing the environmental adaptability
of batteries is the most cost-effective method for mitigating the
influence of ambient temperature on battery performance.
Therefore, in this section, the climate features of NIBs will be
summarized for the first time. NIBs can operate over an
extremely wide temperature range (from 30 to 55 1C) without
using additional temperature control to maintain a proper
working temperature.115 This all-climate feature of stationary
NIBs is critical for ESSs, especially those without temperature-
controlling accessories in remote areas. The strong adaptability
of NIBs to various climatic environments also highlights their
high reliability and safety.
4.1 All-climate electrode materials for stationary NIBs
An all-climate electrode requires materials that have stable
phase structures at high temperatures and an electrolyte inter-
face that can rapidly deliver sufficient charges without being
impacted by temperature. Layered transition metal oxides have
drawbacks of insufficient thermal stability at high temperatures.
Much effort has been devoted toward introducing inactive elements,
such as Li+, Mg2+, Al3+, and Mn4+, into the transition metal layers of
layered oxides compounds to enhance their structural stability.
Compared with layered transition metal oxides, phosphates
compounds are more attractive in terms of maintaining their
structural and thermal stability under extreme conditions.

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Fig. 11 (a) Rate performance of NVP@C at different temperatures. Reproduced with permission from ref. 115. Copyright 2016, Elsevier. (b) Capacity
retention during 100 cycles at a rate of 0.5C. Reproduced with permission from ref. 102. Copyright 2016, Wiley-VCH. (c) Cycling performance at 0.4 A g1
at varied temperatures from room temp. to 25 1C. Reproduced with permission from ref. 188. Copyright 2018, Wiley-VCH. (d) Rate vs. cycling number
curves for NaV1.25Ti0.75O4/Na0.8Ni0.4Ti0.6O2 full cells. Reproduced with permission from ref. 189. Copyright 2018, Wiley-VCH. (e) Rate capabilities of
PB/CNT cathode at different temperatures. Reproduced with permission from ref. 186. Copyright 2018, Wiley-VCH.

Therefore, most pioneering reports related to the all-climate
electrochemical performance of NIB have focused on phos-
phate compounds. For example, Choi et al. investigated the
thermal stability of the desodiated state of Na3V2(PO4)3 using
TG/DSC and in situ XRD techniques, demonstrating that
NaV2(PO4)3 maintained its structural stability up to 450 1C.58
Liu et al. found a class of NASICON-type electrode materials
with all-climate performance. The NVP@C composite exhibited
excellent electrochemical performance in the temperature range of
30 to 55 1C.115 Similarly, Wang et al. constructed a carbon-coated
Na3Ti2(PO4)3 (NTP@C) composite that exhibited excellent all-climate
electrochemical performance. Even at 25 1C, the NTP@C anode
delivered a high specific capacity at a rate of 10C.117 Apart from
phosphate compounds, several other advanced electrode materials
also exhibited excellent electrochemical behavior at low temperature.
Ponrouch et al. investigated the low temperature performances of
hard carbon in NIBs, which delivered a high specific capacity of
265 mA h g1 at 15 1C.185 You et al. prepared a robust and
flexible Prussian blue (Na2Fe2(CN)6)-based composite electrode
for NIBs.186 Benefiting from the fast ionic/electronic transport
kinetics at low temperature, the electrode exhibited outstanding
electrochemical performance at 25 1C.
Notably, most of the NIBs mentioned above were evaluated
in half-cell configurations, in which the high impedance of sodium
metal anodes at low temperatures was ignored. Generally, as the
working temperature decreases, the diameter of semicircles in the
high-to-medium frequency range of EIS plots of NIBs become
significantly larger, suggesting an increase in internal impedance
of the cell. Liu et al. demonstrated that such an increase was
caused by counter sodium metal anodes in NIBs rather than the

Energy Environ. Sci. This journal is © The Royal Society of Chemistry 2019
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Energy & Environmental Science Review

working electrode.115 The high impedance of the sodium metal

electrode leads to the battery having a large overpotential during
cycling, which narrows the actual charge/discharge voltage window
of NVP@C and, finally, results in failure of the NVP@C cathode.
Therefore, to evaluate the kinetic properties of electrode materials
using electrochemical impedance spectroscopy, symmetric cells
consisting of identical working electrodes were better alternatives
to the half-cell system, providing practical information about NIBs
in frigid regions.
Using full-cell cases for low-temperature estimation can
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avoid the above concerns. Guo et al. assembled a full cell with
Na3V2(PO4)2O2F cathode and Na3Ti2(PO4)3 anode (NVPF–NTP).187
When the temperature decreased from 25 to 25 1C, the NVPF–
NTP full cell delivered a specific capacity of 96.1 mA h g1
with two evident plateaus/slopes, corresponding to a capacity
retention of 76.4% compared with that at 25 1C. This implied
that low-temperature kinetics of the NVPF–NTP electrode were
superior. Wang et al. constructed an advanced NIB consisting
of a 3D Se/graphene composite anode and a Na3V2(PO4)2O2F
cathode,188 which had a capacity retention of 475% after
1000 cycles at temperatures ranging from 25 to 25 1C at
0.4 A g1. Post-spinel NaV1.25Ti0.75O4 anodes also exhibited an
excellent wide-temperature rate capability.189 As suggested by Li
et al., the NaV1.25Ti0.75O4 anode delivered discharging capacities
of 93 and 100 mA h g1, respectively, at 20 and 60 1C, while
the variation in average voltages was negligible at different
temperatures, indicating the great potential of NaV1.25Ti0.75O4
in all-climate NIBs.
Fig. 12 DSC heating curves of electrolytes after cooling the sample to
4.2 All-climate electrolyte for stationary NIBs 120C. (a) Electrolytes based on 1 M NaClO4 dissolved in various solvent
Temperature significantly influences ion diffusion in the electro- mixtures and (b) PC-based electrolytes containing various Na salts at 1 M.
lyte and at the solid electrolyte interface. Ponrouch et al. provided Reproduced with permission from ref. 191. Copyright 2012. Royal Society
of Chemistry.
important insights into searching for optimized electrolytes for
NIBs. The authors benchmarked various electrolytes containing
diverse solvent mixtures (including cyclic/acyclic carbonates and Section summary. Currently, the electrochemical performances
glymes) and Na-based salts with either F-based or perchlorate of NIBs are mostly evaluated at constant temperatures in laboratories
anions, and measured the viscosity, ionic conductivity, and rather than in complex practical conditions. Bridging the gap
thermal and electrochemical stability of the electrolytes.190 between laboratory and practical conditions is of vital importance
The binary ethylene carbonate (EC):propylene carbonate (PC) to enable the practical application of rechargeable batteries,
solvent mixture was the best solvent formulation and was used including NIBs. In addition to the all-climate necessity, full-cell
to evaluate the electrochemical performance of Na/hard carbon data for NIBs are also of vital importance to exhibit their
cells with both NaClO4 and NaPF6 salts. Notably, as PC has a application potential. These results from realistic situations
vitreous transition temperature of about 95 1C, no electrolyte useful for reference rather than for apparent performance
solidification can be observed when PC is used as co-solvent. comparison. Currently, phosphate compounds and modified
This is essential for the low temperature application of NIBs layered transition metal oxides are both the primary choice as
because the liquid electrolyte behaves seemingly like an ionic- electrode materials for all-climate NIBs. Furthermore, electrolytes
liquid-based electrolyte at very low temperatures (Fig. 12). should be evaluated at different temperatures for no-matter liquid
Furthermore, high temperatures also pose a threat to organic and solid state configurations.
electrolytes.191 Ponrouch et al. conducted a systematic study on
optimizing electrolyte formulations to decrease interfacial side
reactions and the abuse tolerance of NIBs.190 The authors 5 Environmental advantages of
suggested that solid-state electrolytes have better mechanical stationary NIBs
properties, higher thermal stability, and wider electrochemical
windows compared with nonaqueous organic electrolytes. Therefore, ESS applications require vast numbers of cells. Therefore, large
solid-state NIBs might be the ultimate choice for constructing battery amounts of waste NIBs will be produced by ESS upgrades. These
systems with higher energy densities and safer characteristics.86 hazardous components pose be a significant threat to the

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Review Energy & Environmental Science

environment if they are abandoned without further manipulation.
Furthermore, waste NIBs contain enormous metallic resources
and organic electrolytes that are valuable for recycling, known as
so-called urban mines.192 In this respect, NIBs have significant
advantages compared with LIBs. Al foils are used for both cathode
and anode current collectors in NIBs, simplifying the battery
components. In this section, we provide a comprehensive outlook
on NIB recyclability and their major challenges.
5.1 Sharing experiences and technologies from LIBs
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of LIBs, NIB recycling can be anticipated as follows:197 abandoned
batteries are first crushed into small pieces for further separation,
followed by the collection of stainless steel accessories via magnetic
separation and the separator through a flotation process. After
thermal vacuum processing, organic solvents can be easily removed
and collected from waste scraps. As suggested by Maschler et al., the
recycling efficiency ratio of organic electrolytes can reach 80%.28 The
above manipulations recycle half of the battery cost, as shown in
Fig. 2. As NIBs have similar cell components and system, such as
steel sealing accessories, organic electrolyte, and separator, these

Linda Gaines, an analyst working for the Center for Transportation
Research at Argonne National Laboratory in Illinois, has stated
that ‘‘If you don’t think about recycling early, you could develop
some battery chemistry that’s going to be completely intractable’’.
This situation has occurred in LIB products and recycling.193 Lack
of such foresight is unfortunate for the ecological environment,
resulting in errors similar to the case of white plastics. Further-
more, battery manufacturers often prioritize performance and cost
to increase market share without considering the design of battery
recyclability.29 Fortunately, increasing attention is being paid
to environmental issues associated with the disposal of waste
batteries.192
Generally, recycling is an ideal solution to solve environ-
mental problems induced by waste materials and alleviate shortages
of critical materials through closed-loop recycling.194–196 Both LIBs
and NIBs consist of cathodes, anodes, metallic current collectors,
separators, electrolyte salts dissolved in organic solvents, and stain-
less steel sealing accessories. With reference to the recycling process
cumulative recycling technologies for LIBs can be applied to NIBs.
Remaining components in the waste scraps are the cathode
slurry, anode slurry, and metallic current collectors. For current
LIB components, these waste scraps are difficult to further
separate and recycle using a simple method. Pyro- and hydro-
metallurgical methods are widely adopted to recycle valuable
metal resources.197,198 All waste scraps are smelted and refined by
thermal treatment. Therefore, a high energy and emissions foot-
print accompanies pyro-metallurgical recovery. Furthermore, some
metal materials with low value, such as aluminum, will end up in
the waste stream after the recycling process, leading to a large
amount of solid waste materials for the environment. Conversely,
hydro-metallurgical recovery efficiently separates and collects
valuable metal resources using massive amounts of chemical
reagents. After separating aluminum and copper, filtrates
including Li, Co, Ni, and Mn can be reused as precursors for
the cathode in the co-precipitation method.199 However, the
main concern is the high costs incurred by chemical reagents

Table 6 Comparison of NIB features with those of other chemical energy storage systems

Energy density Power density Temperature

System (W h kg1) (W kg1) Cost ($ per kW h) Efficiency (%) Safety Self-discharge reliability Recyclability
NIBs 70–100 300–1000 500–2000 90–100 High 1–2% per month Advanced Advanced
LIBs 75–200 75–300 600–2500 90–100 High 1–2% per month Moderate Insufficient
LABs 30–50 75–300 200–400 70–80 Advanced 5% per month Moderate Advanced
SCs 2.5–15 500–5000 300–2000 90–100 Advanced 20–40% per day High High
RFBs 10–30 — 150–1000 80 High Very small High Advanced

Fig. 13 Principles of rate performance for bipolar electrode structure.

Energy Environ. Sci. This journal is © The Royal Society of Chemistry 2019

Energy & Environmental Science
and post-wastewater treatment.200 Fortunately, the research and
battery community has made great strides toward low-carbon and
low-cost recovery without secondary environmental pollution. The
combination of pyro- and hydro-metallurgical methods has
achieved benefits in the recycling industry, driving policy and
efforts in LIB recycling.201
Learning lessons from LIB experiences and technologies
means that high-efficiency recycling processes for NIBs have a
great chance of being achieved. Currently, the development of
NIBs is in its infancy. Few research institutes and companies
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have the ability to mass-produce NIB packs. However, the
recyclability of NIBs must be considered in terms of electrode
materials and battery frameworks. Developing recyclable NIB
technologies is the most cost-effective approach to avoiding the
repeated metallurgical process.
Fig. 14 Evaluation of NIBs, LIBs, LABs, SCs, and RFBs.
This journal is © The Royal Society of Chemistry 2019
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Review
5.2 Prescient recycling design of NIBs
Copper current collectors are replaced by Al foil in NIBs,
because Al does not have an alloy reaction with Na, even at
reduced potentials.45 This substitution simplifies the battery
components, especially for the above waste scraps. Al foils can
be easily dissolved by basic solutions and elemental Al can then
be collected from the Al(OH)3 sediments. Therefore, the cathode,
which is the most value component in NIBs, can be recycled and
rejuvenated in a closed-loop cycle. Furthermore, the direct recovery
of electrode materials can be readily achieved in the recycling
process. The objective of direct recovery is to reduce energy,
emissions, and waste, saving money on compliance with air-
pollution regulations and disposal fees, compared with traditional
pyro- and hydrometallurgical processes.192 Such direct recovery
has been achieved for LIBs (Table 6).82–84,202,203
Energy Environ. Sci.

Review
Furthermore, the replacement of Al by Cu as anode current
collector also facilitates the establishment of a unique electrode
framework, such as a bipolar electrode structure. Compared with a
conventional battery configuration, bipolar battery configurations
have advantages of a simple structure and high power. Such a
bipolar electrode structure is enabled by the unified current
collector for cathode and anode. In NIBs, Al foils are stable for
the cathode and anode. Unlike traditional batteries, which
consist of single cells connected in series, as shown in
Fig. 13, bipolar batteries are highly stacked to produce a high
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voltage in a small volume. The construction of a bipolar battery
does not require heavy intercell connectors. Massive battery
accessories are no longer used. Therefore, the battery compo-
nents are further simplified and more easily recycled. This
recyclable feature of NIBs not only addresses the environmental
concerns of waste batteries, but also enables large-scale applica-
tions of high-cost cathode materials (Fig. 14).
Section summary. NIBs have great potential for achieving
full-battery recyclability. Prescient battery design is crucial for
the recycling of heavily regulated disposal in NIBs. The recycling
process of NIBs in the form of bipolar batteries is simple,
allowing for the closed-loop cycling of key materials. As a result,
some high-cost electrode materials, including those containing
Co and Ni, can be recycled economically by one-step treatment.
6 Conclusions and perspectives
NIB research aims to satisfy the demand of large-scale ESS in
applications of renewable energy and smart grids. As summarized
in this review, NIBs have exhibited four attractive features. These
features are generally based on novel host materials, rational
electrolyte formulation, unique electrode architectures, and cell
configurations. Compared with other chemical energy storage
systems (such as LIBs, LABs, SCs, and LFBs), these NIBs are not
the best in each performance indicator, but are the most suitable
candidate for ESS applications. NIBs can be concluded to possess
very good compatibility with ESS. Therefore, for the development
of practically viable ESS, the future direction of NIBs research
should further enhance these competitive features and explore
new features in electrode materials.
Compared with Li ions, Na ions have a larger size and atomic
weight, and suffer from slower ionic transport kinetics and a
lower energy density. These disadvantages can be compensated
by the high-rate ability of sodium-containing compounds.
Traditionally, batteries and supercapacitors are complementary
electrochemical energy storage technologies. Specifically, batteries
have high energy densities, but low power densities, while super-
capacitors offer high power density with low energy. NIBs currently
belong to the batteries category, but have high performance
behavior, which shows potential for extending beyond the
limitations on energy and power density. Firstly, novel electrode
materials and structure designs must be developed. Despite
huge progress in NIB research made in recent years, funda-
mental difficulties in stable Na+ insertion/extraction have yet to
be fully overcome in NIBs.
Energy Environ. Sci.
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Energy & Environmental Science
Furthermore, we propose a bipolar strategy for electrode
materials in NIBs to reduce costs during recycling and enhance
the benefits from waste batteries, making NIB recycling more
economic. To achieve this goal, bipolar electrode materials are
key. The combination of low potential redox TMs (Ti, V, Nb, and
Mo) and high potential redox TMs (Cr, Mn, Fe, Co, Ni, and Ru)
is a promising method for realizing bipolar electrode materials
and, consequently, bipolar electrode structures. For example,
in model polyanion compounds Nax[TMy,TM2y 0 ](PO4)3, the
redox couple of one transition metal is nearly independent of
another, which allows the design of a bipolar electrode structure.
Furthermore, such a symmetrical battery structure based on a
Nax[TMy,TM2y0 ](PO4)3 electrode is also favored for high-efficiency
recycling. Therefore, the rational modification of these bipolar
electrode materials is key to enabling these competitive features
of NIBs on an industrial scale for the energy storage market.204
Herein, we propose several feature-oriented solutions, as follows:
(i) Learning from current experience in advanced LIBs,
cathode research should be directed towards high capacity and
high voltage to enhance the energy density of NIBs. Na-rich
layered metal oxides might be a candidate.
(ii) Reaction mechanisms of sodium insertion/extraction
must be clearly elucidated using in situ or ex situ technologies
to direct further research activities. This basic information is of
vital importance for enhancing the rate capability.
(iii) Innovations in electrode architectures and cell con-
figurations enhancing high rate capacity. The open 3D framework
can provide sufficient interstitial spaces for ionic diffusion. The
direct connect reduces the electric transfer pathway.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by funding from the National Key
R&D Program of China (Grant No. 2018YFB0104300), Thousand
Youth Talents Program, Thousand Talents Program, the National
Natural Science Foundation of China (Grant No. 51572300 and
51774333).
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