Letter

http://pubs.acs.org/journal/aelccp

Ultrafast UV Curing Enabling A Stable

Interphase and Interface for Solid-State
Sodium−Metal Batteries
Fupeng Li, Kun Ren, Minjie Hou, Mingcan Lin, Xiecheng Yang, Yingjie Zhou, Shizhao Xiong,*
and Feng Liang*
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sı Supporting Information

ABSTRACT: Designing advanced solid-state sodium batteries (SSBs)

demands simultaneously overcoming the low ionic conductivity of solid-
state electrolytes (SSEs) and the poor interfacial compatibility between
electrodes and SSEs. Herein, a composite solid-state electrolyte (CSE) with
high ionic conductivity was prepared by using an efficient UV polymerization
in 45 s. A stable interphase and interface were achieved simultaneously
through solvent structure tuning and in situ curing. By introduction of
fluoroethylene carbonate (FEC) to form a competitive solvation structure in
CSE-F, the low lowest unoccupied molecular orbital (LUMO) allowed
preferential reduction of FEC in the solvation shell. A dense and uniform
NaF-rich interphase was constructed to inhibit the growth of the dendrites.
Simultaneously, the integrated cathode and electrolyte constructed a tight-
contact interface, enabling uniform and efficient ion transport. The Na||CSE-F@Na3V2(PO4)3 (NVP) cell showed a capacity
retention of 91.78% after 2100 cycles. This work provides a solution to simultaneously achieve a rational interphase and an
electrode/electrolyte interface design for SSBs.

posed.17−20 Protective interlayers, such as thin polymer or

N a-ion batteries (SIBs) have received widespread

attention for their abundant Na resources and
favorable low-temperature performance.1−4 However,
SIBs with liquid electrolytes have safety concerns of leakage,
combustion, and explosion. To address these issues, introduc-
ceramic coatings, can stabilize the interface, reduce dendrite
growth, and enhance mechanical integrity. Creating a solid-
electrolyte interphase (SEI) helps to form a stable, uniform
layer between the Na and SSE, preventing direct contact and
ing safer solid-state electrolytes (SSEs) for developing solid- reducing dendrite formation. Since the composition of the SEI
state Na batteries (SSBs) is considered as one of the most is closely linked to the solvation structure of the electro-
promising strategies.5−7 Due to the high ionic mobility barriers lyte,21−23 various strategies have been developed, including
within the SSE and the point-to-point contact with the increasing electrolyte concentration,24 designing locally high-
electrodes, the development of SSBs is still limited by low ionic concentration electrolytes,25 and utilizing weakly solvating
conductivity and poor interfacial compatibility.8,9 In recent solvents.26 At the cathode/SSE interface, the main challenges
years, with the substantial advancements in the ionic are poor contact and mechanical stress caused by volume
conductivity of SSEs, the challenges of the electrode/ changes during cycling.27−29 The rigid nature of solid materials
electrolyte interface have emerged as the primary bottleneck hinders efficient ion transport, while volume changes can lead
restricting the development of SSBs.10−12 to cracks, delamination, and interface degradation. To address
The anode/SSE interface faces significant challenges,
these issues, surface modification techniques, such as applying
including primarily dendrite growth and interfacial instability.
Nonuniform deposition of Na+ during cycling usually causes
sodium dendritic growth, which can pierce the solid electro- Received: November 4, 2024
lyte, leading to short circuits and battery failure.13,14 Addition- Revised: December 3, 2024
ally, interfacial instability arises from uneven Na deposition Accepted: December 5, 2024
creating voids and poor contact between the anode and SSE, Published: December 16, 2024
resulting in increased resistance and capacity fading.15,16 To
mitigate these issues, several solutions have been pro-

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Figure 1. Production process and structure of solid-state Na battery. (a) Fabrication of integrated SSBs. (b) In situ polymerization of the
CSE (Process 1 is polymer chain initiation; process 2 is polymer chain growth). (c) Interface design for the integrated solid-state Na metal
battery.

thin, flexible coatings (e.g., polymer or ceramic layers), can without capacity decay at 2C. After the integration of the
improve interfacial contact and minimize resistance.30−32 For cathode with CSE-F, the interfacial resistance of the cell is
example, atomic layer deposition can create ultrathin significantly reduced, and the Na||CSEs-F@NVP cell demon-
protective layers that ensure intimate contact between the strates milestone cycling stability with 91.78% capacity
cathode and electrolyte. Additionally, using elastic or pliable retention after 2100 cycles at 2C. This work provides a
interlayers can absorb the mechanical stress caused by solution to achieve rational interphase and interface design for
expansion and contraction of the cathode, preventing cracks SSBs simultaneously.
and maintaining stability.33,34 It has been demonstrated that The CSEs were prepared by a solvent-free UV curing
with a single target anode or cathode, side interface process, and the photosensitive oligomer poly(ethylene glycol)
modification can be obtained. However, no attempt has been dimethacrylate (PEGDMA) was used as a precursor of the
made to meet the SSB requirements simultaneously due to the polymer backbone. The mixture of PEGDMA, plasticizer
distinctly separate interface challenges on the cathode and succinonitrile (SCN), Na bis(fluorosulfonyl)imide (NaFSI),
anode sides. Thus, we envisage that SSBs with excellent inorganic filler Na3Zr2Si2PO12 (NASICON), and photoinducer
stability could be achieved by simultaneously constructing an 2,2-dimethoxy-2-phenylacetophenone (DMPA) were cast on a
interphase at the anode side to inhibit dendrite growth and glass plate and exposed in light to obtain the CSE. This
interfacial reaction, and an in situ interface at the cathode side preparation process allows a successive production procedure
to enhance material contact and alleviate volume effects. from cathode to full pouch cell (Figure 1a). During the
Herein, organic−inorganic composite solid-state electrolytes photocuring process, the photoinducer is excited by UV to
(CSEs) with high ionic conductivity were prepared by a simple obtain a radical which attacks the −C�C− group of
and efficient UV curing process. Fluorinated ethylene PEGDMA for polymerization (Figure 1b).35 By addition 5
carbonate (FEC) was further introduced in CSEs (CSE-F) wt % FEC to the precursor mixture, the highly polarized C−F
to form a dense and uniform NaF-rich SEI on the Na metal bond modifies the solvated structure of CSE-F and thus creates
anode. Combined with simulations, the roles of the NaF-rich a NaF-rich SEI on the Na−metal surface (Figure 1c).36 The
SEI and formation processes were interpreted. Moreover, the integration of the cathode and electrolyte enables the
CSE-F was cured in situ at the cathode to achieve excellent construction of a close contact interface, while the flexibility
interfacial contact. Benefiting from the SEI and integrated of the electrolyte can alleviate the volumetric strain of the
cathode with electrolyte interface construction, both sym- cathode during cycling, thus realizing the long-term lifespan of
metric and full cells exhibit excellent cycling stability at room SSBs (Figure 1c).
temperature. The Na||Na symmetric cell assembled with the The CSE-F and precursor solutions were characterized by
CSE-F delivers stable cycling for more than 2800 h under a Fourier transform infrared spectroscopy (FTIR) to determine
current density of 0.05 mA cm−2, while the Na||CSE-F|| the completion of the polymerization. As shown in Figure 2a,
Na3V2(PO4)3 (NVP) cell exhibits stable cycling for 500 cycles the −C�C− absorption peak at 1637 cm−1 from CSE-F is
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Figure 2. Structure and properties of CSE-F with different compositions. (a) FTIR spectra of the CSE-F before and after light exposure in the
range of 1590−1750 cm−1. (b) Ionic conductivity of different SCN and NaFSI contents. (c) XRD patterns of NASICON, CSE without
NASICON, CSE, and CSE-F. (d) Ionic conductivity of CSE-F with different NASICON contents. (e) Tensile strength of CSE-F with
different SCN contents. (f) Cross-sectional SEM images of CSE-F. (g) Surface SEM image and EDS mapping of CSE-F.

missing compared with the precursor solution, indicating the DMPA). To balance the mechanical properties and ionic
completed polymerization.37 It is noteworthy that the −C�O conductivity of CSE-F, 40 wt % of SCN was established and
peak was shifted to higher wavenumber after the completed the ionic conductivity of the polymer electrolyte was optimized
polymerization of −C�C− groups, which is due to the according to the content of SCN and NaFSI (Figure 2b, Figure
conjugation effect of the −C�C− and −C�O groups (−C� S2). With an increasing concentration of NaFSI, the Na+
C−C�O) in PEGDMA.38 Excellent mechanical flexibility and concentration in the system rises, and the ionic conductivity of
high ionic conductivity are essential for SSEs. Na+ content and the electrolyte increases. When the ion concentration is
crystallinity are the key parameters affecting the ionic excessive, the interaction between Na+ and anions in the
conductivity of CSEs.39 To investigate the effects of NaFSI system is highly enhanced, and thus the ion transport is
and SCN on the ion transport properties of the electrolyte, a blocked, resulting in a decrease in ionic conductivity.41
rational orthogonal experiment was conducted. As a small It has been reported that the mechanical strength and ionic
molecule, the addition of SCN into electrolytes can affect the conductivity of CSE are increased by adding inorganic fillers.42
cross-linking of polymer segments and reduce the crystallinity. Active fillers provide more ion channels and reduce the
Moreover, it improves the flexibility of polymer electrolytes to crystallinity of polymer, increasing the range of segmental
maintain good interfacial contact with the electrodes. Mean- motion and improving the ionic conductivity of the CSE.43,44
while, the polar −C�N bond in SCN can participate in the As shown in Figure 2c (Figure S3), the superposition of
interaction of Na+, providing more migration paths for Na+.40 diffraction peaks without impurity peaks is generated after the
Consequently, the ionic conductivity of polymer electrolyte coupling of NASICON with a polymer electrolyte, which
increased with higher SCN content (Figure 2b, Figure S1). indicates the stable coexistence of these components. The
The increased content of SCN will also result in reduced typical peak of the polymer electrolyte at 19.68° was weakened
mechanical strength (Figure 2e). The integrity of the after the addition of NASICON, indicating that reduced
electrolyte membrane is hardly maintained when it reaches crystallinity of the CSE. The introduction of FEC leads to a
50 wt % of the polymer electrolyte (PEGDMA-NaFSI- further weakening of the peak intensity of CSE-F, indicating
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Figure 3. Experimental and simulation results of solvated structures in CSE-F. LUMO and HOMO energy level (a) with different substances
and (b) after binding with Na+. (c) Electrostatic potential of components in CSE-F. (d) FITR of CSE and CSE-F. (e) Solid state nuclear
magnetic resonance (SSNR) of CSE and CSE-F. (f) Solvation structure and diagram for SEI formation of CSE and CSE-F.

that FEC reduces the crystallinity of the electrolyte as well. and sulfur, nitrogen, and oxygen indicate the distribution of
Notably, when the NASICON content is too high, fillers NaFSI, SCN, and PEGDMA, respectively.
within the electrolyte can aggregate and impede ion transport. To rationally design the electrolyte, we performed
The highest ionic conductivity of electrolyte was obtained theoretical calculations for different molecules and ion
when the NASICON content was 10 wt % of CSE-F (Figure populations, as shown in Figure 3a−c. The highest occupied
2d, Figure S3). With such a ratio of various components, the molecular orbital (HOMO) and the lowest unoccupied
CSE-F also showed good flexibility, bending 180° without molecular orbital (LUMO) of a molecule represent the
cracking (Figure S4). To observe the morphology of CSE-F, thermodynamic potential energy for oxidation and reduction,
both surface and cross sections were characterized using the respectively. A lower LUMO indicates that the molecule is
readily reduced and forms a SEI on the anode surface, while a
scanning electron microscope (SEM), as depicted in Figure
higher HOMO indicates that the molecule is likely to be
2f,g and Figure S5. The sieving process of NASICON particles
oxidized on the cathode side and form a cathode electrolyte
reduced the agglomeration of powder and enhanced the interphase (CEI).45 As shown in Figure 3a, the calculated
homogeneity of the mixture. The UV-curing method avoids HOMO and LUMO energy levels of FEC, PEGDMA, SCN,
the formation of holes that are easily caused by solvent and FSI− are −8.81/0.11, −7.70/−1.64, −9.56/−0.49, and
volatilization during the solution-casting process, delivering a −3.99/4.01, respectively. Coordination with Na+ leads to a
highly dense structure and a homogeneous surface without simultaneous decrease in the HOMO and LUMO energy
defects. The uniform distribution of components in CSE-F is levels, −13.20/−5.39 eV for Na+−FEC, −10.18/−5.78 eV for
further evidenced by elemental mapping from the energy Na+−PEGDMA, −9.82/−1.12 eV for Na+−SCN, and −8.43/
dispersive spectrometer (EDS) in Figure 2g, where zirconium, −2.22 eV for Na + −FSI − (Figure 3b). Thus, from a
silicon, and phosphorus indicate the distribution of NASICON thermodynamic point of view, FEC preferred to be reduced
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Figure 4. Interface stability and SEI formation on Na metal anode. (a) Electrochemical stability window, (b) activation energy, and (c) ion
mobility of electrolytes. (d) Voltage profile of Na||Na symmetrical cell. (e) Young’s modulus of the SEI on Na metal anode after 100 cycles.
XPS spectra of the surface of (f) CSE and (g) CSE-F surface after 100 cycles with Na metal anode. (h) Full XPS spectra of CSE and CSE-F
before and after 100 cycles. (i) Decomposition pathways of electrolyte components for SEI formation.

at the anode surface to form a F-rich SEI. Figure 3c shows the react preferentially with Na during desolvation to form a F-rich
different electrostatic potentials (ESPs) of the molecules, SEI on the Na metal surface.
indicating the solvation capacities of the various solvents. The FTIR, Raman Spectroscopy (Raman), and Solid State
groups of F and O in FEC, of O in PEGDMA with C�O, and Nuclear Magnetic Resonance (SSNMR) were used to identify
of N in SCN show negative charge densities, indicating that the solvated structure of the CSE-F. As shown in Figure 3d, the
they can coordinate with Na+ in the electrolyte. The binding −C�N bond peak in SCN is shifted from 2284 to 2253 cm−1
energies of Na+ with various solvents are shown in Figure S6 in CSE and 2254 cm−1 in CSE-F, respectively, which resulted
and Table S1. The pairings of Na+−FEC, Na+−PEGDMA, from the coordination of −C�N with Na+.46 The solvation of
Na+−SCN, and Na+−FSI− have binding energies of −1.49, −C�N with Na+ is weakened by the addition of FEC, and the
−1.54, −1.27, and −4.93 eV, respectively. The larger ΔGbinding −C�N peak becomes weaker with a slight red shift in the
indicates a stronger solvating power because of its higher peak position. The same trend is observed for −C�O and
polarity and bidentate nature. Density Functional Theory −C−O in PEGDMA, which are both involved in the solvation
(DFT) theoretical studies have demonstrated that both FEC of Na+. The C�O peak shifts from 1715 to 1724 cm−1 and the
and polymer molecules are coordinate to Na+, and such a −C−O peak shifts from 1167 to 1180 cm−1, and thus the
competing solvation environment effectively weakens the weakening of solvation by FEC leads to the reappearance of
solvation ability and allows more anions to participate in the free −C−O peaks in CSE-F. After the addition of FEC, two
solvation. Additionally, the lower LUMO of FEC enables it to new peaks appear in CSE-F at 1832 and 1806 cm−1, which are
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Figure 5. Electrochemical performance of Na||CSE-F||NVP cells. (a) Cycling performance and (b) voltage profiles of cell at 2C. (c)
Comparison of capacity retention of solid-state Na metal batteries with composite electrolytes reported in previous literature. (d, e) Rate
performance and (f) low-temperature cycling performance of cells.

formed by the coordination of −C�O in FEC with Na+. The electrolyte weakened the Na+−solvent interaction, and FEC-
coordination peak of the −C−F bond with Na+ appears at 730 containing solvation environment appeared in the EDL, when
cm−1, and these results demonstrate that the introduction of close to the Na metal anode; the FEC has a lower LUMO
FEC into CSE-F is successfully involved in the solvated preferentially reducing with the Na to form a NaF-rich SEI.
structure.47 As seen in Figure 3d, the peak of FSI− in the CSE The electrolyte thermal stability is an important parameter
is shifted to 746 cm−1, while the peak in CSE-F is shifted to for evaluating the practical safety of cells, and the thermal
748 cm−1, and the ionic aggregate (AGGs) ligand structure stability of electrolyte was tested by thermogravimetry (Figure
appears at 763 cm−1. It is due to FEC introduction weakening S8). The results indicate that the decomposition temperature
the solvation ability of the PEGDMA and SCN with Na+, of the electrolyte components is up to 119 °C. After the
resulting in more FSI− involved in the solvation formation. introduction of FEC, the decomposition temperature is slightly
The coordination environment of Na+ within the electrolyte reduced to 112 °C, indicating that CSE-F has favorable
shows more CIPs and AGGs therefore. Raman demonstrated thermal stability. Additionally, the prepared CSE-F has an
the same result (Figure S7), which favors the formation of electrochemical window as high as 5.02 V (vs Na/Na+). The
NaF-rich SEI. As shown in Figure 3e, SSNMR revealed a new ion migration is closely related to the activation energy, which
coordination environment for Na+ in CSE-F, which is a is 0.49 and 0.77 eV for CSE and CSE-F, respectively (Figure
competitive solvation structure formed with the participation 4b and Figure S9). The incorporation of FEC modifies the
of FEC. At the same time, the solvation capacity of the solvent interactions between Na+ and the solvent, resulting in ion
with Na+ in CSE-F is reduced, which promotes the dissociation transport within the electrolyte becoming more reliant on
of Na+. Figure 3f shows a schematic diagram of the electric specific intermolecular forces. This modification could
double layer (EDL) composition and the SEI formed on the necessitate overcoming higher energy barriers during ion
Na metal anode surface before and after modification. Due to migration, consequently leading to an increase in activation
the addition of FEC, the competitive solvation within the energy. In addition, the introduction of FEC reduces the
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Figure 6. Electrochemical performance of integrated Na||CSE-F@NVP cells. (a) Cross-section SEM images of integrated electrode−
electrolyte interface. (b) Electrochemical impedance spectra of Na||CSE-F@NVP and Na||CSE-F||NVP. (c) Long-term cycling performance
and (d) voltage profile of Na||CSE-F@NVP cell. (e, f) Rate performance of Na||CSE-F@NVP cell.

crystallinity of the CSE-F and thus both the ionic conductivity metal surface were an organic−inorganic mixture. In CSE-F
and ion transference number of the CSE-F are improved (Figure 4g), however, the dominant component is NaF,49 and
(Figure 4c and Figure S10). The introduction of FEC no SCN decomposition occurred, effectively demonstrating
improves the ionic conductivity of CSE-F and increases the that the formation of NaF-rich SEI enhances the electrolyte
charging and discharging efficiency of the battery. Meanwhile, stability. In the XPS C 1s spectra of the electrolyte surface
a stable NaF-rich SEI is constructed on the anode side to before and after cycling, a decrease in the −C−C− and −C�
inhibit the further reaction of the electrolyte with sodium and O bonds of the organic components was clearly observed.
Na dendrite growth. Consequently, the cell with CSE-F has Among the characteristic peaks of oxygen, the intensity of the
better cycling stability and higher initial capacity compared to −C�O peaks is obviously weakened after cycling, and Na2O
that with CSE (Figure S11). As shown in Figure 4d, the Na|| appeared at 536.5 eV (Figure S15). As seen in Figure 4h, the
CSE-F||Na cell was able to cycle for more than 2800 h under content of organic constituent elements C and O on the CSE-
0.05 mA cm−2 without increased polarization, whereas the Na|| F surface decreased significantly after cycling, while the content
CSE||Na cell showed a short circuit at 480 h. This effectively of F and Na increased. Whereas the F content did not
demonstrates the good dendrite inhibition ability of SEI with significantly shifted before and after cycling on the CSE
solvated structures regulated by addition of FEC. Figure 4e surface, a noticeable N 1s peak intensified (Figure S16). EDS
shows the Young’s modulus of the Na metal surface after elemental mapping exhibited similar results (Figure S17). It
cycling with the CSE-F and CSE. The Young’s modulus of the indicated that the introduction of FEC created a F-rich
Na metal surface after cycling with CSE-F (1.99 GPa) is much environment on the Na metal surface, which promoted the
higher than that with CSE (0.82 GPa). This suggests a dense formation of a NaF-rich SEI and inhibited further reactions of
and uniform SEI generated on the Na metal anode, which SCN and PEGDMA with sodium. A combination of FTIR and
induced the uniform deposition of Na+ during cycling (Figure XPS analysis of the electrolyte surface provided a formation
S12). route for the SEI components, as shown in Figure 4i. The NaF
The XPS results of the Na metal surface after cycling further was derived from the decomposition of FEC and NaFSI, and
confirmed the formation of a NaF-rich SEI (Figure S13). To the decomposition of NaFSI and the solvents (PEGDMA) also
explore the formation process of the SEI, we performed FTIR produced inorganic components such as Na2O and ROCO2−
and XPS measurements on CSE (Figure 4f) and CSE-F Na (Na2CO3). Our results demonstrated that the introduction
(Figure 4g). A broader peak at 1630 cm−1 appeared after of FEC successfully constructed a NaF-rich SEI in situ between
cycling of CSE-F (Figure S14), which is the characteristic peak the electrolyte and Na metal, thus improving the electro-
of −C�C− in VC from the breaking down of the C−F bond chemical performance of SSBs.
in FEC. As shown in Figure 4f, the surface of CSE before and To further verify the practicality of electrolytes and the
after cycling has NaF and −C�N− produced by decom- interphase, Na||CSE-F||NVP full cells were assembled with
position of SCN,48 indicating that the components on the Na CSE-F to evaluate the electrochemical performance under
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practical conditions. As shown in Figure 5a, the Na||CSE-F||

NVP cell exhibits good cycling stability with a capacity up to
■
*
ASSOCIATED CONTENT
sı Supporting Information
89 mAh g−1 at 2C under room temperature. Moreover, there is
The Supporting Information is available free of charge at
almost no capacity loss after 500 cycles and no significant https://pubs.acs.org/doi/10.1021/acsenergylett.4c03043.
change in cell polarization, which is a clear advantage over
previously reported cells with a similar type of electrolyte Calculation and Experimental methods; Impedance
(Figure 5c and Table S2). The cell also shows the enhanced spectroscopy; Digital photographs for CSE-F; SEM
performance at 0.1 and 1C rates (Figures S18 and 19). The and EDS for cross-sectional of CSEs-F; Binding energy;
good rate performance (Figure 5d,e) with capacities of 105.2, Thermogravimetric analysis; Cycle performance; AFM
100, 95, and 86 mAh g−1 at 0.1, 0.5, 1, and 2C is obtained. of sodium metal; XPS spectra of sodium metal; FTIR
When the rate returns to 0.1C, the capacity of the cell returns spectra of CSE-F; Voltage profiles; Table for simulation
to 105 mAh g−1, demonstrating a good reversibility. Benefiting results; Table for electrolyte and cell performance
from the high ionic conductivity of the electrolyte, the Na|| comparison (PDF)
CSE-F||NVP battery also demonstrated good performance
under low temperature, showing a capacity of 92 mAh g−1 at 0
°C and that of 69 mAh g−1 at −20 °C and almost no capacity
loss after 50 cycles (Figure 5f, Figure S20).
■ AUTHOR INFORMATION
Corresponding Authors
To further enhance the solid−solid contact between Shizhao Xiong − Faculty of Materials Science and Engineering,
electrolyte and electrode, the precursor solution of electrolyte Kunming University of Science and Technology, Kunming
was directly cured in situ on the cathode to form an integrated 650093, China; orcid.org/0000-0003-1795-7805;
electrode with the electrolyte by taking advantage of the UV Email: [email protected]
curing process. As shown in Figure 6a, tight contact is Feng Liang − Faculty of Metallurgical and Energy Engineering,
demonstrated between the electrode and the electrolyte. The Kunming University of Science and Technology, Kunming
interfacial resistance of Na||CSE-F@NVP with an integrated 650093, China; National Engineering Research Center of
cathode is significantly lower than that of Na||CSE-F||NVP Vacuum Metallurgy and Key Laboratory for Nonferrous
(Figure 6b). The total resistance with integration is 1732.2 Ω Vacuum Metallurgy of Yunnan Province, Kunming University
of Science and Technology, Kunming 650093, China;
whereas that after integration is 275.1 Ω, which confirms that
orcid.org/0000-0003-4718-652X; Email: liangfeng@
the integration strategy is effective in mitigating the solid−solid
kust.edu.cn
contact for SSBs. In addition, the Na||CSE-F@NVP full cell
has milestone cycling stability and rate performance (Figure Authors
6c,d), delivering a capacity retention of 91.78% after more than Fupeng Li − Faculty of Metallurgical and Energy Engineering,
2100 cycles at 2C and a capacity of 75 mAh g−1 at a high rate Kunming University of Science and Technology, Kunming
of 5C (Figure 6e,f). The flexible CSE-F cured in situ with the 650093, China; National Engineering Research Center of
electrode effectively improves the interfacial contact, and the Vacuum Metallurgy, Kunming University of Science and
good flexibility of the electrolyte mitigates the volumetric strain Technology, Kunming 650093, China
of electrodes during Na+ deposition/exfoliation, thus enhanc- Kun Ren − Faculty of Metallurgical and Energy Engineering,
ing the cycling stability. Kunming University of Science and Technology, Kunming
In summary, we employed a rapid method for the 650093, China; National Engineering Research Center of
preparation of CSEs by UV exposure for 45 s. Its high Vacuum Metallurgy, Kunming University of Science and
efficiency and simplicity enable it to realize continuous Technology, Kunming 650093, China
production from the cathode to pouch cells, which has great Minjie Hou − Faculty of Metallurgical and Energy
potential for the large-scale production of SSBs in the future. Engineering, Kunming University of Science and Technology,
Additionally, an interphase on the Na anode to inhibit dendrite Kunming 650093, China; National Engineering Research
growth and side reaction as well as an in situ interface on the Center of Vacuum Metallurgy, Kunming University of Science
cathode material were constructed simultaneously. By and Technology, Kunming 650093, China
introducing FEC to form a competitive solvation structure in Mingcan Lin − Faculty of Metallurgical and Energy
CSE-F, the low LUMO allows preferential reduction of FEC in Engineering, Kunming University of Science and Technology,
the solvation shell layer. A dense and uniform NaF-rich SEI Kunming 650093, China; National Engineering Research
was constructed in situ during cell operation to inhibit the Center of Vacuum Metallurgy, Kunming University of Science
growth of the dendrites. In conjunction with simulations, the and Technology, Kunming 650093, China
role and formation process of the NaF-rich SEI were Xiecheng Yang − Faculty of Metallurgical and Energy
elaborated. Simultaneously, the integrated cathode/electrolyte Engineering, Kunming University of Science and Technology,
constructed a tight-contact interface, enabling uniform and Kunming 650093, China; National Engineering Research
efficient ion transport through the interface that significantly Center of Vacuum Metallurgy, Kunming University of Science
reduced the interfacial impedance. The high ionic conductivity, and Technology, Kunming 650093, China
good flexibility, and enhanced interfacial compatibility of the Yingjie Zhou − Faculty of Metallurgical and Energy
electrolyte were synchronously achieved by designing the Engineering, Kunming University of Science and Technology,
composition. The Na||CSE@NVP cell showed capacity Kunming 650093, China; National Engineering Research
retention of 91.78% after 2100 cycles, which is a significant Center of Vacuum Metallurgy, Kunming University of Science
advantage over previously reported cells with CSE. This work and Technology, Kunming 650093, China
also provides a new idea for efficient electrolyte preparation Complete contact information is available at:
and interfacial compatibility in future fabrication of SSBs. https://pubs.acs.org/10.1021/acsenergylett.4c03043
202 https://doi.org/10.1021/acsenergylett.4c03043
ACS Energy Lett. 2025, 10, 195−204
ACS Energy Letters http://pubs.acs.org/journal/aelccp Letter

Notes (15) Bao, C.; Wang, B.; Liu, P.; Wu, H.; Zhou, Y.; Wang, D.; Liu, H.;
The authors declare no competing financial interest. Dou, S. Solid Electrolyte Interphases on Sodium Metal Anodes.
Adv.Funct. Mater. 2020, 30 (52), 2004891.
■ ACKNOWLEDGMENTS
The work was financially supported by the National Natural
(16) Zou, P.; Wang, C.; He, Y.; Xin, H. L. Making Plasticized
Polymer Electrolytes Stable Against Sodium Metal for High-Energy
Solid-State Sodium Batteries. Angew. Chem., Int. Ed. 2024, 63 (14),
Science Foundation of China (12175089, 12205127), the Key No. e202319427.
Research and Development Program of Yunnan Province (17) Lv, R.; Kou, W.; Guo, S.; Wu, W.; Zhang, Y.; Wang, Y.; Wang,
(202103AF140006), the Applied Basic Research Programs of J. Preparing Two-Dimensional Ordered Li0.33La0.557TiO3 Crystal in
Yunnan Provincial Science and Technology Department Interlayer Channel of Thin Laminar Inorganic Solid-State Electrolyte
(202001AW070004, 202301AS070051, 202301AU070064), towards Ultrafast Li+ Transfer. Angew. Chem., Int. Ed. 2022, 61 (7),
Yunnan Industrial Innovative Talents Program for “Xingdian No. e202114220.
Talent Support Plan” (KKXY202252001), Yunnan Program (18) Raj, V.; Venturi, V.; Kankanallu, V. R.; Kuiri, B.; Viswanathan,
for Introducing Foreign Talents (202305AO350042), Yunnan V.; Aetukuri, N. P. B. Direct correlation between void formation and
M a j o r S c i e n t i fi c a n d T e c h n o l o g i c a l P r o j e c t s lithium dendrite growth in solid-state electrolytes with interlayers.
Nat. Mater. 2022, 21 (9), 1050−1056.
(202202AG050003), and Yunnan Provincial Education
(19) An, X.; Liu, Y.; Yang, K.; Mi, J.; Ma, J.; Zhang, D.; Chen, L.;
Department Universities Serve Key Industry Science and Liu, X.; Guo, S.; Li, Y.; Ma, Y.; Liu, M.; He, Y.-B.; Kang, F. Dielectric
Technology Projects (FWCY-BSPY2024040). Filler-Induced Hybrid Interphase Enabling Robust Solid-State Li

■ REFERENCES
(1) Deng, J.; Luo, W.-B.; Chou, S.-L.; Liu, H.-K.; Dou, S.-X. Sodium-
Metal Batteries at High Areal Capacity. Adv. Mater. 2024, 36 (13),
2311195.
(20) Lai, X.; Xu, Z.; Yang, X.; Ke, Q.; Xu, Q.; Wang, Z.; Lu, Y.; Qiu,
Ion Batteries: From Academic Research to Practical Commercializa- Y. Long Cycle Life and High-Rate Sodium Metal Batteries Enabled by
tion. Adv. Energy Mater. 2018, 8 (4), 1701428. Regulating 3D Frameworks with Artificial Solid-State Interphases.
(2) Lao, M.; Zhang, Y.; Luo, W.; Yan, Q.; Sun, W.; Dou, S. X. Alloy- Adv. Energy Mater. 2022, 12 (10), 2103540.
Based Anode Materials toward Advanced Sodium-Ion Batteries. Adv. (21) Li, T.; Zhang, X.-Q.; Yao, N.; Yao, Y.-X.; Hou, L.-P.; Chen, X.;
Mater. 2017, 29 (48), 1700622. Zhou, M.-Y.; Huang, J.-Q.; Zhang, Q. Stable Anion-Derived Solid
(3) Lee, H.-W.; Wang, R. Y.; Pasta, M.; Lee, S. W.; Liu, N.; Cui, Y. Electrolyte Interphase in Lithium Metal Batteries. Angew. Chem., Int.
Manganese hexacyanomanganate open framework as a high-capacity Ed. 2021, 60 (42), 22683−22687.
positive electrode material for sodium-ion batteries. Nat. Commun. (22) Tan, J.; Ma, L.; Li, Z.; Wang, Y.; Ye, M.; Shen, J. Structural
2014, 5, 5280. insights into solid electrolyte interphase (SEI) on lithium metal
(4) Yang, X.; Zhang, D.; Zhao, L.; Peng, C.; Ren, K.; Xu, C.; Liu, P.; anode: From design strategies to the stability evaluation. Mater. Today
Zhou, Y.; Lei, Y.; Yang, B.; Xue, D.; Liang, F. Upgrading Cycling 2023, 69, 287−332.
Stability and Capability of Hybrid Na-CO2 Batteries via Tailoring (23) Hou, M.; Zhou, Y.; Liang, F.; Zhao, H.; Ji, D.; Zhang, D.; Li, L.;
Reaction Environment for Efficient Conversion CO2 to HCOOH. Lei, Y. Research progress of solid electrolyte interphase for sodium
Adv. Energy Mater. 2024, 14 (16), 2304365. metal anodes. Chem. Eng. J. 2023, 475, 146227.
(5) Balaish, M.; Gonzalez-Rosillo, J. C.; Kim, K. J.; Zhu, Y.; Hood, Z. (24) Lee, M. H.; Kim, S. J.; Chang, D.; Kim, J.; Moon, S.; Oh, K.;
D.; Rupp, J. L. M. Processing thin but robust electrolytes for solid- Park, K.-Y.; Seong, W. M.; Park, H.; Kwon, G.; Lee, B.; Kang, K.
state batteries. Nat. Energy 2021, 6 (3), 227−239. Toward a low-cost high-voltage sodium aqueous rechargeable battery.
(6) Lu, Y.; Li, L.; Zhang, Q.; Niu, Z.; Chen, J. Electrolyte and Mater. Today 2019, 29, 26−36.
Interface Engineering for Solid-State Sodium Batteries. Joule 2018, 2 (25) Efaw, C. M.; Wu, Q.; Gao, N.; Zhang, Y.; Zhu, H.; Gering, K.;
(9), 1747−1770. Hurley, M. F.; Xiong, H.; Hu, E.; Cao, X.; Xu, W.; Zhang, J.-G.;
(7) Wang, X.; Zhang, C.; Sawczyk, M.; Yuan, Q.; Chen, F.; Mendes, Dufek, E. J.; Xiao, J.; Yang, X.-Q.; Liu, J.; Qi, Y.; Li, B. Localized high-
T. C.; Howlett, P. C.; Fu, C.; Kral, P.; Hawker, C. J.; Whittaker, A.; concentration electrolytes get more localized through micelle-like
Forsyth, M.; Sun, J.; Wang, Y.; Tan, X.; Searles, D. J. Ultra-stable all-
structures. Nat. Mater. 2023, 22 (12), 1531−1539.
solid-state sodium metal batteries enabled by perfluoropolyether-
(26) Ma, T.; Ni, Y.; Wang, Q.; Zhang, W.; Jin, S.; Zheng, S.; Yang,
based electrolytes. Nat. Mater. 2022, 21 (9), 1057−1065.
X.; Hou, Y.; Tao, Z.; Chen, J. Optimize Lithium Deposition at Low
(8) Lou, S.; Zhang, F.; Fu, C.; Chen, M.; Ma, Y.; Yin, G.; Wang, J.
Temperature by Weakly Solvating Power Solvent. Angew. Chem., Int.
Interface Issues and Challenges in All-Solid-State Batteries: Lithium,
Sodium, and Beyond. Adv. Mater. 2021, 33 (6), 2000721. Ed. 2022, 61 (39), No. e202207927.
(9) Tian, Y.; Shi, T.; Richards, W. D.; Li, J.; Kim, J. C.; Bo, S.-H.; (27) Zahiri, B.; Patra, A.; Kiggins, C.; Yong, A. X. B.; Ertekin, E.;
Ceder, G. Compatibility issues between electrodes and electrolytes in Cook, J. B.; Braun, P. V. Revealing the role of the cathode-electrolyte
solid-state batteries. Energy Environ. Sci. 2017, 10 (5), 1150−1166. interface on solid-state batteries. Nat. Mater. 2021, 20 (10), 1392−
(10) Li, F.; Hou, M.; Zhao, L.; Zhang, D.; Yang, B.; Liang, F. 1400.
Electrolyte and interface engineering for solid-state sodium batteries. (28) Pan, J.; Hu, L.; Zhang, Y.; Zhang, T.; Wang, N.; Dou, S.; Fan,
Energy Storage Mater. 2024, 65, 103181. H. J. Internal and External Co-Engineering of Stable Cathode
(11) Richards, W. D.; Tsujimura, T.; Miara, L. J.; Wang, Y.; Kim, J. Interface Improves Cycle Performance of Polymer Sodium Batteries.
C.; Ong, S. P.; Uechi, I.; Suzuki, N.; Ceder, G. Design and synthesis of Adv. Funct. Mater. 2024, 34, 2214904.
the superionic conductor Na10SnP2S12. Nat. Commun. 2016, 7, 11009. (29) Lou, S.; Yu, Z.; Liu, Q.; Wang, H.; Chen, M.; Wang, J. Multi-
(12) Zeng, Y.; Ouyang, B.; Liu, J.; Byeon, Y.-W.; Cai, Z.; Miara, L. J.; scale Imaging of Solid-State Battery Interfaces: From Atomic Scale to
Wang, Y.; Ceder, G. High-entropy mechanism to boost ionic Macroscopic Scale. Chem. 2020, 6 (9), 2199−2218.
conductivity. Science 2022, 378 (6626), 1320−1324. (30) Kim, J.; Ku, M.; Kim, S.; Yang, H.; Lee, D.; Lee, H.; Kim, Y.-B.
(13) Lee, B.; Paek, E.; Mitlin, D.; Lee, S. W. Sodium Metal Anodes: Interdiffusion suppression at the cathode-electrolyte interface of all-
Emerging Solutions to Dendrite Growth. Chem. Rev. 2019, 119 (8), solid-state-batteries by Li3PO4 conformal coating. J. Am. Ceram. Soc.
5416−5460. 2024, 107 (5), 3134−3145.
(14) Liu, J.; Yuan, H.; Liu, H.; Zhao, C.-Z.; Lu, Y.; Cheng, X.-B.; (31) Zhao, L. Q.; Zhong, Y. J.; Cao, C. C.; Tang, T.; Shao, Z. P.
Huang, J.-Q.; Zhang, Q. Unlocking the Failure Mechanism of Solid Enhanced High-Temperature Cycling Stability of Garnet-Based All
State Lithium Metal Batteries. Adv. Energy Mater. 2022, 12 (4), Solid-State Lithium Battery Using a Multi-Functional Catholyte
2100748. Buffer Layer. Nano-Micro Lett. 2024, 16 (7), 124.

203 https://doi.org/10.1021/acsenergylett.4c03043
ACS Energy Lett. 2025, 10, 195−204
ACS Energy Letters http://pubs.acs.org/journal/aelccp Letter

(32) Duan, Z.; Zhu, J.; Lin, J.; Qu, S.; Lin, L.; Gao, G.; Wang, L.; (49) Wang, Y.; Liu, F.; Fan, G.; Qiu, X.; Liu, J.; Yan, Z.; Zhang, K.;
Peng, D.-L. High-Voltage All-Solid-State Thin-Film Lithium Batteries Cheng, F.; Chen, J. Electroless Formation of a Fluorinated Li/Na
Enabled by LiF Interlayer. J. Phys. Chem. Lett. 2024, 15 (14), 3812− Hybrid Interphase for Robust Lithium Anodes. J. Am. Chem. Soc.
3819. 2021, 143 (7), 2829−2837.
(33) Song, Z.; Wang, L.; Jiang, W.; Pei, M.; Li, B.; Mao, R.; Liu, S.;
Zhang, T.; Jian, X.; Hu, F. “Like Compatible Like″ Strategy Designing
Strong Cathode-Electrolyte Interface Quasi-Solid-State Lithium-
Sulfur Batteries. Adv. Energy Mater. 2024, 14 (4), 2302688.
(34) Xin, C.; Wen, K.; Xue, C.; Wang, S.; Liang, Y.; Wu, X.; Li, L.;
Nan, C.-W. Composite Cathodes with Succinonitrile-Based Ionic
Conductors for Long-Cycle-Life Solid-State Lithium Metal Batteries.
Batteries Supercaps 2022, 5 (1), No. e202100162.
(35) Xu, R.; Shen, X.; Ma, X.-X.; Yan, C.; Zhang, X.-Q.; Chen, X.;
Ding, J.-F.; Huang, J.-Q. Identifying the Critical Anion−Cation
Coordination to Regulate the Electric Double Layer for an Efficient
Lithium-Metal Anode Interface. Angew. Chem., Int. Ed. 2021, 60 (8),
4215−4220.
(36) Lin, R.; He, Y.; Wang, C.; Zou, P.; Hu, E.; Yang, X.-Q.; Xu, K.;
Xin, H. L. Characterization of the structure and chemistry of the solid-
electrolyte interface by cryo-EM leads to high-performance solid-state
Li-metal batteries. Nature Nanotechnol 2022, 17 (7), 768−776.
(37) Nirmale, T. C.; Karbhal, I.; Kalubarme, R. S.; Shelke, M. V.;
Varma, A. J.; Kale, B. B. Facile Synthesis of Unique Cellulose
Triacetate Based Flexible and High Performance Gel Polymer
Electrolyte for Lithium Ion Batteries. ACS Appl. Mater. Interfaces
2017, 9 (40), 34773−34782.
(38) Wen, P.; Lu, P.; Shi, X.; Yao, Y.; Shi, H.; Liu, H.; Yu, Y.; Wu,
Z.-S. Photopolymerized Gel Electrolyte with Unprecedented Room-
Temperature Ionic Conductivity for High-Energy-Density Solid-State
Sodium Metal Batteries. Adv. Energy Mater. 2021, 11 (6), 2002930.
(39) Li, Z.; Fu, J.; Zhou, X.; Gui, S.; Wei, L.; Yang, H.; Li, H.; Guo,
X. Ionic Conduction in Polymer-Based Solid Electrolytes. Adv. Sci.
2023, 10 (10), 2201718.
(40) Bao, D.; Tao, Y.; Zhong, Y.; Zhao, W.; Peng, M.; Zhang, H.;
Sun, X. High-Performance Dual-Salt Plastic Crystal Electrolyte
Enabled by Succinonitrile-Regulated Porous Polymer Host. Adv.
Funct. Mater. 2023, 33 (17), 2213211.
(41) Yang, X.; Peng, C.; Hou, M.; Zhang, D.; Yang, B.; Xue, D.; Lei,
Y.; Liang, F. Rational Design of Electrolyte Solvation Structures for
Modulating 2e−/4e− Transfer in Sodium-Air Batteries. Adv. Funct.
Mater. 2022, 32 (23), 2201258.
(42) Zhou, Q.; Yang, X.; Xiong, X.; Zhang, Q.; Peng, B.; Chen, Y.;
Wang, Z.; Fu, L.; Wu, Y. A Solid Electrolyte Based on Electrochemical
Active Li4Ti5O12 with PVDF for Solid State Lithium Metal Battery.
Adv. Energy Mater. 2022, 12 (39), 2201991.
(43) Cheng, M.; Qu, T.; Zi, J.; Yao, Y.; Liang, F.; Ma, W.; Yang, B.;
Dai, Y.; Lei, Y. A hybrid solid electrolyte for solid-state sodium ion
batteries with good cycle performance. Nanotechnology 2020, 31 (42),
425401.
(44) Kim, J.-K.; Lim, Y. J.; Kim, H.; Cho, G.-B.; Kim, Y. A hybrid
solid electrolyte for flexible solid-state sodium batteries. Energy
Environ. Sci. 2015, 8 (12), 3589−3596.
(45) Wang, H.; Yang, Y.; Gao, C.; Chen, T.; Song, J.; Zuo, Y.; Fang,
Q.; Yang, T.; Xiao, W.; Zhang, K.; Wang, X.; Xia, D. An entanglement
association polymer electrolyte for Li-metal batteries. Nat. Commun.
2024, 15 (1), 2500.
(46) Jiang, M.; Li, T.; Qiu, Y.; Hou, X.; Lin, H.; Zheng, Q.; Li, X.
Electrolyte Design with Dual -C = N Groups Containing Additives to
Enable High-Voltage Na3V2(PO4)2F3-Based Sodium-Ion Batteries. J.
Am. Chem. Soc. 2024, 146 (18), 12519−12529.
(47) Wang, Y.; Li, Z.; Xie, W.; Zhang, Q.; Hao, Z.; Zheng, C.; Hou,
J.; Lu, Y.; Yan, Z.; Zhao, Q.; Chen, J. Asymmetric Solvents Regulated
Crystallization-Limited Electrolytes for All-Climate Lithium Metal
Batteries. Angew. Chem., Int. Ed. 2024, 63 (6), No. e202310905.
(48) Chen, J.; Yang, Z.; Xu, X.; Qiao, Y.; Zhou, Z.; Hao, Z.; Chen,
X.; Liu, Y.; Wu, X.; Zhou, X.; Li, L.; Chou, S.-L. Nonflammable
Succinonitrile-Based Deep Eutectic Electrolyte for Intrinsically Safe
High-Voltage Sodium-Ion Batteries. Adv. Mater. 2024, 36, 2400169.

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