Progress in Natural Science: Materials International xxx (xxxx) xxx

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Progress in Natural Science: Materials International

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Research progress on electrolyte key salts for sodium-ion batteries

weimin Zhao a, *, Miao Wang a, Haichen Lin b, Kangwoon Kim b, Rongkai He c, Shijie Feng b,
Haodong Liu b, **
a
College of Chemical Engineering and Safety, Binzhou University, Binzhou, 256503, PR China
b
Center for Memory and Recording Research Building, University of California San Diego, 9500 Gilman Dr, San Diego, CA 92093, USA
c
STATE GRID Liaocheng PowerSupply Company, Liaocheng, 252000, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Sodium-ion batteries (SIBs) are considered potential successors to lithium-ion batteries in the fields of energy
Sodium ion batteries storage and low-speed vehicles, thanks to their advantages such as abundant raw material sources, high energy
Electrolyte density, and a wide operational temperature range. However, several scientific and engineering challenges still
Electrolyte salts
require attention in the development of sodium-ion batteries. Electrolyte salts, as a key component of sodium-ion
Electrochemical performance
battery electrolytes, play a critical role in battery performance. This paper provides a brief overview of the
research progress on different electrolyte salt systems in sodium-ion batteries. It discusses characteristics such as
ionic conductivity, electrochemical windows, electrochemical performance, and thermal safety in various solvent
systems. Furthermore, the paper summarizes a series of strategies for controlling electrolyte and electrode in-
terfaces, offering references for addressing the challenges in the mass production and application of sodium-ion
batteries.

1. Introduction
The development of human society is closely intertwined with energy
[1]. However, the extensive consumption of fossil fuels, such as oil, has
led to a severe energy crisis and environmental pollution [2,3], signifi-
cantly impacting economic and social development and the human living
environment. Consequently, building a new, renewable, and clean en-
ergy infrastructure has emerged as a strategic objective for countries
worldwide. China, in particular, has set ambitious targets to peak carbon
emissions before 2030 and achieve carbon neutrality by 2060 [4–6].
According to statistics from the carbon emission estimation database
Carbon Monitor, in 2021, the power and transportation sectors accoun-
ted for a significant share of global carbon emissions, approximately
38.9% and 20.3%, respectively [7,8]. In light of the dual carbon policy,
adjusting the energy landscape through renewable and clean energy
generation, such as wind and solar power [9–12], and employing elec-
trochemical energy storage and conversion devices for electricity storage,
can effectively mitigate carbon emissions [13,14]. Secondary recharge-
able chemical power sources play a pivotal role in this energy revolution.
Presently, the predominant secondary batteries are lithium-ion batteries,
relying on graphite anodes [15]. However, lithium's abundance in the
Earth's crust is only about 0.002% [16,17], far from satisfying the
pressing requirements of the energy transformation and upgrade. In
contrast, sodium's abundance in the Earth's crust is approximately 2.36%,
and sodium salts can be extracted from seawater, ensuring evenly
distributed resources [18]. Furthermore, sodium-ion compounds are
readily accessible, maintain price stability, and are cost-effective. Uti-
lizing aluminum as the cathode current collector instead of the more
expensive copper foil reduces the overall cost of sodium-ion batteries by
30–50% compared to lithium-ion batteries [19,20]. Sodium-ion batteries
are widely regarded as the most promising electrochemical energy stor-
age devices for large-scale storage applications in the post-lithium era
and have emerged as a leading direction in electrochemical energy en-
gineering research and application development [21,22].
2. Fundamentals of battery electrolytes
The working principle of sodium-ion batteries is akin to that of
lithium-ion batteries [23–25]. They were introduced almost simulta-
neously in the 1970s, primarily because sodium and lithium belong to the
same main group in the periodic table and possess the same number of
outer electrons [26], signifying their similar chemical properties. A

* Corresponding author.
** Corresponding author.
E-mail address: zhaoweimin137@sina.com (Zhao).

https://doi.org/10.1016/j.pnsc.2024.03.003
Received 23 December 2023; Received in revised form 8 March 2024; Accepted 11 March 2024
Available online xxxx
1002-0071/© 2024 Published by Elsevier B.V. on behalf of Chinese Materials Research Society.

Please cite this article as: w. Zhao et al., Research progress on electrolyte key salts for sodium-ion batteries, Progress in Natural Science: Materials
International, https://doi.org/10.1016/j.pnsc.2024.03.003
Zhao et al.
sodium-ion battery consists of key components, including the cathode,
anode, separator, electrolyte, and current collector [27–29]. The struc-
ture and performance of the cathode and anode materials govern the
battery's sodium storage capabilities. The separator, acting as an insu-
lator between the cathode and anode, prevents short circuits [30]. The
electrolyte serves as the medium for ion transport, while the current
collector facilitates electron transmission. During the charging process,
Naþ ions are extracted from the cathode, traverse through the electrolyte
and separator, and intercalate into the anode [31,32]. This leaves the
cathode in a high-potential state with less sodium, and the anode in a
low-potential state with more sodium. The discharge process reverses
this, with Naþ ions de-intercalating from the anode, passing through the
electrolyte and separator, and re-intercalating into the cathode material,
restoring the cathode to a state with more sodium. To maintain charge
balance, an equal number of electrons traverse the external circuit during
both charging and discharging, shuttling between the cathode and anode
alongside Naþ ions, resulting in oxidation and reduction reactions at the
electrodes. The cathode material primarily supplies sodium ions and
determines the battery's energy density. Presently, there are three pri-
mary routes for cathode materials: layered transition metal oxides,
Prussian blue analogs, and polyanion compounds [33]. The anode ma-
terial serves as the carrier for ions and electrons during sodium-ion
battery charge and discharge cycles, dictating energy storage and
release. Carbon-based materials are the preferred choice for the anode
[34]. Due to the instability of compounds formed when sodium inter-
calation into graphite layers, which is challenging with conventional
graphite materials. Currently, anode materials suitable for sodium-ion
batteries encompass amorphous carbon, metal compounds, and alloy
materials. Because of the significant volume change and poor cycling
performance of alloy materials, and the low capacity of metal com-
pounds, hard carbon and soft carbon with amorphous structures are the
predominant anode materials [35]. Soft carbon can be fully graphitized
at high temperatures, providing excellent conductivity. Hard carbon
boasts advantages like high sodium storage capacity, low sodium inter-
calation potential, high specific capacity, and ease of synthesis. Its ca-
pacity in sodium batteries (200- 450mAh g1) rivals that of graphite in
lithium batteries (200- 450mAh g1), rendering it a more versatile
choice.
The electrolyte, often referred to as the 'lifeblood' of the battery,
serves as the conduit linking the positive and negative electrodes and
facilitates ion conduction within the battery [36]. Notably, the electro-
lyte exerts a crucial influence on the performance of the electro-
de/electrolyte interface and significantly affects battery characteristics,
including capacity, internal resistance, charge and discharge rate, oper-
ating temperature, storage, and even the safety of lithium-ion batteries
during overcharging and over-discharging. Typically, the electrolyte
comprises sodium salts, solvents, and additives. Among these, sodium
salts primarily supply Naþ ions in the electrolyte, thereby impacting the
power of battery, cycling performance, capacity, and safety. Sodium salts
must meet fundamental criteria, including high solubility, robust thermal
stability, cost-effectiveness, and environmental compatibility [37–39].
Simultaneously, several other aspects necessitate consideration.
a. Chemical Stability: It is widely recognized that even trace amounts of
water in the electrolyte can react with PF 6 ions to generate Lewis
acids such as HF and POF3. During sodium deintercalation, these
chemicals react with transition metal oxides, resulting in metal
dissolution and an accelerated rate of irreversible reactions within the
battery.
b. Electrochemical Stability: Sodium salts dissolved in non-aqueous
solvents should possess a wide electrochemical window. To main-
tain the thermodynamic stability of sodium-ion batteries, the elec-
trolyte's electrochemical window (ESW) should exceed the oxidation-
reduction potentials of both the anode and cathode. ESW is defined as
the difference between the lowest unoccupied molecular orbital
(LUMO) and the highest occupied molecular orbital (HOMO) [40,41].
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Progress in Natural Science: Materials International xxx (xxxx) xxx
Consequently, the type of anion in sodium salts significantly impacts
the ESW of the electrolyte. For instance, in a mixed solvent of
EC/DEC, the oxidation potentials follow this order: NaPF6 > NaClO4
> NaTFSI > NaFSI, with the PF6- ion having the lowest HOMO level
(11.67 eV), making it less prone to electron loss and decomposition.
Conversely, the ClO 4 ion possesses an HOMO level at 7.89 eV,
suggesting lower chemical stability during oxidation. Nevertheless,
it's essential to understand that chemical stability is relative, and
there's no absolutely stable anion in SIBs. The anions in sodium salts
can participate in the formation of the solid electrolyte interface (SEI)
[42]. For instance, decomposition products of PF 6 ions during
reduction, such as NaF, constitute the primary components of SEI. In
summary, the anions in sodium salts can influence the chemical sta-
bility of the electrolyte in two ways: first, the HOMO level of the anion
constrains the highest electrochemical window of SIBs; second, the
LUMO level of the anion facilitates the formation of SEI to inhibit
further electrolyte decomposition.
c. Ion Dissociation State and Migration Rate Issues: This encompasses
factors like the interaction between anions and cations, solvent
dielectric constant, viscosity, freezing point, and their effects on Naþ
ions and anions. Sodium salts exhibit smaller diffusion rates, more
intricate chemical reactions, and less stable solid electrolyte inter-
phase (SEI) films at the anode when compared to lithium salts [43].
Furthermore, the solvation structures influenced by different sodium
salt anions dictate the de-solvation kinetics of Naþ ions and the
evolution of the interface film. Notably, the weak interaction between
Na þ ions and PF 6 promotes sodium desolvation and storage kinetics.
Solvation structures involving PF 6 induce anion-prioritized decom-
position, resulting in a thin, inorganic-rich electrode-electrolyte
interface phase that enhances interface stability and limits excessive
electrolyte solvent decomposition [44]. This, in turn, ensures elec-
trode stability and facilitates charge transfer kinetics.
d. Compatibility with Cathode, Anode Materials, and current collectors:
for instance, anions such as FSI and TFSI have the potential to
corrode the aluminum current collector at high voltages. However,
this corrosion can be mitigated by incorporating additives, such as
oxalate, to passivate the current collector within the electrolyte.
e. Influence of Anion Type and Concentration: Due to interactions be-
tween cations and anions and variations in anion sizes, different so-
dium salts in the same solvent exhibit discrepancies in conductivity.
The concentration of sodium salts also significantly impacts electro-
lyte conductivity [45]. Typically, in systems with lower sodium salt
concentrations, the electrolyte's conductivity gradually increases
until it reaches a maximum value with increasing sodium salt con-
centration, after which it starts to decline [46]. For instance, in an
EC/DMC solvent, the conductivity of NaPF increases to a maximum of
6.8 mS cm1 at a salt concentration of 0.6 mol L1, and then expe-
riences a slight decrease with the addition of more salts [45]. It's
well-established that at lower salt concentrations, free solvent mole-
cules predominate. Consequently, adding more salt increases ionic
conductivity [45]. However, higher salt concentrations notably
elevate the viscosity of the electrolyte, thereby impacting the elec-
trochemical stability of the electrolyte with highly concentrated so-
dium salts.
3. Electrolytes salts
The sodium salts commonly employed in sodium-ion battery elec-
trolytes primarily include sodium hexa-fluorophosphate (NaPF6), sodium
perchlorate (NaClO4), and bis-(trifluoromethanesulfonyl)imide sodium
(NaTFSI) [47]. Among these, NaPF6 and NaClO4 are recognized as two
key salts with significant industrial application potential. NaPF6, owing
to its synthesis method resembling that of LiPF6 and its compatibility
with lithium-ion battery production processes and equipment, has
emerged as one of the leading electrolyte salts for sodium-ion batteries
(SIBs). On the other hand, NaClO4 boasts advantages such as rapid ionic
Zhao et al.
migration, robust chemical stability, impressive thermal stability, and
cost-effectiveness, rendering it a preferred choice among electrolyte salts
for SIBs. Sodium salts containing the sulfonyl fluoride group (NaTFSI,
NaFTFSI, NaFSI, etc.) exhibit higher thermal stability and non-toxicity
but are seldom used independently due to the corrosive impact of their
anions on aluminum foil current collectors. Moreover, when selecting
sodium salts for electrolytes, it is imperative to consider toxicity concerns
and potential harm to human health. Sodium salts based on AsF 6 and
SbF6 are rarely employed. In essence, the choice of sodium salts should
encompass not only the intrinsic physical and chemical properties of the
sodium salts themselves, including viscosity, conductivity, and thermal
stability but also their compatibility with electrodes when mixed with
solvents. This includes considerations of electrochemical stability and
thermal stability under various operational conditions [48].The author's
review encompasses recent research on the application of both inorganic
and organic electrolyte salts in sodium-ion batteries, while also offering
insights into the anticipated trends in the use of sodium salts in
sodium-ion battery electrolytes.
3.1. NaClO4
NaClO4 offers several advantages, including high ionic conductivity,
excellent compatibility with electrodes, and cost-effectiveness, which
have led to its extensive study as one of the earliest sodium salts. In 1980,
Delmas et al. made a pivotal discovery, demonstrating that the P2-type
cathode material NaCoO2 could exhibit remarkable electrochemical
performance when used with a PC-based NaClO4 electrolyte [49]. Sub-
sequently, in 2000, Stevens employed a 1 M NaClO4- EC/DEC (3:7, V/V)
electrolyte, achieving the reversible intercalation of Naþ ions in hard
carbon materials at room temperature [50]. However, it's important to
note that the stability of the interfacial film formed by NaClO4- based
electrolytes can be susceptible to the strong oxidizing nature of per-
chlorates. This can lead to the detachment of some interfacial films from
the electrode surface, resulting in renewed contact between the
Fig. 1. (a)Schematic of the SEI compositions formed in different electrolytes and a comparison of the charge transfer energy barriers [52]. (b) (b-1)SEM images of the
(Ni0.5Mn0.5)(OH)2 precursor and (b-2) of the final Na(Ni0.5Mn0.5)O2 compound [54]. (c) Schematic of the SnC/NaNi0.5Mn0.5O2 full cell [54]. (d) Schematic illustration
of the sodium ion storage process in charging [55].
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Progress in Natural Science: Materials International xxx (xxxx) xxx
electrolyte and materials and excessive solid electrolyte interphase (SEI)
formation, ultimately deteriorating battery performance. To address
these challenges and further enhance battery performance, the addition
of certain film-forming additives to the electrolyte has proven effective.
Komaba et al. [51], for instance, conducted battery tests with different
additives in a 1 M NaClO4– PC electrolyte, including fluorinated ethylene
carbonate (FEC), trans-difluoroethylene carbonate (DFEC), ethylene sul-
fonate (ES), and vinylene carbonate (VC). They observed that FEC could
significantly improve the cycle stability of the NaNi1/2Mn1/2O2||hard
carbon full battery. This enhancement was attributed to FEC preferential
decomposition on the hard carbon surface, forming a dense SEI layer rich
in NaF, which inhibited the reduction decomposition of PC and thus
contributed to improved battery performance.
In the quest to suppress sodium metal dendrites, Li [52] developed an
innovative ultra-thin (8 μm) external non-porous separator composed of
a honeycomb structure of fibers. As shown in Fig. 1(a) schematic of the
SEI compositions formed in different electrolytes and a comparison of the
charge transfer energy barriers. This honeycomb-like fiber structure
exhibited an exceptional electrolyte absorption rate (376.7%) and
inherent polymer transmission capability, enabling unimpeded ion
transfer. They utilized a 1.0 M NaClO4-EC/PC electrolyte with 5.0 wt%
FEC as an additive, employing polyethersulfone SPF and polyvinylidene
fluoride PVDF-HFP coated separators. This setup resulted in the assembly
of a high-performance NaNi1/3Fe1/3Mn1/3O2||hard carbon pouch bat-
tery, achieving a remarkable energy density of 229.4 Wh kg1 and 157.6
Wh L1, along with excellent cycling stability. Additionally, Liu [53]
employed ab initio molecular dynamics (AIMD) simulations and reactive
molecular dynamics (RMD) to investigate the NaClO4– PC system with 2
% FEC. This research elucidated the solvent decomposition process, the
formation of key SEI components (such as NaF, NaOH, and Na2CO3), and
potential reaction mechanisms. The study provided insights into the
formation process of crucial components like OH and CO2 3 within the
SEI layer. The computational results confirmed that NaOH, NaF, and
Na2CO3 are indeed inorganic constituents of the SEI, aligning with
Zhao et al.
experimental findings.
In addition to research on additives, optimizing solvent composition
represents a crucial avenue of investigation. Alc
antara et al. [56] con-
ducted a study using hard carbon as the negative electrode and NaClO4 as
the electrolyte salt. They compared the electrochemical performance of
hard carbon in different solvents or solvent combinations, including
EC/DMC (1:1, v/v), dimethyl ether (DME), tetrahydrofuran (THF), and
EC/THF (1:1, v/v). Their findings revealed that THF could effectively
enhance the electrochemical performance of the hard carbon negative
electrode. It is important to note that these solvent systems all exhibited
an initial capacity decline trend. Furthermore, Oh et al. [54] reported the
characteristics and performance of a sodium-ion battery based on a Sn–C
anode and a Na(Ni0.5Mn0.5)O2 cathode especially in the micrometer scale
spherical morphology optimized by Na(Ni0.5Mn0.5)O2, it can lead to a
continuous increase in the vibrational density, about 2.5 g cm3. High
vibrational density is a very popular characteristic for battery electrodes,
as it reflects high volumetric energy density. The SEM images in Fig. 1
reveal that the co-precipitated Na(Ni0.5Mn0.5)O2 hydroxide precursor
powder exhibits a spherical morphology (Fig.b-1) that persisted also in
the final Na(Ni0.5Mn0.5)O2 compound obtained by sodiation at the high
temperature of 820  C (Fig.b-2). Fig. 1(c) shows the scheme of the Sn–
C/NaClO4 PC-FEC/Na(Ni0.5Mn0.5)O2 sodium-ion battery developed in
this work. They replaced PC with EMC as a solvent and incorporated 2 %
FEC as a film-forming additive, with NaClO4 as the electrolyte salt. This
electrolyte demonstrated an impressive electrochemical stability window
of up to 5.6 V and an ionic conductivity of up to 6.0 mS cm1. Despite
NaClO4 thermal stability at 310  C, it often contains crystalline water,
resulting in higher water content in the electrolyte system. Additionally,
its intrinsic oxygen content contributes to its strong oxidizing properties,
posing safety concerns and hindering its practical commercial-scale use.
To address these issues, researchers have shown significant interest in
gel electrolytes and ionic liquid-like electrolytes based on NaClO4. Wu
et al. [55] reported a highly porous PVdF- HFP gel polymer electrolyte
using 1 M NaClO4, with a thermal stability temperature of up to 130  C
(matching that of the commercial separator Celgard-2730). This elec-
trolyte exhibited a room temperature ionic conductivity of 0.60 mS cm1,
a broader electrochemical window (4.6 V), and excellent mechanical
properties, including a tensile strength of 7.6 MPa. As shown in Fig. 1(d),
schematic illustration of the sodium ion storage process in charging.
Goodenough [57] designed a sodium-ion battery featuring Sb as the
anode, Na3V2(PO4)3 as the cathode, and a cross-linked PMMA composite
gel polymer as the electrolyte. This gel polymer employed NaClO4 as the
electrolyte salt and achieved an electrochemical window of 4.8 V, a room
temperature ionic conductivity of up to 6.2 mS cm1, and an assembled
battery with impressive discharge capacities of 106.8 mAh g1 at 0.1C
and 61.1 mAh g1 at 10C, showcasing its potential for large-scale
applications.
Additionally, Lai et al. [58] demonstrated a polymer electrolyte
comprising NaClO4 as the electrolyte salt, silane-modified β- Al2O3
powder, and a crosslinked PVDF- HFP matrix. This electrolyte design
aimed to suppress side reactions at the electrode/electrolyte
inorganic-organic interface, thereby enhancing electrochemical perfor-
mance. Results indicated that the composite electrolyte maintained an
ionic conductivity of 1.37 mS cm1 at 20  C, with a sodium ion trans-
ference number reaching 0.424. Furthermore, the sodium symmetric cell
based on this composite electrolyte displayed robust cyclic performance,
exceeding 800h of stable cycling at 0.5 mA cm2 without significant
voltage polarization. This underscored its effective protective role for the
sodium anode, with the assembled Na3V2(PO4)3||hard carbon battery
retaining 92.2% of its capacity after 1000 cycles at 3  C, providing a
valuable strategy for constructing highly stable sodium-ion batteries.
To mitigate the exothermic reactions associated with highly volatile
organic solvents and address dendrite formation on the negative elec-
trode, Guzm
an et al. [59] synthesized an ionic liquid, M3STFSI, through
ion exchange within a trimethylthorium-bis(trifluoromethylsulfonyl)
imide/sodium perchlorate/polyepoxide ternary system. They prepared
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Progress in Natural Science: Materials International xxx (xxxx) xxx
a gel-state polymer solid polymer electrolyte (SPE) membrane. XRD
spectra of M3STFSI and the SPE membrane demonstrated efficient Na þ
ion diffusion in the ionic liquid and polymer membrane. By utilizing a
ratio of 8.51:0.25:0.26 mM, they achieved high ionic transference
numbers (~0.26) and substantial ionic conductivity (~0.58 mS cm1),
coupled with an electrochemical stability window of 4.25 V. After 70
cycles at 0.1C, the discharge capacity remained at 75 mAh g1, with a
coulombic efficiency exceeding 99%. These results offer valuable guid-
ance for the potential commercialization of low-cost and high-safety
batteries [60].
In summary, NaClO4 presents several advantages, including its
affordability and impressive electrochemical and air stability, which
make it convenient for transport and storage. Consequently, it is often
preferred in the development of new electrolyte formulations. However,
its high oxidizing properties raise safety concerns, posing a challenge to
its widespread commercial use. Moreover, anhydrous NaClO4, being a
potentially explosive compound, is subject to regulatory controls. Future
research on NaClO4 should prioritize enhancing the safety of commercial
batteries utilizing this electrolyte system.
3.2. NaPF6
In a study by Eshetu [61], NaPF6 exhibits minimal mass loss even at
temperatures up to 300  C, demonstrating its high thermal stability.
Nevertheless, studies have shown that NaPF6 is highly hygroscopic and
readily undergoes hydrolysis to produce NaF, HF, and other phosphate
species (such as POF3). Remarkably, this hydrolysis can still take place in
battery-grade electrolytes with <20 ppm of trace water, highlighting the
highly hygroscopic nature of NaPF6. Consequently, this means that the
quality of commercially purchased NaPF6 may be variable, and it de-
pends on the degree of hydrolysis that has occurred (either through
storage or as a result of the synthetic route used to make it). This property
allows NaPF6 to be compatible with various positive and negative elec-
trode materials [62].
Kim [63] used NaPF6- DME as an electrolyte to test the electro-
chemical performance of graphite anodes in SIB systems, maintaining a
stable capacity of 150mAh g1 after 2500 cycles. Among the sodium salts
(NaPF6, NaCF3SO3, and NaClO4) with three different anions used in DME
solvents in the alloy negative electrode, only NaPF6 demonstrated stable
cycling performance, while NaCF3SO3 and NaClO4 proved incompatible
with the alloy negative electrode. Lucht [64] utilized NaPF6 as the
electrolyte salt and EC/DEC (1:2, v/v) as the solvent, resulting in an
initial coulombic capacity of 162 mAh g1 for hard carbon materials
within the 0.05–2 V charge-discharge range. By employing attenuated
total reflection infrared spectroscopy (IR-ATR) and X-ray photoelectron
spectroscopy (XPS), the study revealed that the primary components of
the SEI film formed on the hard carbon anode included NaF, along with
minor quantities of alkyl carbonates and Na2CO3. This suggests that the
SEI components and reaction mechanisms in sodium-ion batteries share
fundamental similarities with those in lithium-ion batteries [64]. As
shown in Fig. 2, the sodium salt anion participates in the solvation
structure, where PF 6 preferentially decomposes to form a stable inor-
ganic compound-rich position-electrolyte interface phase (CEI), inhibit-
ing solvation and ensuring interfacial stability. Furthermore, it's worth
noting that the interaction between Naþ and PF 6 is significantly weaker
than the interaction between Naþ and ClO 4 , which promotes the
de-solvation of Naþ, improves charge transfer kinetics [63]. The
Na4Fe3(PO4)2P2O7 (NFPP)||Na battery, using NaPF6 electrolyte, exhibi-
ted a high capacity retention rate of 81.2 % after 800 cycles at 4.3 V.
Additionally, it achieved a high specific capacity of 70 mAh g1 at a high
rate of 20C.
In order to construct a stable electrode/electrolyte interface and
enhance the cycling performance of the battery, Che [65] incorporated
three additives (FEC, PST, DTD) into a 1 M NaPF6-PC/EMC-based elec-
trolyte. The combination of these three additives resulted in the forma-
tion of a SEI layer rich in organic components and a dense CEI layer at the
Zhao et al. Progress in Natural Science: Materials International xxx (xxxx) xxx

Fig. 2. Electrochemical performance of NFPP based batteries: (a) initial charge and discharge curve of NFPP/Na battery, (b) cycle performance of NFPP/Na battery,
(c, d) corresponding charge and discharge curve, (e) rate performance, (f) cycle performance of NFPP/hard carbon battery, and (g, h) Corresponding charge-discharge
curve (1C ¼ 129 mAh g1).

Fig. 3. Electrochemical performance of Na2Ti3O7@C/Na half-cells containing different electrolytes:(a) cycle curve,(b) first charge and discharge curve,(c) rate
performance,(d) radar diagram.

5
Zhao et al.
electrode interface, contributing to improved cycling stability. The CEI
generated by NaPF6-E was more uniform and much thinner (4 nm) than
the CEI generated by NaClO4-E, indicating that the PF6-anion-induced
CEI layer remained relatively stable even at 4.3 V cutoff voltage
(Fig. 4(a), (a-1)). In contrast, the CEI generated by NaClO4-E is uneven
and thicker (>10 nm), with a large uncovered area on the cathode sur-
face (Fig. 4(b), (b-1)), which may be due to severe interfacial reactions
occurring on the cathode surface. Fig. 4(c) shows the action mechanism
of NaPF6 and NaClO4 electrolytes. Ponrouch et al. [66] systematically
studied the viscosity, ionic conductivity, electrochemistry, and thermal
stability of the electrolyte after the combination of different solvents (PC,
EC, DMC, DME, DEC, Diglyme, and Triglyme) or their mixtures with
different sodium salts (NaClO4, NaPF6, and NaTFSI). The results showed
that the binary EC:PC solvent mixture is considered the best solvent
formulation for sodium-ion batteries. The combination of NaClO4 or
NaPF6 with binary EC:PC solvents promotes the formation of a stable SEI
layer, leading to excellent reversible capacity and good magnification
performance of the hard carbon electrode. In the study of co-intercalation
behavior with 1 M NaPF6 in PC or FEC for various CFx materials, Chen
[67] found that 1 M NaPF6 in FEC is conducive to solvent
co-intercalation. Among them, F-CF0.88 cathodes exhibited a
discharge-specific capacity of 1094 mAh g1 for the first time, main-
taining a stable rechargeable specific capacity of 344 mAh g1. This
improved rechargeable behavior is attributed to solvent co-intercalation,
mainly due to the larger solvation energy of fluoroethylene carbonate
(FEC), making it easier to embed. This study offers new insights and a
deeper understanding of solvent co-intercalation in CFx as a Na-ion
rechargeable battery.
Moreover, Yan [70] prepared a composite electrolyte formulation by
adding additives VC, butanedinitrile (SN), 1,3-propanesultone (PS), and
sodium difluoroborate (NaDFOB) into the baseline electrolyte (1.0 M
NaPF6-EC/PC). These additives synergistically formed stable SEI and CEI
layers on the hard carbon anode and Na3V2(PO4)2F3 cathode, enhancing
cycling performance at 55  C. Using EIS spectroscopy, XPS, and theo-
retical calculations, they confirmed the key role of NaF and sulfate de-
posits at the interface. Considering the special process of
oxidation-reduction in ether-based electrolytes, Xu [71] designed a
NaPF6-DME electrolyte with a sodium salt concentration of 2 M. This
design aimed to reduce the co-intercalation voltage of the graphite
anode, resulting in a higher average working voltage (3.1 V) and a long
cycle life (1000 cycles) for the Na1.5VPO4.8F0.7||graphite batteries. The
combination of ether electrolytes and DOL presents a promising solution
for achieving high-performance full cells [68]. For ether solvents, the
electrons generated during the discharge process attack an electrophilic
Fig. 4. (a, b) TEM images of the cycled NFPP cathode of NFPP/Na cells: (a, a-1) NaPF6-E, (b, b-1) NaClO4-E [65]. (c) Schematic diagrams of the mechanism of action of
different electrolytes [65]. (d) Schematic diagram of decomposition pathways of (d) ether solvent (DEGDME) [68]. (e) The schematic diagram of Al2O3 layers
improving ICE of HC electrode. HC, hard carbon; ICE, initial Coulombic efficiency [69].
6
Progress in Natural Science: Materials International xxx (xxxx) xxx
center such as the carbon atom of the ether solvent, leading to the
breakage of chemical bonds. As illustrated in Fig. 4(d), schematic dia-
gram of decomposition pathways of ether solvent (DEGDME). Tarascon
[72] used 1.0 M NaPF6-DEGDME as the electrolyte. They achieved a
specific capacity of 768.0 mAh g1 after 100 cycles for micron-sized Sn
electrodes, with a capacity retention rate of 88.0 %. The authors attrib-
uted the improved cycling stability of the battery to the evolution of
micron-sized Bi into a porous structure after cycling in the ether elec-
trolyte. This structural transformation was found to be related to the
contact wetting angle between the ether electrolyte and the Bi electrode.
Seh [73] reported a highly reversible sodium deposition process in
ether electrolytes, with a long cycle life of over 300 cycles at a current
density of 0.5 mA cm2 and an average coulombic efficiency of 99.9 %.
Further cryo-EM and XPS results suggested that the high reversibility of
metallic sodium was attributed to the formation of a stable and thin SEI.
Qin et al. [74] conducted a comparison of the electrochemical perfor-
mance between a 1 M NaPF6-DGME electrolyte and a typical carbonate
electrolyte (1 M NaPF6 in PC with 5.0 wt% FEC as the additive), using the
high-voltage poly-anion material Na3V2(PO4)2F3 as the cathode. When
using the 1 M NaPF6-DGME electrolyte, they observed a capacity reten-
tion rate as high as 96.2% after 300 cycles at 0.5C, which significantly
surpassed the 77.5 % observed with 1 M NaPF6 PC-FEC. Furthermore, the
capacity retention rate remained at 95.0 % after 500 cycles at 1C and
reached 98.8 % at 20C after 1000 cycles, demonstrating excellent cycling
stability. The authors attribute the higher cycling efficiency in the NaPF6-
ether electrolyte to the absence of large agglomerates in the material
particles, resulting in reduced electrochemical polarization.
In contrast, the poor cycling performance in the carbonate electrolyte
results from the high solubility of Na2CO3 produced by oxidation, which
fails to stabilize the positive electrode-electrolyte interface. To effectively
mitigate side reactions and the continuous decomposition of the elec-
trolyte caused by active sites (defects, pores, and functional groups) on
the surface of the hard carbon anode, Yu [69] engineered an amorphous
Al2O3 layer on the hard carbon (HC) surface. This layer suppressed the
continuous decomposition of NaPF6 in carbonate solvents, reducing the
accumulation of NaF. As a result, it formed a thinner, denser solid elec-
trolyte interface, effectively reducing interface resistance. This straight-
forward and effective surface engineering method significantly increased
the initial coulombic efficiency of the hard carbon anode, raising it from
64.7 % to 81.1 %. Furthermore, the optimized HC- Al2O3 exhibited a
higher reversible capacity, reaching 321.5 mAh g1 at 50.0 mA g1,
along with excellent cycling stability, retaining 89.3 % of its capacity
after 2000 cycles at 1.0 mA g1. Fig. 4(e) shows the schematic diagram of
how homotype heterogeneous HC-Al2O3 material improves ICE.
Zhao et al.
Homotype refers to both HC and Al2O3 as amorphous materials, while the
disorder degree of HC is significantly higher than that of Al2O3
In order to enhance the wide temperature range operation of sodium-
ion batteries, Li [75] utilized Na4Fe3(PO4)2P2O7 (NFPP) as the cathode
and natural graphite (NG) as the anode. They employed a 1.0 M NaPF6
electrolyte dissolved in an ether-based solvent to create a low-cost
NFPP||NG battery. This battery achieved a discharge specific capacity
of 153.2 mAh g1 at 0.2 A g1, maintained a discharge capacity of
90.8mAh g1 even at a discharge current density of 10 A g1, and
exhibited a capacity retention rate of 60%. Notably, during the charging
process, it took only 32.6 s to reach a 60% capacity. Even after 1000
cycles at room temperature, the battery still exhibited an outstanding
capacity retention rate of 81%. The excellent performance of the NFPP||
NG battery across a wide temperature range was attributed to the high
boiling point of 162.1  C and low freezing point of 72.0  C of the NaPF6
diglycol ether electrolyte. This, coupled with the solvent co-intercalation
process at the anode and the high Naþ diffusion rate of the NFPP elec-
trode material, allowed the battery to achieve discharge capacities of
148.7 and 130.3 mAh g1 at 20  C and 40  C, respectively.
Remarkably, even at the ultra-low temperature of 70.0  C, the NFPP||
NG battery operated effectively, maintaining a discharge capacity of 61.9
mAh g1. Furthermore, the high boiling point of the electrolyte and the
excellent thermal stability of the electrode materials enabled the entire
battery to operate at elevated temperatures, reaching as high as 130.0  C.
At this temperature, the battery maintained a discharge capacity of 129.8
mAh g1 and a coulombic efficiency of 93.0 %. Therefore, the full battery
can operate in a wide temperature range from 70.0  C to 130.0  C [76].
Darren demonstrated a new synthesis method for NaPF6. This
involved the reaction of ammonium hexafluorophosphate with sodium
metal in THF solvent, resulting in the production of electrolyte salt free
from common impurities found in commercial NaPF6. The NaPF6 salt was
dissolved in a binary mixture of ethylene carbonate: diethyl carbonate
(EC:DEC ¼ 1:1,v/v) solvent. It's worth noting that when the concentra-
tion of NaPF6 reached up to 3.5 M, the electrolyte exhibited a very high
viscosity, a gel-like appearance, and contained undissolved NaPF6. The
maximum electrolyte conductivity, measured at 358  C, was obtained
with a 1 M electrolyte solution, reaching 19.0 mS cm1. This conductivity
value was higher than those observed for 0.5 M, 2.0 M, and 3.0 M
electrolyte solutions, which recorded conductivities of 8.2, 16.1, and
11.0 mS cm1, respectively. Electrolyte conductivity and the aging of the
native SEI were measured in Na–Na symmetric cells within the concen-
tration range of 1.0–3.0 M using electrochemical impedance spectros-
copy. For ultraconcentrated (>2.0 M) electrolytes, the interface
impedance was approximately 300 W (6.3 mS cm1), while for 1.0 M
electrolyte, it measured around 500 W (3.8 mS cm1) at the same storage
time.Notably, the interface stabilization is slower for the 1.0 M electro-
lyte, and this phenomenon may be attributed to differences in SEI com-
positions, structures, or dissolution rates.
3.3. Imides
Compared to traditional inorganic sodium salts like NaClO4 and NaPF6,
sodium salts containing the fluorosulfonyl group (NaTFSI, NaFTFSI, NaFSI,
etc.) offer higher thermal stability and non-toxicity. However, they are
rarely used alone as sodium salts, primarily due to their anions' corrosive
effect on aluminum foil current collectors and the high cost of synthesizing
these types of sodium salts. As mentioned before, the electrolyte, as a
crucial component of the battery, significantly influences battery perfor-
mance. Even in the same organic solvent system, when the concentration
of the electrolyte salt reaches a certain level (3.0 M), referred to as high
concentration electrolytes (HCE), the electrolyte exhibits unique properties
not typically found in traditional low-concentration electrolytes. High
concentration electrolytes have demonstrated excellent electrochemical
performance, including reduced side reactions, an expanded working
temperature range, a broader electrochemical window, improved rate
performance, and enhanced cycling stability.
7
Progress in Natural Science: Materials International xxx (xxxx) xxx
Song et al. [77] developed a 1.2 M NaFSI electrolyte blend, incor-
porating DME and BTFE to create a locally high salt concentration elec-
trolyte formulation. This formulation effectively suppressed the
formation of rock salt on the surface of NaNi0.68Mn0.22Co0.1O2. They
assembled a NaNi0.68Mn0.22Co0.1O2||hard carbon full cell with a high
load exceeding 2.5 mAh cm2, and this cell maintained 82% of its ca-
pacity after 450 cycles. Yan et al. [78] demonstrated an electrolyte based
on NaFSI with triethyl phosphate (TEP) and 1,1,2,2-tetrafluoroethyl-2,2,
3,3-tetrafluoropropyl ether (TTE) as solvents. They assembled a
NaCu1/9Ni2/9Fe1/3Mn1/3O2||hard carbon full cell. Cryo-EM analysis
confirmed the presence of an inorganically rich solid electrolyte interface
(SEI), which reduced side reactions between hard carbon and the elec-
trolyte. Additionally, a thin but robust cathode-electrolyte interface (CEI)
inhibited the dissolution of transition metals and surface reconstruction.
As a result, the full cell exhibited high safety and a long cycle life, with a
capacity retention rate of 82.5 % after 200 cycles. More recently, Yang
et al. [79] proposed a similar electrolyte formula, combining NaTFSI with
trimethyl phosphate (TMP), BTFE, and VC for Prussian blue||hard carbon
pouch cells. Leveraging hydrogen bond regulation, they achieved the
formation of an optimized SEI. This allowed the full cell to maintain a
high capacity retention rate of over 85 % after 120 cycles.
In typical sodium-ion electrolytes, there are three main sodium ion
solvation structures present, including solvent-separated ion pairs, con-
tact ion pairs, and aggregates. However, in high salt concentration
electrolytes, the predominant structures are aggregates and contact ion
pairs. As a result, most solvents are coordinated, and anions are likely to
coordinate with two or more sodium ions, leading to the formation of an
anion-based solid electrolyte interface (SEI). The high solubility of NaFSI
and NaTFSI in carbonate/ether solvents has opened up possibilities for
designing and implementing high concentration electrolyte or locally
high concentration electrolyte systems in sodium-ion battery applica-
tions. Patra et al. [80] reported a 3.0 M NaFSI-EC/PC electrolyte with an
ionic conductivity of 6.3 mS cm1, a viscosity of 22 cP, and relatively low
flammability. Notably, this medium concentration electrolyte facilitated
the formation of an organic-inorganic composite component on the hard
carbon electrode. The initial discharge coulombic efficiency and average
coulombic efficiency of the hard carbon anode reached 85.2% and
>99.9%, respectively. Even after 500 cycles, the capacity loss was only
5.0%. Compared to the thicker SEI layer (~20 nm) formed in the 1.0 M
NaPF6-EC/PC electrolyte, the SEI thickness remained at ~5 nm.
Hwang et al. [81] utilized a molten salt system to enhance the solu-
bility of sodium salts in organic solvents and introduced a composite
electrolyte salt consisting of 5.0 M NaFTFSI-NaFSI-NaOTF in PC as the
solvent. This innovative electrolyte effectively mitigated the corrosion of
the aluminum current collector and exhibited a wide electrochemical
stability window. When assembled in a NaCrO2||hard carbon full cell, it
maintained an impressive capacity retention rate of 86.9% after 100
cycles at 1.0C. In a parallel study, Wen et al. [82] conducted a compar-
ative analysis to assess the compatibility of NaCF3SO3 and NaClO4 as
electrolyte salts with a Na2Ti3O7 anode. Their findings indicated a sig-
nificant difference in first-cycle coulombic efficiency. Na2Ti3O7@C||Na
cells using a NaClO4-based electrolyte achieved a first-cycle coulombic
efficiency of 55.5 %, while Na2Ti3O7@C||Na cells using a NaCF3SO3--
based electrolyte achieved a substantially higher first-cycle coulombic
efficiency of 76.5 %, as illustrated in Fig. 3. The authors attributed this
improvement in coulombic efficiency to the decomposition of NaCF3SO3
in carbonate solvents. This decomposition produced additional
sulfur-containing compounds that exhibited favorable sodium conduc-
tivity and stability, ultimately enhancing the interface transport prop-
erties of the material and inhibiting the increase in solid electrolyte
interface (SEI) film thickness. As a result, this contributed to improved
cycling and rate performance of the battery.
Fan et al. [83] utilized a NaCF3SO3-DEGDME-based electrolyte to
effectively enhance the first-cycle coulombic efficiency to 96.2% and
achieve a long cycle specific capacity of 341.7 mAh g1 at 0.2 A g1 for
250 cycles when using NiCo2S4 as a sodium-ion battery anode material.
Zhao et al.
Their research, complemented by techniques like DFT, in situ XRD, and
other characterization methods, substantiated the optimization impact of
NaCF3SO3 on the formation process of sulfide intermediates. Further-
more, Li et al. [84] conducted a comparative study to evaluate the so-
dium storage performance of high surface area carbon materials (HSAC)
in various electrolytes. Their findings revealed that the NaCF3SO3--
DEGDME electrolyte demonstrated the highest initial cycle coulombic
efficiency at 69.28 % and delivered a reversible capacity of 283 mAh g1.
This particular electrolyte exhibited relatively superior electrochemical
performance when compared to others.
Wang et al. [85] discovered that the positive electrode, NNMO,
exhibited superior performance in a 1.0 M NaPF6 diethylene glycol
dimethyl ether (G2) - based electrolyte. In this G2 electrolyte, NNMO
achieved a reversible capacity of 97.5 mAh g1 at 2000 mA g1,
compared to only 48.9 mAh g1 in a PC-based electrolyte. The discharge
capacity remained at 140 mAh g1 under a 50 mA g1 discharge current,
with a retention rate of 94.6 % after 100 cycles. The G2 electrolyte also
demonstrated excellent rate performance in the 1.0V to 4.0 V charge and
discharge range. This enhanced performance is attributed to the forma-
tion of a dense and stable cathode-electrolyte interface (CEI) layer rich in
Na–F and C–O species, facilitating Naþ diffusion and transport channels
on the NNMO positive electrode during cycling.
3.4. Other-type sodium salts
Boron-based anion sodium salts often exhibit superior electro-
chemical and thermal stability, while effectively improving the film-
forming properties of the electrolyte on the electrode surface, resulting
in enhanced cycling stability. Notably, NaBF4 demonstrates high ionic
conductivity at 0.9833 mS cm1 and finds extensive use in ionic liquids
[86]. In a study by Du and colleagues, the performance of two different
electrolytes was investigated in Na2Ti3O7@C half cells: a 1.0 M NaBF4 -
diglyme electrolyte and a 1.0 M NaClO4-EC/PC electrolyte (1:1, v/v)
[86]. The results revealed that the battery employing the 1.0 M NaBF4-
diglyme electrolyte exhibited a first-cycle coulombic efficiency of 73.0%
and lower SEI film impedance. Importantly, this electrolyte formulation
also proved suitable for use with hard carbon anodes.
In comparison to NaBF4, NaODFB stands out as a novel chelating
sodium salt, featuring an anion comprising half BOB and half BF 4 , as
exemplified by B(C2O4)F 2 . Research indicates that in carbonate elec-
trolytes, NaODFB forms a dense and smooth SEI film on the cycled so-
dium anode, effectively mitigating sodium dendrite growth. NaODFB
boasts several outstanding properties, including compatibility with
common SIB solvents, a wider electrochemical window than NaClO4 and
NaPF 6 based electrolytes, impressive rate and cycling performance in
Na0.44MnO2||Na half cells compared to commercially available sodium
salts, and excellent chemical stability, with no production of harmful
gases upon exposure to air or reaction with trace water [86].
The electrochemical performance of NaODFB-based electrolytes was
investigated in NVP cathode materials. Specifically, a NaODFB-based
diglyme electrolyte was employed in NVP||HC button cells. The use of
1.0 M NaODFB diglyme electrolyte contributed to the cycling stability of
NVP||Na half cells, resulting in a specific capacity of 95 mA h g1 and a
capacity retention rate of 86.0 % after 100 cycles at room temperature at
0.5C. This improvement can be attributed to the formation of a thinner
CEI film on the NVP material surface after cycling in the 1.0 M NaODFB
diglyme electrolyte, along with a low B2O3 content in the battery,
ensuring favorable cycling stability. It's worth noting that NaBOB salts
exhibit desirable thermal stability (>300  C) and chemical stability in
air, making them effective in passivating aluminum current collectors.
However, NaBOB is susceptible to hydrolysis with water, resulting in the
production of oxalic acid and other insoluble compounds. Additionally,
NaBOB has extremely low solubility in most organic solvents [87].
Regarding the practical application of NaBOB, its use is currently
restricted to amide solvents like N-methyl-2-pyrrolidone (NMP) and
phosphate esters such as trimethyl phosphate (TMP) and triethyl
8
Progress in Natural Science: Materials International xxx (xxxx) xxx
phosphate (TEP). These solvents have higher polarity compared to car-
bonates or ethers, which enhances the solubility of NaBOB. In NMP,
NaBOB can achieve a dissociation of 0.66 M, resulting in an ionic con-
ductivity of 8.83 mS cm1. Although there is limited literature on the
utilization of NaBOB in batteries, it has demonstrated an initial
coulombic efficiency of up to 82 % when used with hard carbon anodes.
During cycling voltammetry on TMP-coated aluminum foil with NaBOB
as the electrolyte salt, the reduction potential is approximately 1.5 V vs.
Naþ/Na, and the oxidation potential is around 3.0 V. Since NaBOB de-
composes at the positive electrode to form a passivation layer, it can
extend the electrolyte window to as high as 4.0 V. In a full cell comprising
hard carbon and Prussian white, a capacity retention rate of 57.0% was
achieved after 1000 cycles. When using TEP, a capacity retention rate of
80 % was achieved after 2000 cycles. However, it's important to note that
the high viscosity of TEP can lead to significant power decay and reduced
rate performance in the battery.
Similar to NaBOB, other salts like NaBSB have been explored for their
solubility and conductivity characteristics. For NaBSB, it was found to
have solubility exceeding 1.0 mol kg1 in GBL, but its ionic conductivity
was relatively low at 2 mS cm1 at 1 mol kg1. In a button cell with
chromium oxide as the cathode and metallic Na, the cell exhibited a
higher charging cutoff voltage during constant current cycling [88].
Another noteworthy salt, sodium tetraphenylborate (NaBPh4), has
gained attention due to its strong anti-reduction properties. NaBPh4 is
highly soluble in ether solvents, with an ionic conductivity of up to 6.0
mS cm1 at 0.5 M. When used in a full cell with hard carbon and
Na2V3O7, it demonstrated good cycling stability and high-rate perfor-
mance. However, its oxidative stability is limited to 3.4 V, which may
pose challenges with certain cathode materials. Cyan-based sodium salts,
such as NaTIM, NaPCPI, and NaTCP, show promise in terms of solubility
and ionic conductivity [89]. These cyan-substituted anions have delo-
calized negative charges, leading to higher solubility and conductivity.
For example, the conductivity of NaTIM and NaTCP in EC/DMC at 0.75
mol kg1 reached 16.53 and 13.53 mS cm1, respectively, surpassing the
10.2 mS cm1 of NaClO4 in PC. Additionally, these cyan-based salts
exhibit excellent thermal stability, remaining stable at temperatures
exceeding 500  C. In terms of electrochemical stability, NaTCP and
NaTIM show promise with oxidative stability exceeding 4 V when used in
a PC solvent, making them attractive for various applications.
Bitner-Michalska et al. [90] investigated the use of Na0.68CoO2 as a
cathode material in an electrolyte consisting of 0.75 M NaTDI-EC/DMC
(1:1) at C/10 for 50 cycles of constant current charge and discharge.
The initial capacity was 80.68 mAh g1, and after 50 cycles, the capacity
was well-maintained, with a discharge capacity of 63.0 mAh g1 on the
50th cycle (more than 78.0% of the first cycle). This research suggests
that NaTDI is compatible with the positive electrode material and can be
successfully applied as an electrolyte in sodium-ion batter-
ies.Plewa-Marczewska et al. [91] examined electrolytes containing new
sodium salts and found that both NaTDI and NaPDI electrolytes exhibited
excellent ionic conductivity. The highest conductivity was observed at
concentrations of 0.5 M and 1.0 M in the tested temperature range. For
example, at 20  C, the ionic conductivity was 4.0 mS cm1 for both
NaTDI (0.5 M, 3.71 mS cm1; 1.0 M, 3.78 mS cm1) and NaPDI (0.5 M,
3.79 mS cm1; 1.0 M, 3.83 mS cm1). NaTDI exhibited higher conduc-
tivity than the most conductive concentration (0.5 M and 1.0 M) at
temperatures above 40  C. However, 1.5 M samples showed lower con-
ductivity for both salts.
Bitner-Michalska and Michalczewski et al. [92] observed that the
Sb2O3/C composite anode achieved an initial capacity of 584.0 mAh g1
at C/10 constant-current charge and discharge in 0.75 M NaTDI EC/DMC
electrolyte. Ether solvents, which have been rarely used in lithium-ion
batteries, have gained traction in sodium-ion batteries due to their ad-
vantages. They form thinner SEI films, exhibit solvent intercalation ef-
fects, and facilitate rapid sodium ion migration. Ether-based solvents
enable highly reversible embedding and release of sodium ions, resulting
in denser, thinner, and more stable SEI films. This significantly reduces
Zhao et al. Progress in Natural Science: Materials International xxx (xxxx) xxx

sodium ion diffusion lengths, enhances sodium ion transmission effi-
ciency, and prevents additional electrolyte decomposition on the nega-
tive electrode surface. As a result, when using ether-based electrolytes,
graphite negative electrodes can provide high coulomb efficiency, stable
capacity of 100 mAh g1, and long cycling performance up to 1000 cycles
[93]. Reber et al. [94] employed Na(FSI)0.71(FTFSI)0.29 electrolytes at
concentrations of 20.0 M, 25.0 M, 30.0 M, or 35.0 M in NVPOF||NTP and
NaMnHCF||NTP full battery configurations. Among these, 30.0 M and
35.0 M concentrations exhibited superior capacity retention rates. The
hybrid electrolyte, utilizing the highly fluid TFSI anion, achieved
coulomb efficiencies of 98–99% (NTP-NVPOF) and 96–98 %
(NTP-NaMnHCF). This innovative electrolyte enabled the stable opera-
tion of a 2V sodium-ion battery, featuring the NaTi2(PO4)3/Na2Mn
[Fe(CN)6] electrode pair, at 1C for 300 cycles. The battery demonstrated
a coulomb efficiency exceeding 99.5 % and an energy density up to 77
Wh kg1.
Liu et al. [95] reported that solid-state sodium batteries employing a
PEO/NaFSI–Al2O3-AQ electrolyte and Na3V2(PO4)3 as the active material
demonstrated excellent reversibility, high rate capability, long-term
cycle stability, and high coulomb efficiency. Comparative experiments
evaluating the electrochemical performance of SPE (FSI1-Al2O3-AQ)
were conducted, with control groups using SPE (FSI1-Al2O3-AN) and
TFSI-Al2O3-AQ. In Fig. 5, the NVP|FSI–Al2O3-AQ||Na coin battery,
charged and discharged at 0.1C between 2.5 and 3.8 V at 80  C, exhibited
a highly reversible specific capacity of 110 mAh g1 and a coulomb
efficiency of up to 93.8 % in the first cycle when using SPE. In contrast,
the control groups showed lower reversible capacities (89 and 97 mAh
g1), initial coulomb efficiencies (84.8 and 88.4%), and higher polari-
zation (88 mV and 91 mV). Batteries utilizing SPE (FSI–Al2O3-AQ)
maintained high and stable coulomb efficiency (~100%) even up to the
2000th cycle. The reversible capacity of NVP|FSI–Al2O3-AQ||Na at
various rates (0.1C, 0.2C, 0.5C, 1.0C, 2.0C, and 5.0C) was 110.0, 103.7,
100.6, 95.2, 91.5, and 76.8 mAh g1, respectively, while the other two
control SPEs exhibited poor performance. The Al2O3 suspension in
different solutions is centrifuged and washed six times with the corre-
sponding solvent to filter out the soluble salt, and then dried. TEM images
of the resulting powder (Fig. 5(e)) provided visual evidence that the
Al2O3 powder did react with NaFSI aqueous solution according to the
obvious morphological changes of Al2O3 in FSI-AQ. Completely trans-
formed from the original nanorods >20 nm in length (Al2O3– P) to
nanoparticles less than 10 nm. The crystal plane spacing of the outer
layer of the particle is about 0.2027 nm (Fig. 5(f)). The XPS spectrum of
Al2O3–FSI-AQ is shown in Fig. 5(g), and the fitted Al2p spectrum shows
two peaks associated with Al–O (73.8 eV) and Al– F(75 eV). Sun et al.
[96] studied the interface characteristics of carbon anode in sodium ion
battery (nib) when it was in contact with super concentrated sodium
(fluoromethane) sulfonimide (NaFSI)/N-methyl-n-propyl pyridinium
(fluoromethane) sulfonimide (C3mpyrFSI). In order to more fundamen-
tally understand the effect of the SEI layer on the interfacial dynamics,
temperature dependent EIS measurements were performed to reveal the

Fig. 5. Electrochemical performance of the cells NVP|SPEs|Na with FSI - Al2O3- AQ, FSI - Al2O3- AN, or TFSI-Al2O3-AQ as he electrolyte at 80  C. (a) First charge and
discharge curves at the 0.1C rate. (b) Coulombic efficiencies at the 1C rate. (c) Typical charge and discharge curves at the 1C rate. (d) Rate performance from 0.1C to
5C. (e) Optical photographs and TEM images of the Al2O3 particles filtrated out from NaFSI aqueous solution (Al2O3–FSI-AQ), NaFSI acetonitrile solution (Al2O3–FSI-
AN), and NaTFSI aqueous solution (Al2O3-TFSI-AQ) after stirring at 55  C for 12 h followed by washing six times [95]. (f) High resolution TEM image of Al2O3–FSI-AQ
[95]. (g) XPS spectra of Al2p and F1s of the Al2O3–FSI-AQ [95].(h) Comparison of new sodium salt NaCF3SO3 and NaClO4 at the Na2Ti3O7/electrolyte interface layer.
(i)Schematic illustration of Na solvation and diffusion across the SEI layer and CMK bulk material, respectively [96]. -

9
Zhao et al.
Naþ diffusion dynamics. The weak binding energy associated with the
high coordination number 5 in the 50 mol% NaFSI system can promote
the Na ion jumping process, resulting in high Naþ mobility, and also
facilitate the desolvation ability, as shown in Fig. 5(i). A long cycle life of
the cell, up to 3500 cycles with 320 mAh g1, is achieved, which is
contributed by the anion-derived inorganic solid electrolyte interphase
(SEI) layer on the anode [97].
4. Conclusion
Over the past few decades, substantial strides have been taken in
lithium-ion and sodium-ion battery research, leading to their growing
market share in the energy storage sector. However, the development
and enhancement of sodium-ion battery electrolyte systems have pre-
dominantly centered on two sodium salt systems, NaClO4 and NaPF6,
with other sodium salts primarily serving as additives to improve elec-
trolyte performance. To achieve superior cycling performance in sodium-
ion battery (SIB) systems, further comprehensive investigations are
warranted in the following areas: 1) The application of theoretical cal-
culations, in-situ spectroscopy, and similar techniques to delve deeper
into the solvation structure of electrolyte systems and the compatibility
of the electrode/electrolyte interface; 2) The creation of novel, highly
stable sodium salts and electrolyte additives to expand the electro-
chemical stability window of the electrolyte, mitigate excessive electro-
lyte decomposition, and adapt to high-voltage cathode materials, thereby
further boosting the energy density of sodium-ion battery systems; 3)
Streamlining the synthesis methods for sodium salts to reduce production
costs of NaPF6, NaClO4, NaTFSI, NaFSI, and others, ultimately enhancing
the cost-effectiveness of sodium-ion batteries. Addressing these chal-
lenges will propel sodium-ion battery technology forward and enhance
its competitiveness within the energy storage landscape.
Declaration of competing interest
The authors declare no competing financial interest.
Data availability
Data will be made available on request.
Acknowledgments
This work was financially supported by Shandong Provincial Natural
Science Foundation (Grant No. ZR202011050003)
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