RESEARCH ARTICLE

www.afm-journal.de

A Quasi-Solid-State Polyether Electrolyte for

Low-Temperature Sodium Metal Batteries
Tong Zhao, Xueying Zheng, Donghai Wang, Liqiang Huang, Bin Li, Xuyang Liu,
Hao Yang, Yiming Dai, Yunhui Huang, and Wei Luo*

1. Introduction
Taken the unlimited Na reservoir worldwide, battery technology based on
Na-ion chemistry poses as an ideal candidate for large-scale energy storage In the past decades, lithium-ion batter-
systems. Especially, with metallic Na replacing traditional carbon anodes, it’s ies have revolutionized the development of
portable electronics and electric vehicles.[1]
able to maximize the energy density inexpensively. Nevertheless, sodium
With urgent demand for large-scale en-
metal batteries (SMBs) face intrinsically poor stability due to their ergy storage systems, developing next-
highly-reactive nature, where low Coulombic efficiency and short lifetime are generation battery systems with geograph-
often witnessed. The situation can be further aggravated at low temperatures ical abundancy has become a research
due to insurmountable kinetic barriers. Herein, a 1,3-dioxolane-based hotspot.[2] Sodium metal possesses mul-
quasi-solid-state electrolyte (PDGE) is proposed with a high ionic conductivity tiple advantages as an anode for next-
generation batteries, including high spe-
of 3.68 mS cm−1 even at −20 ◦ C for SMBs. Moreover, a weak solvation
cific capacity (1165 mA h g−1 ), low re-
environment is tailored by PDGE, which possesses a high Na+ transference dox potential (−2.71 V vs SHE), and
number of 0.7. Concurrently, the solid electrolyte interphase induced from low cost.[3] However, sodium metal an-
PDGE presents inorganic Na2 O, NaF as the major components, which offers odes (SMAs) also come with a series of
accelerated Na+ diffusion and superior stability upon long-term cycling. With challenges. For example, severe side reac-
tions between SMAs and electrolytes usu-
such a quasi-solid-state electrolyte, the Na/Na3 V2 (PO4 )3 full cell exhibits great
ally result in low Coulombic efficiency (CE)
stability over 1000 cycles at −20 ◦ C. This study has significant implications to and terrible capacity decay. Sodium den-
the development for SMBs under low-temperature conditions. drites accumulation during electrochem-
ical stripping/plating can readily punc-
ture the separator, inducing short circuit
of the battery. Various liquid electrolyte
recipes have been reported to stabilize
SMAs recently. Among carbonate-based
electrolytes, a high-fluorinated electrolyte is used to improve the
T. Zhao, X. Zheng, D. Wang, L. Huang, X. Liu, H. Yang, Y. Dai, W. Luo
average CE to 95% over 100 cycles.[4] Ether-based electrolytes
Institute of New Energy for Vehicles
School of Materials Science and Engineering make Na anodes highly reversible deposition, however, continu-
Tongji University ous decomposition under high-voltage (>4 V) occurs.[5] Together
Shanghai 201804, China with leakage, flammability, and volatilization risks, liquid-based
E-mail: weiluo@tongji.edu.cn SMBs for practical applications have been sluggish.
B. Li Different from liquid electrolytes, solid-state electrolytes
School of Materials Science and Engineering
Tongji University (SSEs) exhibit many advantages in terms of mechanical strength,
Shanghai 201804, China thermal stability, and safety.[6] Specially, polymer-based SSEs not
Y. Huang only guarantee a maximum cell energy density with their low
State Key Laboratory of Materials Processing and Die and density (∼1.21 g cm−3 for PEO), but can also be massively pre-
Mould Technology pared into thin films for flexible electronic devices. However,
School of Materials Science and Engineering
polymer-based SSEs typically exhibit low ionic conductivity at
Huazhong University of Science and Technology
Wuhan, Hubei 430074, China room temperature that tremendously hinders battery operation.
W. Luo In general, an ideal polymer SSE for SMBs should be equipped
Institute of Carbon Neutrality with the following properties: 1) A high ionic conductivity in a
Tongji University wide temperature range; 2) ability to passivate sodium metal an-
Shanghai 201804, China ode; 3) tight contact with cathodes; 4) low cost and suitable for
traditional preparation process.[7] Actually, all-solid-state batter-
The ORCID identification number(s) for the author(s) of this article ies exhibit several insurmountable obstacles toward practical ap-
can be found under https://doi.org/10.1002/adfm.202304928 plications. Taking the above four views into consideration, gel
DOI: 10.1002/adfm.202304928 electrolytes pose a good-matched choice via in situ or ex situ

Adv. Funct. Mater. 2023, 33, 2304928 2304928 (1 of 8) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
Figure 1. Schematic diagram of PDGE with weakly solvated structure and
in situ formed thin SEI with inorganic components.
synthesis approaches. The progress of ex situ preparation refers
that prefabricated polymer films are transformed into gel elec-
trolytes by swelling themselves in liquid electrolytes.[8] This
method is more complicated, and high interfacial resistance
would further arise from the poor solid-solid contact between
electrodes and electrolytes.[9] Overcoming the issues of ex situ
preparation, in situ gel electrolytes (IGPEs) are state-of-the-
art obviously. Consisting of liquid plasticizers, polymerizable
monomers, and initiators,[10] the IGPE is formatted via the poly-
merization reaction that happens inside the cell. It is worth men-
tioning that 1,3-dioxolane (DOL) monomer has been used in
many lab-scale applications for lithium metal batteries, which
demonstrates its superiority of high ionic conductivity, mild re-
action conditions, mechanical strength, and compatibility with
the highly reactive lithium metal. The breakthrough has been ful-
filled by Guo et al. using in situ polymerization method. With the
poly-DOL-based IGPE, the practical 10 Ah pouch cell achieves a
high energy density of over 450 W h kg−1 .[11]
In this work, a 1,3-dioxolane-based quasi-solid-state elec-
trolyte (PDGE) is in situ prepared in SMBs, where the
tris(pentafluorophenyl)borane (TPFPB) is chosen as an in-built
trigger for DOL polymerization. Specifically, the boron atom
from TPFPB attacks DOL, then DOL monomers are transformed
to polymer frameworks by the ring-opening reaction. Further,
due to the higher lowest unoccupied molecular orbital (LUMO)
of diglyme (G2), it is introduced as the plasticizer to increase the
ionic conductivity. As such, a gel electrolyte is formulated consist-
ing of 0.5 M NaPF6 in poly-DOL/G2, where the ionic conductiv-
ity reaches as high as 3.68 mS cm−1 at low temperature (−20 ◦ C).
Additionally, poly-DOL chains are soaked in G2 to form a local
high concentration of Na+ , which make Na ions de-solvation get
tremendously accelerated. Furthermore, with inorganic Na2 O,
NaF as major solid electrolyte interphase (SEI) components, the
thin SEI between PGDE and SMAs restrains side reactions and
speeds up Na+ interfacial migration (Figure 1). Resultantly, the
Na/Na3 V2 (PO4 )3 (NVP) cell presented near 99% capacity reten-
tion at −20 ◦ C (1000 cycles with 3 C), which was even better than
the regular liquid electrolyte. These results demonstrate that an
impressive low-temperature performance has been achieved for
SMBs with the poly-DOL-based quasi-solid-state electrolyte.
Adv. Funct. Mater. 2023, 33, 2304928 2304928 (2 of 8)
16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.afm-journal.de
2. Results and Discussion
2.1. In situ Polymerization
The detailed preparation process of PDGE involves two steps: (i)
dissolving NaPF6 into DOL/G2; (ii) adding TPFPB to the solu-
tion, where DOL can be initiated by TPFPB to accomplish the
ring-opening polymerization. As shown in Figure 2a, the solu-
tion located on the left side is well-fluidic, whereas after curing
PDGE on the right has no mobility in the state of being inverted.
The in situ polymerization progress is displayed in Figure 2b.
Since TPFPB is a Lewis acid, the boron atom attacks the lone
pair electron of oxygen in DOL. The locations are used as ac-
tive reaction sites to open C–O bonds of DOL monomers and
complete polymer chains growth immediately. The polymeriza-
tion mechanism is verified by the nuclear magnetic resonance
(NMR) results, as shown in Figure 2c,d. The two carbon peaks
of DOL are at 64.3 and 94.8 ppm, which are from -O-CH2 -CH2 -
and -O-CH2 -O-, respectively.[12] After gelation, the two new peaks
signals occur in 66.8 and 95.5 ppm, which are the C signals of
-CH2 -O-CH2 -CH2 -O- reduplicative units of PDGE. Meanwhile,
for the reason that DOL monomers were consumed, the car-
bon peaks of DOL become weaker. The two hydrogen peaks of
DOL locate at 3.86 and 4.87 ppm.[13] After the polymerization
reaction, the two new peaks are found in 3.73 and 4.76 ppm,
which belong to PDGE. The trend of the hydrogen peaks is con-
sistent with the carbon peaks. According to the Fourier trans-
form infrared spectroscopy (FTIR) information (Figure S1, Sup-
porting Information), these components undergo a conversion
as the molecular structure evolves. The feature peaks at 1083
and 915 cm−1 represent C-O-C and C-H out-of-plane peaks, re-
spectively. After gelation, chemical bonds breaking results in the
weaker peaks of DOL monomers. At the same time, new peaks
emerged at 987 and 846 cm−1 , as attributed to the vibration of
C–B and long chains, and their occurrence clearly confirms the
formation of poly-DOL.[14] The samples were further character-
ized by X-ray diffraction (XRD). PDGE shows no new crystalliza-
tion peaks, which is typically amorphous without salt precipita-
tion (Figure 2e). Next, we adopted gel permeation chromatogra-
phy to scale molecular weights of PDGE (Table S1, Supporting
Information). Specifically, the average molecular weight reaches
≈11 500, which suggests that PDGE is formed by the polymer
skeleton wrapping the plasticizer around. In situ generation of
long chains enhances thermal stability of PDGE (Figure S2, Sup-
porting Information). The weight loss of the 0.5 M NaPF6 in G2
(LGE) electrolyte is 50 wt% at 125.8 ◦ C due to abundant volatiliza-
tion of G2 and thermo-degradation of NaPF6 , whilst the equiva-
lent weight loss of PDGE is positioned at 167.4 ◦ C, indicating
strong thermal decomposition is delayed by ≈40 ◦ C.[15] The great
wettability between precursor liquid of PDGE and NVP indicates
that the quasi-solid electrolyte can fill in holes of the electrode
(Figure S3, Supporting Information).
2.2. Electrochemical Characterizations of PDGE
The ionic conductivity of PDGE was gained from electrochemical
impedance spectroscopy (EIS) measurements. It should be noted
that the value is as high as 3.68 mS cm−1 at −20 ◦ C (Figure 3a).
The reason is not only attributed to the addition of liquid
© 2023 Wiley-VCH GmbH
 16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.afm-journal.de

Figure 2. In situ polymerization reaction and characterizations of PDGE. a) Digital photographs of PDGE (i) before and (ii) after polymerization.
b) Schematic diagram of the in situ polymerization process. c) Carbon and d) hydrogen NMR spectra of DOL, LGE, PDGE, respectively. e) XRD patterns
of PDGE and NaPF6 .

Figure 3. a) Nyquist plots of PDGE from −40 to 40 ◦ C with blocking electrodes. b) Ionic conductivity and calculated by fitting activation energy of PDGE.
c) Chronoamperometry curve of Na/Na cell under a polarization voltage of 10 mV. Inset shows Nyquist plots of the symmetric cell with PDGE before
and after polarization. d) Tafel curves of symmetric cells with PDGE and LCE.

Adv. Funct. Mater. 2023, 33, 2304928 2304928 (3 of 8) © 2023 Wiley-VCH GmbH
 16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.afm-journal.de

Figure 4. Nyquist plots of the Na/Na symmetric cells after five formation cycles with a) PDGE and b) LCE at temperatures from −40 to 20 ◦ C. Activation
energies of d) RCT and e) RSEI with different battery systems by fitting impedance spectroscopy. Voltage profiles of the symmetric cells with (c) LCE and
f) PDGE at different rates from 0.2 to 3 mA cm−2 under the conditions of −20 ◦ C and 0.5 mA h cm−2 .

plasticizers that promotes ions transport and polymer frag-
ments motion, but also comes from the Na-O coordinate en-
vironment of poly-DOL chains, which is more favorable under
cold conditions.[16] More importantly, as depicted in Figure 3b,
the value of activation energy calculated from the Arrhenius
formula[17] is only 0.067 eV. It means facile migration of sodium
ions, which is advantageous to operate SMBs in a wide temper-
ature range. Unique from low Na+ transference number (tNa+ )
of routine liquid electrolytes, the tNa+ of PDGE reaches up to 0.7
(Figure 3c). Such a high number facilitates reduction of concen-
tration polarization,[18] which will be verified in the subsequent
charge/discharge process. To measure the kinetics of sodium ion
plating/stripping on electrode surfaces, we collected Tafel plots
using symmetric Na/Na cells. As seen in Figure 3d, the exchange
current density is 3.197 mA cm−2 while the cells have access to
PDGE, a substantial increase versus 0.016 mA cm−2 of the cells
using the 1 M NaPF6 in EC/PC (LCE) electrolyte. The higher an
exchange current density, the lower overpotentials for Na+ nucle-
ation during electrodeposition process.[19]
2.3. Electrochemical Impedance Spectroscopy Analysis of
Symmetric Cells
To explore the mechanism behind the superiority of PDGE at low
temperature, we used a temperature-dependence EIS method to
compare PDGE with LCE-based symmetric cells. Obviously, the
symmetric cells with PDGE show lower impedance values from
20 to −40 ◦ C after five formation cycles. The cell using LCE has
a large impedance of 2400 Ω cm2 at −20 ◦ C. Surprisingly, the
cell resistance plunges to 17 Ω cm2 with substitution of PDGE
(Figure 4a,b). The EIS curves can be deconstructed depending
on the equivalent circuit model (Figure S4, Supporting Informa-
tion). The Ea1 value of cells employing LCE reaches as high as
64.38 kJ mol−1 . This implies a large energy barrier during de-
solvation process, as attributed to Na+ strong binding with sol-
vent molecules. After replacing with PDGE, the Ea1 value brings
a sharp decrease to 11.47 kJ mol−1 (Figure 4d), which is evi-
dence of a significant change in the electrolyte solvation envi-
ronment. The details are discussed in Raman results later. Simi-
larly, with the substitution of PDGE for LCE, the Ea2 value also
declines from 23.58 to 14.50 kJ mol−1 . The poor conductor of
sodium ions caused by LCE took shape, whereas the superior
SEI layer induced by PDGE accelerated Na+ diffusion at the in-
terface (Figure 4e). The reason is that higher LUMO coordinat-
ing ether-based solvents with sodium leads to greater reduction
stability.[20] Symmetric cells with PDGE were also used to esti-
mate rate and cyclic performances at low temperatures. As seen
in Figure 4c, the cell using LCE shows high overpotential for
Na+ plating/stripping. When the current density elevates to 3 mA
cm−2 , the overpotential reaches above 5 V. By replacing the elec-
trolyte with PDGE, the overpotential only arrives ≈6 and 115 mV
at 0.2 and 3 mA cm−2 , showing the tiny and controlled voltage
fluctuation at all rates (Figure 4f). With setting the current density
back to 0.5 mA cm−2 , the overpotential is continuously steady at
≈12 mV and the cycle life lasts over 1500 h at −20 ◦ C with a capac-
ity of 0.5 mA h cm−2 (Figure S5, Supporting Information). In con-
trast, the cell using LCE fails within 170 h (Figure S6, Supporting
Information).
2.4. Comparison of Solvation Environment
For investigating Na+ solvation environment in different elec-
trolyte systems, Raman spectra of LCE, NaPF6 , G2, LGE, PDGE
are displayed in Figure 5a with magnified areas in Figure 5b.

Adv. Funct. Mater. 2023, 33, 2304928 2304928 (4 of 8) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
Figure 5. a,b) Raman spectra of LCE, NaPF6 , G2, LGE, and PDGE. c) Schematic of the solvation environment in LCE and PDGE electrolyte
systems.
First, the peak at 717.8 cm−1 is associated with a large amount
of free PF6− in LCE, which disappeared in LGE and PDGE. In-
stead, the peak of solvated PF6− is observed at 742.1 cm−1 in LGE,
which indicates that increased PF6− took part in the solvation en-
vironment. Low dielectric constant of the ether solvent dominates
the formation of a special solvation environment with anions.[21]
With further introducing of DOL and in situ polymerization, the
solvated PF6− peak shifts to higher wavenumber (745.1 cm−1 ). We
speculated that polymer segments in PDGE make PF6− anions be
more spatially limited. This leads to a high local concentration of
NaPF6 , which has been demonstrated to insure rapid ionic trans-
port (Figure 5b(i)).[22] Secondly, we looked into the stretching vi-
bration of C—O–C functional group in G2 (Figure 5b(ii)). Com-
pared with pure G2 molecules (850.7 cm−1 ), deviation values of
the C—O–C peak in LGE and PDGE systems are ≈−3.0 and −6.0
cm−1 , respectively. It can be concluded that G2 molecules coordi-
nate with NaPF6 and poly-DOL synchronously. At last, the rock-
ing vibration of R-CH2 -R functional group also can verify above
analysis (Figure 5b(iii)), where the corresponding peak was de-
tected at 1453.5 cm−1 in pure G2 and LGE. The peak undergoes a
shift to a higher wavenumber by ≈22.5 cm−1 in PDGE, because R-
CH2 -R bend mode of poly-DOL was formed.[23] Based on these re-
sults, a unique solvation environment is realized in PDGE, where
more PF6− are limit to provide a local high concentration of Na+ .
In addition, poly-DOL segments by in situ generated participate
in the solvation environment to weaken the interaction between
Na+ and ether oxygen lone pairs.[22] The schematic is shown in
Figure 5c, different from the strong interaction between EC/PC
and Na+ , the solvation environment in PDGE can speed up Na+
de-solvation process.
2.5. Study on Deposition Morphologies and Interfacial
Components of the Cycled Na Electrodes
To further explain the improved interface kinetics of sodium plat-
ing/stripping process using PDGE, we used scanning electron
microscope (SEM) to observe deposition morphologies of cycled
Na electrodes at low temperatures. As shown in Figure 6a, the
Adv. Funct. Mater. 2023, 33, 2304928 2304928 (5 of 8)
16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.afm-journal.de
Na electrode surface appeared numerous cracks and holes when
the cell was cycled using LCE. By substituting with PDGE, a uni-
form and dense deposition was observed. The microstructure is
flatter and smoother, without most cracks and holes, showing
higher compatibility with sodium metal (Figure 6b). From optical
photos of the disassembled cells (Figure S7, Supporting Informa-
tion), Na surface is covered with a loose and black material, which
demonstrates severe side effects happened between LCE and Na
anode. The separator is ubiquitously studded with dead Na, evi-
dencing heterogeneous distribution of Na ion fluxes as a result of
by-products both LCE and Na anode. By contrast, the clean sepa-
rator and flat Na surface recycled from PDGE-based cells suggest
minimal side effects.
Next, we analyzed the cycled Na electrodes in detail by way of
X-ray photoelectron spectroscopy (XPS) depth-profile. As shown
in Figure 6c, high peak intensities of C–C, C–O, C═O, and O═C–
O kinds are detected on Na electrodes retrieved from LCE with-
out Ar+ ions sputtering, which manifested accumulation of side
reaction products between solvents and Na.[24] These organic car-
bon peaks are still strong even after 138 s of Ar+ ions sputtering.
The O═C–O and C–O peaks are also seen in the O 1s spectra.[25]
However, these organic components exist in the Na/electrolyte
interface and cannot form an effective passivation layer. Simi-
larly, the P-F[26] signal is in F 1s spectra, and peaks of P-P, [27]
P-O[28] in P 2p spectra indicate that the NaPF6 -induced decom-
position reaction persists. With PDGE electrolyte, in sharp con-
trast, intensities of the carbon-containing peaks are significantly
reduced. One major component in SEI is Na2 O at ≈530.5 eV in-
stead of carbon-containing organics, and the other major inor-
ganic component is NaF. It is found that phosphorus-containing
side-products apparently decrease. Hence PDGE promotes the
formation of Na2 O and NaF in the SEI, and these inorganic com-
ponents inhibit the continuous consumption of PDGE. This de-
sign reduces the production of undesirable substances in SEI and
provides faster channels for Na ions transport (Figure 6d). Inter-
estingly, both cycled electrodes show the high peak intensity of
Na KLL Auger, presuming that the side reactions rate between
Na electrodes and electrolytes is weak at low temperature and the
formed SEI is a little thin.
© 2023 Wiley-VCH GmbH
 16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.afm-journal.de

Figure 6. Top-view SEM images of Na electrodes from cells with a) LCE and b) PDGE after five cycles with 0.1 mA cm−2 , 0.5 mA h cm−2 at −20 ◦ C.
In-depth C 1s, O 1s, F 1s, and P 2p XPS spectra of cycled Na electrodes in c) LCE and (d) PDGE electrolytes at −20 ◦ C.

2.6. Electrochemical Performance of the Na/NVP Cell at Low
Temperatures
Based on the PDGE-tailored solvation environment and facili-
tated interfacial transport kinetics, we assembled Na/NVP cells
with PDGE to validate the long-term stability. Figure 7a first dis-
plays that the cell using LCE has a lower initial discharge ca-
pacity (63.2 mA h g−1 ) at −20 ◦ C and suffers an extensive decay
with a capacity retention of 62.8% at a charge/discharge rate of
3 C. In contrast, with PDGE, the first-cycle discharge capacity and

Adv. Funct. Mater. 2023, 33, 2304928 2304928 (6 of 8) © 2023 Wiley-VCH GmbH
 16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.afm-journal.de

Figure 7. Electrochemical performances of Na/NVP cells with different electrolytes. a) Long-term cyclability of cells with PDGE and LCE at 3 C and
−20 ◦ C. b,c) Temperature-dependent performance of cells with PDGE and LCE ranging from 25 to −40 ◦ C at 1 C and corresponding voltage profiles
of the cell with PDGE. d,e) Rate performance of cells with PDGE and LCE from 1 to 10 C at −20 ◦ C and corresponding voltage profiles of the cell with
PDGE.

capacity retention can give rise to 68.8 mA h g−1 and 99% after
1000 cycles, which proves the compatibility between PDGE with
NVP electrodes at low temperatures. The temperature-dependent
performances of Na/NVP cells with different electrolytes were
further measured from −40 to 25 ◦ C. The discharge capacities
show a slight difference when the temperature stays above 0 ◦ C.
After the temperature goes down to −10, −20, and −30 ◦ C, ca-
pacities of the cells with LCE are 90.9, 77.9, and 59.2 mA h g−1 ,
respectively. Given the high melting points of EC/PC solvents,
the frozen state in the bulk electrolyte dramatically hinders Na+
ions transport, where the capacity has approached zero at −40 ◦ C.
Instead, with PDGE, the cell can still deliver capacities as high as
94.1, 83.3, and 66.8 mA h g−1 at −10, −20, and −30 ◦ C, respec-
tively (Figure 7b). Even if the temperature is as low as −40 ◦ C, the
discharge capacity still reaches 53.9 mA h g−1 . The polarization
voltage of the full cell reduces from 308 to 146 mV using PDGE
instead of LCE at −20 ◦ C, which laterally confirms the strong ion
transport ability of PDGE (Figure 7c and Figure S8, Supporting
Information). The rate capability of the Na/NVP cells was tested
from 1 to 10 C at −20 ◦ C. As shown in Figure 7d, the cells with
LCE have discharge capacities of 80.3, 69.0, 59.5, and 44.4 mA
h g−1 at 1, 2, 3, and 5 C, respectively. Exchanging to PDGE, the
corresponding values increase to 82.5, 73.0, 66.2, and 56.2 mA h
g−1 (Figure 7e and Figure S9, Supporting Information). The sta-
ble and high CE reveals that PDGE has the excellent ability of fast
charge/discharge.
3. Conclusion
In summary, a quasi-solid-state polymer electrolyte named PDGE
was prepared, which is suitable for SMBs at low temperatures.
PDGE is formed by the ring-opening polymerization of DOL
monomers adding few TPFPB as the initiator. The ionic conduc-
tivity and activation energy value of PDGE reach 3.68 mS cm−1
(at −20 ◦ C) and 0.067 eV, respectively. The weak solvation en-
vironment of PDGE makes decoupling behaviors happen more
easily. One reason is that ether solvents have low dielectric con-
stants and the other is that polymer segments existing in G2 also

Adv. Funct. Mater. 2023, 33, 2304928 2304928 (7 of 8) © 2023 Wiley-VCH GmbH

www.advancedsciencenews.com
promote a local high concentration of Na ions. Furthermore,
PDGE induces the thin SEI with Na2 O and NaF as major com-
ponents, which offers faster channels of Na+ through SEI. Due
to rapid de-solvation process and interfacial transport of Na+ , the
Na/NVP cell has a high-capacity retention of 99% over 1000 cy-
cles at −20 ◦ C. The superior performance of PDGE is worthwhile
for SMBs to expand more possibilities in various polymer elec-
trolytes.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
T.Z, X.Z., and D.W. contributed equally to this work. This work was sup-
ported by the National Natural Science Foundation of China (21975186)
and the Institute of Carbon Neutrality of Tongji University.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the cor-
responding author upon reasonable request.
Keywords
batteries, low temperature, polyether electrolyte, quasi-solid-state, sodium
metal
Received: May 4, 2023
Revised: July 2, 2023
Published online: July 19, 2023
[1] a) M. Li, J. Lu, Z. Chen, K. Amine, Adv. Mater. 2018, 30, 1800561; b)
Q. Zhao, S. Stalin, C.-Z. Zhao, L. A. Archer, Nat. Rev. Mater. 2020, 5,
229; c) B. Dunn, H. Kamath, J. M. Tarascon, Science 2011, 334, 928.
[2] a) S. Wang, Y. Jiang, X. Hu, Adv. Mater. 2022, 34, 2200945; b) D. Lin,
Y. Liu, Y. Cui, Nat. Nanotechnol. 2017, 12, 194.
[3] a) J. Zhang, Q. Li, Y. Zeng, Z. Tang, D. Sun, D. Huang, Y. Tang, H.
Wang, ACS Energy Lett. 2023, 8, 1752; b) C. Hu, J. Qi, Y. Zhang, S.
Xie, B. Liu, G. Xue, D. Chen, Q. Zheng, P. Li, S. H. Bo, Y. Shen, L.
Chen, Nano Lett. 2021, 21, 10354.
[4] X. Zheng, Z. Gu, X. Liu, Z. Wang, J. Wen, X. Wu, W. Luo, Y. Huang,
Energy Environ. Sci. 2020, 13, 1788.
[5] X. Ren, L. Zou, S. Jiao, D. Mei, M. H. Engelhard, Q. Li, H. Lee, C. Niu,
B. D. Adams, C. Wang, J. Liu, J.-G. Zhang, W. Xu, ACS Energy Lett.
2019, 4, 896.
Adv. Funct. Mater. 2023, 33, 2304928 2304928 (8 of 8)
16163028, 2023, 48, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202304928 by National Cheng Kung University, Wiley Online Library on [12/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.afm-journal.de
[6] a) T. Deng, X. Ji, L. Zou, O. Chiekezi, L. Cao, X. Fan, T. R. Adebisi, H.
J. Chang, H. Wang, B. Li, X. Li, C. Wang, D. Reed, J. G. Zhang, V. L.
Sprenkle, C. Wang, X. Lu, Nat. Nanotechnol. 2022, 17, 269; b) H. Fu,
Q. Yin, Y. Huang, H. Sun, Y. Chen, R. Zhang, Q. Yu, L. Gu, J. Duan,
W. Luo, ACS Mater. Lett. 2019, 2, 127.
[7] a) Y. G. Cho, C. Hwang, D. S. Cheong, Y. S. Kim, H. K. Song, Adv.
Mater. 2019, 31, 1804909; b) Z. Yu, H. Wang, X. Kong, W. Huang, Y.
Tsao, D. G. Mackanic, K. Wang, X. Wang, W. Huang, S. Choudhury,
Y. Zheng, C. V. Amanchukwu, S. T. Hung, Y. Ma, E. G. Lomeli, J. Qin,
Y. Cui, Z. Bao, Nat. Energy 2020, 5, 526; c) Z. Li, P. Liu, K. Zhu, Z.
Zhang, Y. Si, Y. Wang, L. Jiao, Energy Fuels 2021, 35, 9063; d) S. J. Tan,
W. P. Wang, Y. F. Tian, S. Xin, Y. G. Guo, Adv. Funct. Mater. 2021, 31,
2105253.
[8] M. Montazer, M. M. Amiri, J. Phys. Chem. B 2014, 118, 1453.
[9] a) N. Mittal, S. Tien, E. Lizundia, M. Niederberger, Small 2022, 18,
e2107183; b) H. Lai, Y. Lu, W. Zha, Y. Hu, Y. Zhang, X. Wu, Z. Wen,
Energy Storage Mater. 2023, 54, 478; c) Z. Lin, X. Guo, Z. Wang, B.
Wang, S. He, L. A. O’Dell, J. Huang, H. Li, H. Yu, L. Chen, Nano Energy
2020, 73, 104786.
[10] V. Vijayakumar, B. Anothumakkool, S. Kurungot, M. Winter, J. R. Nair,
Energy Environ. Sci. 2021, 14, 2708.
[11] Q. Ma, J. Yue, M. Fan, S. J. Tan, J. Zhang, W. P. Wang, Y. Liu, Y. F. Tian,
Q. Xu, Y. X. Yin, Y. You, A. Luo, S. Xin, X. W. Wu, Y. G. Guo, Angew.
Chem., Int. Ed. 2021, 60, 16554.
[12] H. Cheng, J. Zhu, H. Jin, C. Gao, H. Liu, N. Cai, Y. Liu, P. Zhang, M.
Wang, Mater. Today Energy 2021, 20, 100623.
[13] Q. Zhao, X. Liu, S. Stalin, K. Khan, L. A. Archer, Nat. Energy 2019, 4,
365.
[14] a) Q. Liu, B. Cai, S. Li, Q. Yu, F. Lv, F. Kang, Q. Wang, B. Li, J. Mater.
Chem. A 2020, 8, 7197; b) J. Xiang, Y. Zhang, B. Zhang, L. Yuan, X. Liu,
Z. Cheng, Y. Yang, X. Zhang, Z. Li, Y. Shen, J. Jiang, Y. Huang, Energy
Environ. Sci. 2021, 14, 3510.
[15] F. N. Jiang, X. B. Cheng, S. J. Yang, J. Xie, H. Yuan, L. Liu, J. Q. Huang,
Q. Zhang, Adv. Mater. 2023, 35, 2209114.
[16] J. Zhou, H. Ji, Y. Qian, J. Liu, T. Yan, C. Yan, T. Qian, ACS Appl. Mater.
Interfaces 2021, 13, 48810.
[17] X. Zheng, L. Huang, X. Ye, J. Zhang, F. Min, W. Luo, Y. Huang, Chem
2021, 7, 2312.
[18] K. M. Diederichsen, E. J. McShane, B. D. McCloskey, ACS Energy Lett.
2017, 2, 2563.
[19] Z. Tu, S. Choudhury, M. J. Zachman, S. Wei, K. Zhang, L. F.
Kourkoutis, L. A. Archer, Nat. Energy 2018, 3, 310.
[20] a) S. Lu, B. Wang, P. Zhang, X. Jiang, X. Zhao, L. Wang, Z. Yin, J. Wu,
Molecules 2022, 27, 6949; b) Z. W. Seh, J. Sun, Y. Sun, Y. Cui, ACS Cent.
Sci. 2015, 1, 449.
[21] G. Song, Z. Yi, F. Su, L. Xie, Z. Wang, X.-X. Wei, G. Xu, C.-M. Chen,
ACS Energy Lett. 2023, 8, 1336.
[22] X. He, Y. Ni, Y. Hou, Y. Lu, S. Jin, H. Li, Z. Yan, K. Zhang, J. Chen,
Angew. Chem., Int. Ed. 2021, 60, 22672.
[23] K. Qian, S. Seifert, R. E. Winans, T. Li, Energy Fuels 2021, 35, 19849.
[24] N. Vandencasteele, F. Reniers, J Electron Spectros Relat Phenomena
2010, 394, 178
[25] A. K. Friedman, W. Shi, Y. Losovyj, A. R. Siedle, L. A. Baker, J. Elec-
trochem. Soc. 2018, 165, H733.
[26] L. Huang, H. Fu, J. Duan, T. Wang, X. Zheng, Y. Huang, T. Zhao,
Q. Yu, J. Wen, Y. Chen, D. Sun, W. Luo, Y. Huang, Chem 2022, 8,
1928.
[27] D. H. Kwak, H. S. Ra, J. Yang, M. H. Jeong, A. Y. Lee, W. Lee, J. Y.
Hwang, J. H. Lee, J. S. Lee, Small 2018, 14, 201703194.
[28] M. Kalapsazova, R. Stoyanova, E. Zhecheva, G. Tyuliev, D.
Nihtianova, J. Mater. Chem. A 2014, 2, 19383.
© 2023 Wiley-VCH GmbH