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Sodium-ion capacitors: Materials, Mechanism, and Challenges
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DOI: 10.1002/cssc.201903440
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Accepted Article
Title: Sodium ion capacitors: materials, mechanism and challenges
Authors: Yadi Zhang, Jiangmin Jiang, Yufeng An, Langyuan Wu, Hui
Dou, Jiaoxia Zhang, Yu Zhang, Shide Wu, Xiaogang Zhang,
Mengyao Dong, and Zhanhu Guo
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
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content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201903440
Link to VoR: http://dx.doi.org/10.1002/cssc.201903440
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ChemSusChem 10.1002/cssc.201903440
Sodium ion capacitors: materials, mechanism and challenges
Yadi Zhang,1,6† Jiangmin Jiang,1† Yufeng An,1 Langyuan Wu,1 Hui Dou,1 Jiaoxia Zhang,2,6 Yu
Zhang,3 Shide Wu,4 Mengyao Dong,5,6 Xiaogang Zhang,1* Zhanhu Guo6*
Accepted Manuscript
1. Jiangsu Key Laboratory of Electrochemical Energy Storage Technologies, College of Material
Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016,
China. E-mail: azhangxg@nuaa.edu.cn
2. School of Materials Science and Engineering, Jiangsu University of Science and Technology,
Zhenjiang 212003, China
3. College of Chemical and Environmental Engineering, Shandong University of Science and
Technology, Qingdao, Shandong 266590, China
4. Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of
Light Industry, No. 136, Science Avenue, Zhengzhou, 450001, China
5. Key Laboratory of Materials Processing and Mold (Zhengzhou University), Ministry of
Education, National Engineering Research Center for Advanced Polymer Processing Technology,
Zhengzhou University, Zhengzhou, China
6. Integrated Composites Laboratory, Department of Chemical and Biomolecular Engineering,
University of Tennessee, Knoxville, TN 37996, USA. E-mail: zguo10@utk.edu
†
: Y. Zhang and J. Jiang contributed equally to this work.
*E-mail: azhangxg@nuaa.edu.cn (Xiaogang Zhang)

E-mail: zguo10@utk.edu. (Zhanhu Guo)
This article is protected by copyright. All rights reserved.

Abstract
Sodium ion capacitors (SICs), as designed to deliver high energy density, rapid energy delivery,
and long lifespan, have attracted much attention because of their comparable performance to
lithium ion capacitors (LICs), albeit with abundant sodium sources. The conventional SICs design
is based on battery-like anode and capacitive cathode, in which the battery-like anode materials
Accepted Manuscript
involve various reactions such as inserted reaction, alloying reaction and conversion reaction, and
the capacitive cathode materials usually depend on activated carbon (AC). However, researchers
attempted to construct SICs based on battery-like cathode and capacitive anode or a combination
of both in recent years. Here, the charge storage mechanism and material design strategies in SICs
are summarized, with a focus on battery-like anode materials from inorganic to organic materials.
Additionally, the challenges in the fabrication of SICs and future research directions are discussed.
Keywords: Battery; Supercapacitor; Hybrid ion capacitor; Energy density; Power density
1. Introduction
Being stimulated by the frequent and afflictive haze and the drastically reduced fossil fuels,
researchers have vigorously made a lot of efforts on renewable and new energy such as solar power,
wind power and wave energy.[1] However, the climate and sunshine duration often lead to
intermittent energy supply and/or volatility. Therefore, electrochemical energy storage is being
rapidly developed and popularized in our daily life, such as electronic equipment and urban rail
transit, even aviation and space flights because of the superior performance.[2] Currently, secondary
batteries and supercapacitors (SCs) are primarily electrochemical energy storage systems because
of their excellent performances.[3] The former one based on the ion intercalation/deintercalation in
insertion compounds displays high energy density (> 200 Wh kg–1) and low self-discharge process.
However, the sluggish kinetic process leads to a low power density (< 350 W kg–1) and short cycle

life, which limits their application in the high-power devices.[4] On the other side, supercapacitors
can deliver ultrahigh power density (> 10 kW kg–1) and excellent cycling stability (>100 000
cycles), but the low energy density (5–20 Wh kg–1) restricts their large-scale applications in long-
range devices.[5] In order to achieve the advanced energy-storage systems effectively combining
high energy density with high power density and long cycle life, hybrid ion capacitors were put
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forward involving two energy storage mechanisms, as shown in Figure 1.
Figure 1. The comparison of energy density and power density for different energy storage devices.
Reproduced with permission.[3a] Copyright 2014, American Chemical Society.
The first hybrid ion capacitor was constructed by Amatucci et al. in 2001, in which
nanostructured Li4Ti5O12 (LTO) acted as anode and activated carbon (AC) served as cathode,
called as lithium ion capacitor (LIC).[6] However, the scarce and reduced lithium sources result in
a sharp rising cost of lithium compound. Fortunately, the abundant sodium sources and reasonable
redox potential (Na/Na+=–2.7 V) make it possible to construct sodium ion based hybrid ion
capacitors.[7] The first sodium ion capacitor (SIC) was designed in 2012, in which V2O5/CNT
composite acted as anode and AC served as cathode.[8] The assembled SIC with a high cell voltage
of 2.8 V displayed a maximum energy density of ∼40 Wh kg–1. The following research on

potassium ion capacitors (KICs) also began in 2017, as shown in Figure 2.[9] However, it is hard
to integrate high energy density, power density and excellent cycle stability in an individual SIC,
mainly resulted from the capacity or kinetics mismatching between anode and cathode.
Additionally, the coupling mechanism of anode and cathode is unclear. Here, we will summarize
the latest advances in charge storage mechanisms and related materials from inorganic to organic
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compounds for SICs. In addition, the prospects and challenges associated with SICs in practical
applications are also discussed.
Figure 2. The history process of hybrid metal ion capacitors.
2. Charge storage mechanism and equations of SICs
According to whether the electrolyte is consumed in the electrochemical process, SICs can be
classified into three types: electrolyte consuming mechanism, Na-ion exchange mechanism and
hybrid mechanism (Figure 3). There are briefly described as follows:
a. Electrolyte consuming mechanism. In this system, battery materials, including Na+
de/intercalation compounds, metal oxides and carbonaceous materials, act as anode, while
capacitor-type materials such as AC derived from biomass and metal-organic-framework,
graphene and CNTs usually serve as cathode. During the charging process, cations and anions are
separated to move to anode and cathode under the action of a voltage, respectively, which is similar
to the mechanism of supercapacitors, but Na+ intercalates into Na+-including compounds or

reduction reaction takes place in the anode rather than a simple physical Na+ adsorption. During
the discharging process, Na-ions take off from the anode and go back to the electrolyte
accompanied by the desorption of anions from cathode to make the charge balance. The classic
example is the Na2Ti3O7//AC system and so on.[10]
b. Na-ion exchange mechanism. With the respect to this system, cathode is battery materials
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which provide Na-ions and anode is capacitor-type materials. During the charging-discharging
processes, the electrolyte concentration remains constant and only plays a part in transferring Na-
ions, which is analogous to “Rocking-Chair” Na-ion batteries. Unlike the batteries, Na-ions de-
intercalate from cathode and adsorb on the surface of anode while SIC is charging, and vice versa.
The successful design includes MXene//Na2Fe2(SO4)3, AC//NVOPF@PEDOT systems, etc.[11]
c. Hybrid mechanism. The prominent feature of this type of SIC is that one or both of the
electrodes contain both battery-materials and capacitor-materials. During charging, Na-ions de-
intercalate from cathode and enter the electrolyte, and AC contained in the cathode absorbs free
anions in the electrolyte while all Na-ions de-intercalated from cathode and provided by electrolyte
intercalate into anode. During the discharging process, AC releases the absorbed anions into
electrolyte to balance a part of Na-ions de-intercalated from anode, another part of Na-ions
intercalate into the cathode to recover to Na-including state, such as NTP@rGO//Na3V2(PO4)3/C
system, etc.[12]
Figure 3. Schematic illustration of three kinds of energy storage mechanisms for SICs.

The capacitance (CSIC, F g–1) can be obtained using the relationship: CSIC = it/ΔV, where i (A)
is the applied current density, t (s) is the discharge time and ΔV (V) is the absolute potential
difference. Additionally, the specific capacitance of SIC is calculated from CSP = 4CSIC/m (m refers
to the total mass of anode and cathode materials).[13] Nevertheless, the galvanostatic charge-
discharge (CD) curve of SIC is non-linear as a result of the combination of battery behavior and
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capacitive behavior, therefore, the energy density (E, Wh kg–1) of SIC is normally estimated by
directly integrating the area below the CD curve (Figure 4) using the following formula:
t1 Vmax
E   iVdt   QdV (1)
t2 Vmin
and the power density (P, W kg–1) can be calculated based on the equations:
P  U 2 /(4mRs ) (2)
Rs  U IR / 2 I (3)
where U (V) is the maximum cell voltage, m (g) is the total mass of active materials, Rs (Ω) is the
equivalent series resistance of the cell, and UIR (V) is the initial iR drop.
Figure 4. Schematic of the electrochemical profile of a typical SIC with a non-linear CD curve.
3. Materials for SICs
The electrochemical performances of SIC are closely related to the physicochemical properties
of electrode materials regarded as the soul of SICs, including particle size, crystal structure, defect

level, redox potential and theoretical capacity. Figure 5 shows the promising battery-type materials
for SICs renewed on the basis of the previous report.[14] In this review, we mainly focus on the
electrode materials for electrolyte consuming mechanism based SICs, in which battery-behavior
materials act as anode, and capacitive materials serve as cathode.
Accepted Manuscript
Figure 5. Plot of the theoretical capacity and operation potential of promising electrode materials
for SICs.
3.1 Battery-behavior anode materials
3.1.1 Hard carbon materials
The first practical assessment of SICs began in early 2012 and remained in its infancy stage.
As we all know, graphite is widely used as an anode material for commercial LIBs and LICs since
it has a low Li+ insertion potential (< 0.1 V vs. Li) and cheap production cost. However, the relative
atomic mass and ionic radius (22.99, 1.02 Å) of Na+ are significantly larger than those of Li+ (6.94,
0.76 Å), the Na+ could hardly intercalate into graphite, limiting its application as anode materials
for SIBs and SICs. In view of this, the critical point is to develop an anode material with large
tunnels in the crystal. Along this line, Kuratani et al. first assembled the SIC by the pre-doped
carbon microbeads (MCMB) anode materials and activated carbon (AC) cathode, respectively.[15]
Because of the difference of the open-circuit voltage, the output potential of SIC was lower (~0.3

V) in comparison to the LIC. Thus the charge-discharge voltage range was chosen as 1.7–3.7 V
for the SICs in their work. They found that the pre-doping condition was very crucial to deliver a
high performance of the carbon-based anode electrode for SICs. Although the capacity (maintained
70% at a current density of 10 mA cm1) and cycle lifespan (decreased with 9% after 1000 cycles)
can be further improved and optimized, this original work has demonstrated the possibility of
Accepted Manuscript
manufacturing SICs.
With the successful use of the hard carbon as anode material for SICs, lots of the carbonaceous
materials derived from the nature biomaterials have been reported as electrode materials for SICs
recently. For example, Madhavi et al. utilized the natural plant-derived hard carbon (HC) as anode
materials and coconut shell derived mesoporous carbon as cathode materials to construct LICs and
SICs.[16] The HC anode exhibited an initial discharge capacity of ~216 and ~350 mAh g1 for the
Na and Li-ion based half-cells, respectively. The irreversible capacity loss was very huge in the
initial cycle for the HC material. This is still a common challenge for the carbon-based anode.
Based on such performance, the assembled LICs and SICs delivered a maximum energy density
of 121 and 82 Wh kg1, respectively. However, the SICs showed an inferior cycle stability (~60%)
after 8000 cycles under the same testing condition. In addition, the olive pits derived HC anode
material and chemical activation of the HC with KOH as cathode electrode had been employed in
SICs.[17] There were some graphitic features after the pyrolytic process of the HC, which delivered
a specific capacity of 360 mAh g1 in the initial discharge step in the half cell. A SIC was fabricated
successfully with 1 M NaFP6 EC:PC (volume ratio=1:1) electrolyte and tested potential range
between 1.5–4.2 V, it displayed a capacity retention of 90% after 1000 cycles and retained 70%
after 5000 cycles at a current density of 2 A g1.
SICs can be successfully constructed by using biomass-derived HC as anode materials, while

their energy density and cycle stability need to be further improved to some extent. For this, Mitlin
et al. employed polypyrrole hydrogel (P-HG) as a precursor for preparing the N-doped carbon
anode,[18] owing to its appropriate nitrogen content and high level of nanoporosity. The P-HG
precursors had been treated at the temperature of 650, 800, and 950 C, which were named as
NOFC-650, NOFC-800, and NOFC-950, respectively. The P-HG precursor showed a three-
Accepted Manuscript
dimensional (3D) networks of interconnected granules (Figure 6a). The granule sizes of the NOFC-
650 had been shrunk after the pyrolysis process with the inherited architecture similar to P-HG
precursors (Figure 6b). It also had interconnected carbon granules interspersed with macroporosity
(Figure 6c). Beyond that, all of the NOFC samples were heteroatom-doped structures, in which
NOFC-650 was the highest heteroatom-doping sample (13 wt% nitrogen and 11 wt% oxygen).
Due to the huge heteroatom-doping level and porous structure, it exhibited a reversible capacity
of 437 mAh g1 at 100 mA g1 and maintained 185 mAh g1 at a higher current density of 1600
mA g1. The NOFC-650 anode and peanut shell derived carbon cathode (PSNC) were employed
to fabricate a SIC, which delivered an energy density of 111 Wh kg1 and 38 Wh kg1 at a power
density of 67 W kg1 and 14550 W kg1, respectively, and also obtained 90% capacity retention
over 5000 cycles. Similarly, Lu et al. used the commercial pyrrole monomer as the raw material
to synthesize nitrogen-doped porous carbon anode (NPHCs).[19] According to Figure 6d, the
surface of NPHCs was rough and a lot of micropores had been formed after thermal polymerization
at 1000 C. TEM image of the NPHCs further confirmed its microporous and amorphous structure
(Figure 6e), which accommodated the large volume expansion during the cycle process. Besides,
the element mapping illustrated the uniform distribution of C, O, N elements on the surface of
NPHCs (Figure 6f). A SIC had been constructed by utilizing the NPHCs cathode and soft carbon
anode with a wide voltage range of 0.01–4.7 V, which had a maximum energy density of 245.7

Wh kg−1 at a power density of 1626 W kg−1, long cycle lifespan (1000 cycles), outstanding rate
capability, and superior temperature characteristics. As we all know, the template method is an
effective method to adjust carbon-based material properties. Kado et al. used MgO as template and
polyvinyl alcohol (PVA) as precursors to design carbon-based anode materials with different
porous structures.[20] Besides, the effect of Na+ storage capacity had been evaluated by annealing
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at a different temperature, in which the sample annealed at 1000 ℃ possessed the highest rate
capability. Furthermore, they employed MgO-templated carbon anode and active carbon cathode
to assemble a SIC (1.7–3.7 V), which exhibited an energy density of 37 Wh L−1 and maintained
90% capacity retention after 1000 cycles with the coulombic efficiency almost 100%.
Figure 6. (a) SEM image of P-HG precursor, (b) SEM and (c) TEM images of the NOFC-650.
Reproduced with permission.[18] Copyright 2016, Elsevier. (d) SEM image, (e) TEM image and (f)
Elemental mapping of the NPHCs. Reproduced with permission.[19] Copyright 2018, Wiley-VCH.
3.1.2 Transition metal sulfides and selenide compounds
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Although carbon-based anode allows a high specific capacity (~300 mAh g1) for Na+ storage,
the low sodiated potential (~0.1 V) trends to produce dendrite formation, leading to a safety
problem. Thus, a series of conversion-type and alloy-type anode materials have been attempted to
be used as anode materials for SICs.[21] Among them, transition metal sulfides (TMSs) have
attracted increasing research interests for SICs, because of their outstanding chemical, physical,
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and mechanical performances.
Molybdenum disulfide (MoS2) has a 2D atomic layered structure with a large interplanar
spacing (~0.62 nm), and is considered as potential alternative anode materials for Na+ storage.
However, MoS2 also has some issues, including easy agglomeration, poor electronic conductivity
and huge volume change, limiting the practical application in SICs. Zhang et al. utilized an
interlayer-modification method to build a MoS2-carbon monolayer inter-overlapped structure.[22]
The MoS2-C composite anode displayed a 3D microflower-like morphology, which was made up
of ultrathin 2D nanosheets (Figure 7a). The interlayer space of MoS2-C composite was about 1.02
nm (Figure 7b-c), demonstrating a rapid ion channel for Na+ transport. As a result, MoS2-C
composite anode delivered a specific capacity of 200 mAh g1 at 0.1 A g1 and a capacity retention
of 86.7% after 800 cycles at 1 A g1. The constructed full SIC in this work exhibited a maximum
energy density of 111.4 Wh kg1and high power density of 12 000 W kg1, as well as an ultra-long
cycle lifespan (10 000 cycles). Composited with carbon-based material is an effective approach to
improve the overall performance of MoS2. However, how to combine carbon matrix and expand
interlayer spacing as well as decrease the interface resistance is still a challenge that needs to be
addressed.
To this end, Zhang et al. presented a dual-function sacrificing template (Sb2S3) strategy to
prepare the MoS2/carbon hybrid nanotubes (MoS2/C-HNTS).[23] Notably, the Sb2S3 not only was
11

used as a sulfur source upon the high-performance decomposition but also played a critical role in
the formation of hollow structures upon the sublimation of antimony. The acquired MoS2/C-HNTS
had a hollow tubular-like structure (Figure 7d and e). The interplanar distances of 0.227 and 0.27
nm observed in the composited anode were indexed to the (103) and (100) crystal planes for MoS2
phase (Figure 7f-h). The elemental mapping indicated that the Mo, S, C, N and P uniformly
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distributed on the surface of MoS2/C-HNTS (Figure 7i). They used the MoS2/C-HNTS anode and
AC cathode to construct a high-performance SIC, which delivered a maximum energy density of
107.2 Wh kg1. Besides that, Hu et al. prepared a composited anode of TiO2-coated MoS2@N-
doped carbon by a solid-phase reaction and atom-layer deposition (ALD) process.[24] The
amorphous TiO2 coating layer effectively extended its cycle lifespan. The SIC was fabricated using
the TiO2-coated MoS2@N-doped carbon anode and AC cathode and its electrochemical
performance was investigated (Figure 7j-n). Particularly, with an applied working voltage range
of 0–4 V, this device displayed a high energy density (148 Wh kg1) and long cycle stability
(capacity retention of 70% after 3000 cycles). Not only that, they also used the bagasse-derived
porous carbon (BPC) to synthesize the Mo2S@BPC composited anode.[25] Our group have
employed the N-doped porous carbon microsphere (N-NPCM) as a scaffold for the in situ growth
of expanded interlayer spacing MoS2 (MoS2/N-NPCM) as composited anode material.[26]
12

Accepted Manuscript
Figure 7. (a-b) TEM and (c) high-resolution TEM images of the as-prepared MoS2-C sample.
Reproduced with permission.[22] Copyright 2017, American Chemical Society. (d-e) high-
magnification TEM images and (f-h) HRTEM analysis and (i) the corresponding HAADF-STEM
image and elemental mapping results of MoS2/C-HNTs. Reproduced with permission.[23]
Copyright 2019, Royal Society of Chemistry. (j-n) Electrochemical performance of the SICs
device. Reproduced with permission.[24] Copyright 2019, Elsevier.
Tin disulfide (SnS2) has attractive features including layered structure (~059 nm), high
pseudocapacitance and low potential plateau (~0.7 V), and is regarded as a new anode material for
SICs. For example, Kim et al. developed a pressurized sulfidation and self-assembled method to
prepare the SnS2/graphene-carbon nanotube aerogel composites (Figure 8a).[27] The as-prepared
composite as anode for Na+ storage exhibited a high specific capacity of 600.3 mAh g−1 and 304.8
mAh g−1 at an ultrahigh current density of 10 A g−1, resulting in an exceptional energy density of
108.3 Wh kg−1 for SICs. In addition, Fan et al. reported the vertical ultrasmall sized-SnS
nanosheets and carbon microtubes (SnS/aCMT) by using solvothermal and high-performance
calcined approaches (Figure 8b).[28] The SnS/aCMT displayed the oriented SnS nanosheet
13

sandwich architectures uniformly distributed on carbon microtubes. SIC was assembled based on
SnS/aCMT anode and porous carbon microtubes cathode, and exhibited a maximum energy
density of 115 Wh kg−1. However, it is difficult to control the valence state of Sn in the synthesis
process of SnS. Moreover, Lee et al. employed a solvothermal route to synthesize Fe1−xS
nanoplates.[29] The sample presented a specific capacity of 340 mAh g−1 at 50 mA g−1, a superior
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rate capability and cycle stability for Na+ storage. A high-performance SIC was fabricated using
the Fe1−xS nanoplates anode and N-doped carbon nanosheets cathode, and delivered an excellent
energy density of 88 Wh kg−1 at 150 W kg−1, as well as long-term cycle life.
14

Figure 8. (a) Schematic representation of the fabrication of the SnS2/GCA. Reproduced with
permission.[27] Copyright 2018, Wiley-VCH. (b) Schematic illustration of the preparation process
of SnS/aCMT and the assembled sodium hybrid capacitor. Reproduced with permission.[28]
Copyright 2019, Royal Society of Chemistry.
Beyond that, molybdenum diselenide (MoSe2) is an intrinsic semiconductor with a narrower
Accepted Manuscript
band gap (~1.1 eV) than that of MoS2 (~1.7 eV), indicating a higher electronic conductivity, which
is beneficial to realize a better rate capability when used as anode for SIBs. For example, Cao et
al. used hexadecyltrimethyl ammonium bromide (CTAB) as a guiding agent to synthesize the
ordered MoSe2/graphene composites through the hydrothermal method.[30] They found that the
charge transfer of the composites can be reinforced via the Mo–C chemical bond between MoSe2
and graphene. A SIC was assembled using AC cathode and MoSe2/graphene anode, and displayed
a maximum energy density of 82 Wh kg−1 and a high capacity retention of 81% over 5000 cycles.
Besides, they also immobilized MoO2 nanoclusters on the surface of MoSe2, resulting in a
MoO2/MoSe2-graphene heterostructure.[31] Because the novel interface was of benefit to promote
the reversible conversion of MoSe2, making a high reversible specific capacity and excellent
cycling stability for SIBs and SICs. In addition, Ji et al. used carbon nanospheres to encapsulate
the exfoliated MoSe2.[32] They found that the C–O–Mo bonds improved the ions transfer and also
promoted the reversible conversion of MoSe2. As a result, it delivered a specific capacity of 441
mAh g−1 at 1 A g−1 even after 120 cycles.
3.1.3 Ti/Nb based compounds
Compared with transition metal sulfides and selenide, Ti-based compounds have longer cycling
life because of the potentials of Ti-redox normally ranging from 0.5 to 1.0 V, avoiding dangerous
sodium plating and thus providing high safety during charge/discharge process.[33] Moreover, the
15

low lattice change of Ti-based compounds also benefits the long-term cycling. Among them,
typical anatase TiO2 based on the Ti3+/Ti4+ redox couple is the widest anode material investigated
in SICs. However, the sluggish sodium reaction kinetics of wide-band gap TiO2 is a big challenge
to obtain high-performance SICs. Thus, various nanostructured TiO2 have been reported to achieve
the fast ion diffusion. For example, Lu et al. reported mesoporous single-crystal-like TiO2-
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graphene nanocomposite prepared through microwave-assisted method.[12b] As shown in Figure
9a, anatase TiO2 displayed a single-crystal structure with abundant mesopores resulted from the
voids between TiO2 building nanocrystals. These voids effectively shortened the ion diffusion
pathway. The kinetic studies of TiO2 anode indicated that the kinetics was controlled by the
pseudocapacitive process at low scan rates (< 5 mV s–1), but it was dominated by diffusion process
at high scan rates (> 5 mV s–1), presented in Figure 9b and c. At a scan rate of 3 mV s–1, about 73%
of the total charge belonged to the capacitive process as depicted by the shadow area shown in the
inset. The co-existence of mesoporous texture and small primary building blocks of TiO2 benefited
fast Na+ ion insertion/deinsertion and short diffusion distance. Additionally, the robust
submicrometer architecture of TiO2 enhanced stable cycling performance. Coupling with
commercial AC, the as-fabricated SIC delivered a high energy density of 64.2 Wh kg–1 as well as
long cycle life (a high capacity retention of 90% after 10 000 cycles). Moreover, Shaijumon et al.
prepared semicrystalline and crystalline anatase brown TiO2 nanotubes (BTNT) with flower-like
structure by using hydrothermal route, as shown in Figure 9d.[34] As an efficient pseudocapacitive
Na+ intercalation material, the as-prepared brown TiO2 exhibited good electrochemical
performances. They designed and constructed SIC based on BTNT anode and AC cathode, as
displayed in Figure 9d (right). Figure 9e indicated that the specific capacitance was well retained
with the increase of scan rate and current density. Additionally, the assembled BTNT//AC SIC
16

presented a maximum energy density of ∼68 Wh kg−1 and ultralong cycle life. Recently, TiO2
nanorods,[35] metal-organic framework-derived TiO2[36] and titanium oxynitride mesoporous
nanowires[37] also have been studied as intercalation-type anode to construct SICs, all the SICs can
deliver outstanding electrochemical properties including high rate capacity and excellent cycle
stability. However, the sodium-free anode should be pre-sodiated before fabricating SICs, making
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a complicated process. And the pre-sodiated degree is not definite yet, which significantly
determines the performance of SICs.
Layered sodium titanates have two main differences from TiO2. On one hand, layered sodium
titanates deliver obvious charge/discharge plateaus based on the electrochemical Na-ion
de/intercalation mechanism. On the other hand, layered sodium titanates are sodium-containing
and can match with the Na-deficient cathode directly without pre-sodiated process. The first
reported layered sodium titanate is NaTiO2, which was studied for reversible Na-ion
(de-)intercalation in 1983, but the environmentally unstable property made it unreliable. Therefore,
researchers attempted to design and prepare various sodium titanates to obtain high structural
stability. Shaijumon and co-workers employed hydrothermal technique to synthetize layered
sodium titanium oxide hydroxide, Na2Ti2O4(OH)2, with a unique flower-like morphology.[38] The
kinetic study illustrated that Na2Ti2O4(OH)2 had a pseudocapacitive mature. The full SIC based on
Na2Ti2O4(OH)2 anode and activated porous carbon delivered an energy density of 65 Wh kg–1.
Wang et al. have successfully synthetized sodium titanate nanotubes by hydrothermal treatment of
TiO2 precursors in concentrated NaOH followed by heat treatment.[39] The as-prepared samples
displayed different electrochemical performances based on different synthesis conditions. But the
resistance needs to be reduced by introducing conducting matrix or defects, and fabricating
integrated electrode to remit the kinetic discrepancy between the sluggish anode and the rapid
17

cathode.[40] For example, Wang et al. designed and introduced oxygen vacancies in sodium titanate
to enhance electrical conductivity and maintain the crystal structure stability.[41] They grew
Na2Ti2O5−x nanowire arrays on Ti-foil vertically (Figure 9f). The integrative Na2Ti2O5−x nanowire
arrays anode presented superior rate capability and ultralong cycle lifespan with a capacity
retention of 100% after 20 000 cycles at 25 C (Figure 9g). When combining with rGO/AC film
Accepted Manuscript
cathode to construct SIC, a high energy density of 70 Wh kg–1, and a high volumetric energy
density of 15.6 Wh L–1 were obtained. Additionally, our team reported an integrative Na2Ti3O7
nanosheet arrays/carbon textiles (NTO/CT) anodes through a simple hydrothermal process, as
shown in Figure 9h.[10a] The introduction of flexible carbon textiles not only improved electrical
conductivity of Na2Ti3O7, but also avoided the addition of binder to reduce the impedance of
electrode. Flexible SIC based on NTO/CT anode and graphene film cathode exhibited a maximum
volumetric energy density of 1.3 mWh cm−3 (Figure 9i). In addition, more and more Ti-based
compounds with different crystalline structures have been explored to be used as anode materials
for SICs, including NASICON-type NaTi2(PO4)3,[42] monoclinic Na2Ti9O19,[43] two-dimension
Ti3C2T MXene.[44] However, the stability of interface between electrode and electrolyte is still an
object worthy of study for practical applications.
18

Figure 9. (a) TEM image of single-crystal-like structure TiO2 (inset shows its SAED image), (b)
b-value for anodic and cathodic peak current, (c) plot of capacity vs. v–1/2 (inset is the capacitive
Accepted Manuscript
contribution at a scan rate of 3 mV s–1). Reproduced with permission.[12b] Copyright 2017,
American Chemical Society. (d) SEM image of brown TiO2 and illustration of as-fabricated SICs,
(e) rate capability of SICs at different scan rates and current densities, respectively. Reproduced
19

with permission.[34] Copyright 2018, American Chemical Society. (f) SEM image of Na2Ti2O5-x
nanowire arrays, (g) cycle performance of Na2Ti2O5-x nanowire arrays anode at 25 C. Reproduced
with permission.[41] Copyright 2017, American Chemical Society. (h) Illustration of the preparation
of NTO/CT composites, (i) the geometric density of flexible SICs. Reproduced with permission.[12c]
Copyright 2016, Wiley-VCH.
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Except for Ti-based compounds, Nb-based compounds are also the hot new anode materials for
SICs. Typically, orthorhombic Nb2O5 with a large interplanar lattice spacing of 3.9 Å has access
to Na-ion de/intercalation that has been proved to be the best one in all the reported Nb2O5, such
as the pseudohexagonal and amorphous phases.[45] However, the poor electrical conductivity
(⁓3×10–6 S cm–1) of Nb2O5 plays a key role in the release of electrochemical performance. As
reported, the enhanced performances have been achieved via the introduction of conductive
materials such as carbon materials. For example, Lee et al. prepared Nb2O5@Carbon core-shell
nanoparticles and rGO composites (Nb2O5@C/rGO).[46] Thanks to the well synergistic effects of
nanosized Nb2O5@C core-shell structures and rGO, this composite displayed much enhanced
capacity and excellent rate capability. Matching with commercial AC (MSP-20), the hybrid SIC
exhibited a high energy density of 76 Wh kg−1. Our group reported Nb2O5 with different structures
by adjusting pH value and found the advanced architecture of Nb2O5 nanosheets with exceptional
sodium ion storage performance.[47] The SICs based on Nb2O5 nanosheets anode and peanut shell
carbon (PSC) cathode had an exceptionally high performance. Additionally, the performance is
highly depended on the micro/nanostructures and the particle size, so Nb2O5 nanocrystal has been
widely explored to shorten the ionic diffusion pathway to improve electrochemical performance.[48]
For example, Yan et al. synthesized ultrafine Nb2O5 nanocrystal with an average particle size of 3
nm on rGO sheets.[49] The voids among ultrafine Nb2O5 nanosheets effectively facilitated ionic
20

diffusion and remitted the huge volume expansion, while the high conductivity of rGO was capable
of electron transfer, resulting in outstanding rate and cycle performance. Even so, the low
theoretical capacity of Nb2O5 due to a single redox element limits the improvement in energy
density of SIC. So, mixed titanium-niobium oxides, such as Ti2Nb2O9, TiNb2O7, have been
identified and developed to be used as anode materials for sodium ion storage because of multiple
Accepted Manuscript
redox couples of Ti4+/Ti3+, Nb5+/Nb4+.[50] For example, Shen et al. reported an ultrathin Ti2Nb2O9
nanosheets with a thickness of 1.2–1.3 nm by using liquid exfoliation combined with topotactic
dehydration.[51] The Ti2Nb2O9 nanosheets anode delivered a Na+ storage capacity of 250 mAh g–1
at 50 mA g–1 with the first cycle coulombic efficiency (CE) of 82%. Even the current density was
increased to 4000 mA g–1, the capacity was still 134 mAh g–1, meaning a good rate capability. But
the complex synthesis process and the low yield limit its large-scale applications. Huang et al.
adopted a solid-state method via high-temperature calcination to obtain high-yield TiNb2O7.[52]
Importantly, they employed ball-milling method to adjust the electrode interface by changing the
size and structure of TiNb2O7. As a result, a specific capacity of 180 mAh g–1 was obtained at 15
mA g–1 as well as a good cycle stability. Beyond that, other Nb-based mixed metal oxides were
aslo designed and applied for sodium ion storage because they delivered excellent lithium store
performance. [53]
3.1.4 Organic materials
Organic materials have attracted much attention in energy storage devices because of the
advantages of low cost, easy preparation/degradability, high theoretical capacity and flexible
structure applying to various metal ion batteries, which can realize a truly ‘green’ energy storage
device. [54] For example, Lee and co-workers reported a novel SIC employing perylene-3,4,9,10-
tetracarboxylic acid dianhydride (PTCD) battery material as anode and typically capacitive
21

material, polyaniline (PANI) as cathode, as shown in Figure 10a.[55] During the charging process,
Na+ moved to PTCD anode accompanied by an enolation reaction, while PANI cathode suffered a
quick surface pseudocapacitive reaction, and Na+ and ClO4- got back to electrolyte by means of
reversible reactions. Owing to the special energy storage mechanism and highly reversible
reactions, the assembled SIC delivered a higher energy density (Emax=95 Wh kg–1) than
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supercapacitors as well as a higher power density (Pmax=7 kW kg–1) than rechargeable batteries, as
displayed in Figure 10b. And then this group reported a SIC based on disodium rhodizonate
(DSRH) anode and AC derived from cardamom shells cathode (Figure 10c).[56] In this work,
authors compared the electrochemical performances of DSRH with different sizes, and confirmed
that nano DSRH had the best performance because of short ion diffusion pathway. The non-linear
CD curves of organic SIC at different current densities within a cell voltage of 0–3 V demonstrated
the synergistic effect of battery and capacitive materials, as shown in Figure 10d. Meanwhile, the
shape of the curves can well retain at high current density, signifying high rate capability and power
density. It is noteworthy that the SIC displayed a ultralong cycle life (Figure 10e), as a result of
low solubility of DSRH and AC materials.
22

Accepted Manuscript
Figure 10. (a) Schematic diagram of the working principle of the SIC, and (b) Ragone plot
comparing the SIC with other energy storage systems. Reproduced with permission.[55] Copyright
2017, American Chemical Society. (c) The scheme of the working mechanism of the SIC, and (d)
CD curves at different current densities and (e) cycling stability at 4 A g–1 of the SIC. Reproduced
with permission.[56] Copyright 2018, American Chemical Society.
Additionally, our group designed novel aqueous hybrid ion capacitors based on Na+ and NH4+
as charge carriers, in which aqueous salt solution acted as electrolyte.[32, 57] Compared with organic
SICs, the power density had been boosted obviously, and the stability also was enhanced as many
as 10 000 cycles with little decay. Additionally, the use of aqueous electrolyte not only decreased
the cost, but also realized truly ‘green’ energy storage. It is a pity that the narrow potential window
arising from water decomposition limited the cell voltage of SICs, which restricted the
23

enhancement of energy density. In order to boost the electrochemical performances including
capacity, rate capability and cycle stability to satisfy the practical applications, the following
solutions could be used for reference, as shown in Figure 11. First, combining with carbon. This
method not only improves the conductivity of organic materials, but also employs the adsorption
or confined effect of carbon on remitting the self-charge phenomenon. Second, molecule
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engineering. The tailor of functional groups in organic molecules can effectively adjust the redox
potentials. Third, electrolyte modification. The selections of high concentrated or solid electrolytes
can reduce the solubility of organic materials to prolong the cycle lifetime. Last, polymerization.
Porous and conjugated structures can not only shorten ionic transfer pathway to enhance the
response capability to a large current density, but also improve the cycle performance.
Figure 11. Design strategies of organic materials for SICs.
3.2 Capacitive cathode materials
For electrolyte consuming mechanism based SICs, the cathode materials mainly base on
capacitive materials, especially commercial AC.[15, 39, 42b, 58]

However, the relatively low
capacitance limits the improvement in energy density of SICs. Given this, researchers attempt to
24

design carbon materials with various structures ranging from 1D to 3D to expand the specific
surface area and further to enhance the capacitance. Our previous review has summarized the
progress of nanostructured carbon materials and discussed the influence of morphology on the
electrochemical properties.[59] Recently, bio-mass or organic compounds derived carbon,[18, 60]
graphene,[61] and CNTs[62] etc. have been employed to act as cathode materials for SICs. However,
Accepted Manuscript
the capacitance is still far less than battery materials, leading to a mass mismatching. Therefore,
researches on the modification of pure carbon have achieved a significantly enhanced performance.
The classic modification method is heteroatomic doping to enhance wettability and to provide
pseudocapacitance. Up to now, as a “neighbor” of carbon, N-doped carbons have been reported
incalculably. Frackowiak and co-workers put forward that pyridinic N at graphitic edges
contributed to major pseudocapacitance via protonation reaction while quaternary N affected the
change of electronic structure, as shown in Figure 12a.[63] Currently, overviews of N-doped carbon
materials have been presented widely including the synthesis method and potential applications.[64]
Beyond N-doping, B-doped carbon is capable of boosting the electrochemical performance
because of the redox reaction of B-containing groups or oxygenated groups around the B-doping
sites. Kim et al. reported B-doped 3D porous carbon pattern (B-3D-PCP) prepared by lithographic
processes and following heat treatment to obtain different B-doping levels and conductivity
(Figure 12b).[65] After B-doping, B-3D-PCP delivered obvious redox peaks in the CV curves and
expected capacitance that was ten times larger than un-doped 3D-PCP, and increased with
increasing the B-doping level (Figure 12c). Moreover, Li et al. employed the facile hydrothermal
method to synthesize B-doped graphene aerogels (B-GAs).[66] Thanks to more defects caused by
B atom in the graphene lattice, a high capacitance of 308.3 F g−1 at 1 A g−1 was obtained, being
superior to undoped graphene aerogels. However, different from B- and N-doping, S- or P-doping
25

could lead to expanded interlayer spacing and structural defect sites due to the larger atomic radii
than C.[67] The first application of S-doping carbon as EDLC materials with superior performance
was reported by Hasegawa et al.[68] But the mechanism was unclear. Zhao et al. employed H2O2 to
adjust the ratio of aromatic sulfide, sulfoxide, and sulfone groups in the S-doped carbon.[69] They
postulated that the improved capacitance stemmed from a polarized surface and reversible redox
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faradic reactions (Figure 12d). Therefore, the good understanding in energy storage mechanism of
S-doping carbon is an important research point in enhancing the performance, which is expected
to be proved through FT-IR and XPS technologies. In addition, P-doping in carbon matrix benefits
to reduce the electrophilic oxygen species and enhance the oxidation stability, leading to an
enhanced performance.[70] And the reason needs to be further confirmed. Based on the independent
property of B, N, S, P-doping carbon, multiatomic co-doping carbon could achieve synergistic
effects, which have been reported widely.[71] Unfortunately, it is an intractable problem to
distinguish the respective contributions for the total capacitance. And the heteroatomic doping
level is harder to control. Besides electric double-layer materials, pseudocapacitive materials were
also explored to construct SICs because of the higher capacitances. Besides carbon materials,
Wang et al., introduced Ti2CTx MXene nanosheets in SIC because the MXene Ti2CTx nanosheet
delivered a higher specific capacity than double-layer capacitive electrodes and a faster kinetic
process than ion intercalation bulk electrodes.[72] Moreover, our group designed a novel aqueous
SIC based MnO2 cathode and polyimide anode.[57a] The enhancement in capacitance of MnO2
cathode resulted in a high energy density of 78.5 Wh kg–1 and a long cycle lifespan. With this
respect, typical pseudocapacitive materials such as electroactive organic small molecule
(methylene blue, quinones, etc.), polypyrrole, polythiophene and RuO2 are promising candidates
because of their high capacitance and fast kinetics.
26

Accepted Manuscript
Figure 12. (a) Possible redox reactions of pyridinic groups. Reproduced with permission.[63]
Copyright 2007, Elsevier. (b) Plot of carbonization temperature, B doping configuration level and
the electrical conductivity of the corresponding samples in B-3D-PCP samples, (c) CV curves of
B-3D-PCP samples. Reproduced with permission.[65] Copyright 2018, Elsevier. (d) The proposed
electrochemical reaction of S-doping mesoporous carbon. Reproduced with permission.[69]
Copyright 2012, Elsevier.
3.3 Dual carbon-based SICs
Up to now, several types of SICs based on different cathode and anode materials have been
reported, whereas they suffered from limited power density and shorter cycle life in the meantime.
This is mainly attributed to the inevitable difference in the structural stability of different materials
in the same organic electrolyte. In view of this, Ding et al. assembled a novel SIC by using the
active materials derived from the peanut shells in both cathode and anode.[10b] As shown in Figure
13a, the peanuts shells were separated into two parts. In particular, the cathode (PSNC) synthesized
by using the outer rough peanut shells as the precursor underwent a thermal treatment and high-
temperature KOH chemically activated process. The as-prepared PSNC delivered ultrahigh surface
27

area of 2396 m2 g–1 and high fraction of mesopores, benefiting for ion adsorption and rapid
electrolyte diffusion. The PSNC cathode had a specific capacity of 161 mAh g–1 at 0.1 A g–1 and
retained 73 mAh g–1 at 25.6 A g–1, illustrating a good rate capability. In addition, the inner portion
of the peanut shells was used as the precursor to obtain anode materials (PSOC) that was prepared
by high-temperature carbonization and followed low-temperature activated process. The PSOC
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anode also displayed a high specific capacity and an ultra-long cycle lifespan (capacity retention
of 75% after 10 000 cycles). As a result, the fully assembled SIC (PSNC//POSC) showed a wide
operation temperature and potential range, and high energy density of 201 and 50 Wh kg−1 at the
power density of 285 and 16 500 W kg−1 (based on the total active mass), respectively, as shown
in Figure 13b. Beyond that, they also used the biomass-peanut skin as the precursor to produce
both anode and cathode electrodes.[73] Both displayed hierarchical porous and heteroatom-doped
structure, allowing facilely ion transport and electrolyte infiltration during the charge-discharge
processes. The optimized SIC (SCN-A//SCN-A) can deliver a maximum energy density of 112
Wh kg1 and retain 85% capacity after 3000 cycles (Figure 13c).
Designing a superior carbon material through green and sustainable precursors is very
essential, and it more potential for large-scale application. For example, Wang and colleagues
presented the garlic derived hard carbon (GDHC) anode by a simple high-performance
pyrolysis.[74] The porous carbon (GDPC) cathode was obtained by using the garlic precursor
through a carbonization and activation method (Figure 13d). They used the garlic derived carbon
as the anode (GDHC) and cathode (GDPC) to fabricate a high-performance SIC, which displayed
a maximum energy density of 156 Wh kg1 and a long life of 10 000 cycles. Besides that, Wang et
al. used the low-cost fish scale as a carbon precursor to prepare N, O-doped hierarchical porous
carbons (HPCs) (Figure 13e).[75] The HPCs had been used as cathode and anode electrode to
28

construct SIC with a high energy density of 103.2 Wh kg1. However, the biomass-derived carbon
materials are usually prepared through direct carbonization, lacking the structural design and
regulation process, thus it is difficult to achieve optimal electrochemical performance. Recently,
our group presented using the polyimide to prepare N-doped porous carbon microsphere (NPCM)
anode and hierarchical porous carbon microsphere (NPCM-A) cathode.[76] The test results
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indicated that both NPCM anode and NPCM-A cathode delivered excellent performance including
rate capability and cycle stability because of the special structure.
Figure 13. (a) Schematic diagram of materials and charge storage mechanisms for PSNC//POSC
SICs, (b) electrochemical performances of PSNC cathode and SICs. Reproduced with
permission.[10b] Copyright 2015, Royal Society of Chemistry. (c) Electrochemical performances of
SCN//SCN-A SICs. Reproduced with permission.[73] Copyright 2016, Royal Society of Chemistry.
(d) Illustration of the preparation process of GDHC and GDPC and the mechanism of the
fabricated SICs. Reproduced with permission.[74] Copyright 2019, American Chemical Society. (e)
29

Schematic illustration of HPCs. Reproduced with permission.[75] Copyright 2019, Elsevier.
In general, carbon materials with special microstructure are prepared by employing temples,
which makes a complex process. Additionally, oxygen-doping carbon can effectively improve
wettability to increase the accessibility to electrolyte, and thus decrease the charge-transfer
resistance. For example, Yan et al. prepared 3D framework carbon (3DFCs) through directly
Accepted Manuscript
calcining sodium citrate without any template or catalyst (Figure 14a).[19] The 3DFCs exhibited
different interlayer distance, O-doped level and electrical conductivity under different calcination
temperatures (600, 700, 800, and 1000 ℃). In order to achieve a higher yield and graphitization
degree, 3DFC-700 sample was used as the raw material and annealed at 1000 ℃ to obtain 3DFC-
1000 anode, which displayed a typical battery behavior. Meanwhile, the 3DFAC cathode was
prepared by KOH activation of 3DFC-700, and showed a typical capacitance behavior. Finally, a
dual-carbon SIC delivered a high energy density of 110 Wh kg1 and excellent power density (67
Wh kg1 at 20 000 W kg1), as well as an ultra-long cycle life (80% capacity retention after 10 000
cycles). Interestingly, Qiu et al. used the low-cost cattle bone as the precursor to prepare
hierarchical porous carbon nanosheets (HPCNS),[77] which suffered from hydroxyapatite/KOH-
synergetic pyrolysis, resulting in a well surface-doped with N (6.4 at%) and O (17.1 at%),
respectively. The presence of defects can provide efficient storage sites to adsorb Na ions and react
with Na ions, but also shorten the Na-ion diffusion distance. A full SIC delivered a maximum
energy density of 105.2 Wh kg1 and a long cycle lifespan (85.5% capacity retention after 4000
cycles). In addition, Yang et al. reported a novel SIC using porous hollow N-doping carbon spheres
(HPCS) anode and hierarchical porous hollow N-doping carbon bowls (HPCB, chemical activation
of HPCS) cathode (Figure 14b).[78] The SIC presented a high energy density of 128.5 Wh kg1 and
a superior power density of 11.9 kW kg1, as well as a long cycle lifespan.
30

Accepted Manuscript
Figure 14. (a) Schematic illustration of the dual-carbon SIHC using 3DFC as battery-type anode
and 3DFAC as capacitor-type cathode. Reproduced with permission.[79] Copyright 2017, WILEY-
VCH. (b) Schematic illustration of the synthesis of HPCS and HPCB. Reproduced with
permission.[78] Copyright 2018, American Chemical Society. Schematic illustration of (c) the
arrays of nitrogen-doped mp-CNSs, (d) VO2@ mp-CNSs and NVP@mp-CNSs, (e) the flexible
quasi-solid-state SICs. Reproduced with permission.[80] Copyright 2018, WILEY-VCH.
Currently, most SICs are fabricated by using organic liquid electrolytes that are faced with
volatility, flammability, environmental pollution and leakage, leading to a series of safety issues.
Thus, constructing a solid-state SIC using solid-state or quasi-solid-sate electrolytes might be a
feasible solution. For example, Fan et al. utilized 2D metal-organic frameworks (MOFs) array as
the reactive template to prepare N-doped mesoporous carbon nanosheets (Figure 14c).[81] N-doped
mesoporous carbon nanosheets (mp-CNSs) can be used as the reactor in situ to support VO2
(VO2@mp-CNSs) and Na3V2(PO4)3 (NVP@mp-CNSs) nanoparticles uniformly (Figure 14d),
which were used as anode and cathode materials for SIC, respectively. Noted that the porous
P(VDF-HFP) membrane was employed as separator and electrolyte to construct flexible quasi-
solid-state SIC (Figure 14e). The fabricated SIC delivered both high energy density (161 Wh kg1)
and power density (48 kW kg1), as well as high safety performance. In addition, Zhao et al.
31

prepared a quasi-solid-state SIC, which was constituted of nanoporous disordered carbon
nanoparticles anode and N-doped carbon hollow microspheres cathode, along with a Na+
conducting gel polymer electrolyte.[82] This device displayed an operating voltage of 4.4 V and an
energy density of 157 Wh kg1 at 620 W kg1. Furthermore, our group also reported a graphene-
based quasi-solid-state SIC based on the surface oxygen-functionalized crumpled graphene (OCG)
Accepted Manuscript
as both cathode and anode, and also applied the Na+ conducting gel polymer as the electrolyte.[83]
This device was reported to have a high energy density of 121.3 (Wh kg1), high power density (8
000 W kg1), and long cycle life. Compared with traditional SIC, the safety in quasi-solid-state
SIC has been improved to some level, but there are a lot of problems for practical applications.
4. Conclusion and Outlook
Sodium ion capacitors (SICs) have emerged in the last few years as new energy storage
devices utilizing the combination of battery and capacitive type electrodes. But unlike LICs, the
larger cation size (1.02 Å) than Li (0.76 Å) makes a limited selectivity of insertion hosts. Thus,
numerous efforts have been made to explore materials for SICs and to solve the kinetic issue,
further to obtain high energy density, high power density and long cycle lifespan. Currently, there
are two main methods, including employing Na+-storage materials based on different mechanisms
and designing materials with different nanostructures.
In this review, we summarize the latest advances in charge storage mechanisms and related
materials from inorganic to organic compounds for SICs. A series of transition metal sulfides and
selenides are attempted to be used as anode materials for SICs. Besides that, insertion-type
pseudocapacitive materials (such as Ti-based, Nb-based and carbon-based, etc.) as anodes for SICs
result in a dramatic improvement in power density and energy density. The carbon-based cathode
should be required with a large specific surface area and high specific capacitance (such as AC,
32

graphene, polymer and biomass-derived carbon, etc.). Additionally, carbon doped by functional
groups/heteroatoms is also an effective approach to enhance both gravimetric and volumetric
capacitance dramatically. Finally, porous dual carbon-based SICs are built using the high-
performance carbon materials as cathode and anode electrodes, which avoid the utilization of metal
elements, and improve the electrochemical performance by the good dynamic matching. Although
Accepted Manuscript
there are a lot of research reports for SICs at present, more potentials are still needed to exploit for
high-performance SICs. The key problem is to solve the mismatch of internal kinetics and
capacitance simultaneously between anode and cathode. Therefore, advanced in situ detection
technology should be explored to investigate potentials and mass changes of anode, cathode and
full cell, synchronously, during the charge-discharge processes of SICs. As for practical application.
SICs suffer from a complicated pre-sodium process prior to charge the devices, leading to an
increase of the manufacturing costs. Beyond that, the intrinsic instability of liquid electrolytes
easily results in safety issues owing to their flammability, the possibility of leakage and internal
short-circuits. In view of this, future research should focus on the safety issue of organic
electrolytes (replaced by the quasi-solid-state and all-solid electrolytes) and the complex process
of the pre-sodium ways.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (U1802256,
51672128, 21773118, 21875107, and 51802154), the Key Research and Development Program in
Jiangsu province (BE2018122), Funding for Outstanding Doctoral Dissertation in NUAA
(BCXJ19-07) and Postgraduate Research & Practice Innovation Program of Jiangsu Province
(KYCX18_0279 and KYCX19_0174), China Scholarship Council (201906830060) and a Project
Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
33

(PAPD).
Conflict of Interest
The authors declare no conflict of interest.
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Table of contents
This paper reviews the electrode materials and their energy storage mechanisms in sodium ion
44

capacitors.
Accepted Manuscript
45

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Sodium-ion capacitors: Materials, Mechanism, and Challenges

Article in ChemSusChem · February 2020

Zhang Yadi Jiang Jiangmin

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Langyuan Wu Hui Dou

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To be cited as: ChemSusChem 10.1002/cssc.201903440

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Sodium ion capacitors: materials, mechanism and challenges

Zhang,3 Shide Wu,4 Mengyao Dong,5,6 Xiaogang Zhang,1* Zhanhu Guo6*

China. E-mail: azhangxg@nuaa.edu.cn

Zhenjiang 212003, China

3. College of Chemical and Environmental Engineering, Shandong University of Science and

Technology, Qingdao, Shandong 266590, China

Light Industry, No. 136, Science Avenue, Zhengzhou, 450001, China

5. Key Laboratory of Materials Processing and Mold (Zhengzhou University), Ministry of

Zhengzhou University, Zhengzhou, China

6. Integrated Composites Laboratory, Department of Chemical and Biomolecular Engineering,

University of Tennessee, Knoxville, TN 37996, USA. E-mail: zguo10@utk.edu

*E-mail: azhangxg@nuaa.edu.cn (Xiaogang Zhang)

This article is protected by copyright. All rights reserved.

This article is protected by copyright. All rights reserved.

Reproduced with permission.[3a] Copyright 2014, American Chemical Society.

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applications are also discussed.

Figure 2. The history process of hybrid metal ion capacitors.

2. Charge storage mechanism and equations of SICs

hybrid mechanism (Figure 3). There are briefly described as follows:

a. Electrolyte consuming mechanism. In this system, battery materials, including Na+

capacitor-type materials such as AC derived from biomass and metal-organic-framework,

to the mechanism of supercapacitors, but Na+ intercalates into Na+-including compounds or

This article is protected by copyright. All rights reserved.

example is the Na2Ti3O7//AC system and so on.[10]

The successful design includes MXene//Na2Fe2(SO4)3, AC//NVOPF@PEDOT systems, etc.[11]

intercalate into the cathode to recover to Na-including state, such as NTP@rGO//Na3V2(PO4)3/C

This article is protected by copyright. All rights reserved.

3. Materials for SICs

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materials act as anode, and capacitive materials serve as cathode.

3.1 Battery-behavior anode materials

3.1.1 Hard carbon materials

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after 5000 cycles at a current density of 2 A g1.

SICs can be successfully constructed by using biomass-derived HC as anode materials, while

This article is protected by copyright. All rights reserved.

This article is protected by copyright. All rights reserved.

3.1.2 Transition metal sulfides and selenide compounds

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interlayer-modification method to build a MoS2-carbon monolayer inter-overlapped structure.[22]

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AC cathode to construct a high-performance SIC, which delivered a maximum energy density of

of expanded interlayer spacing MoS2 (MoS2/N-NPCM) as composited anode material.[26]

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image and elemental mapping results of MoS2/C-HNTs. Reproduced with permission.[23]

device. Reproduced with permission.[24] Copyright 2019, Elsevier.

nanosheets and carbon microtubes (SnS/aCMT) by using solvothermal and high-performance

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energy density of 88 Wh kg−1 at 150 W kg−1, as well as long-term cycle life.

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Copyright 2019, Royal Society of Chemistry.