LaCl3-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl3-based Na+ superionic conductor (Na1−xZrxLa1−xCl4) with high ionic conductivity of 2.9 × 10−4 S cm−1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na2Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P63/m) of Na1−xZrxLa1−xCl4, with Na+ ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na1−xZrxLa1−xCl4 is mainly determined by the size of Na+-channels and the Na+/La3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO2||Na0.7Zr0.3La0.7Cl4||Na3PS4||Na2Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g−1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g−1 can be maintained at 1 C current density.


REVIEWER COMMENTS
Reviewer #1 (Remarks to the Author): This review paper summarizes a new halide-based sodium ion conductor Na1-xZrxLa1-xCl4, that has a conductivity in the 10^-4 S/cm range.
While the methodology in the paper is quite thorough, there are a few concerns that need to be addressed before it can be recommended for publication.
• It is unclear why Na2.9PS3.9Cl0.1 was chosen as a barrier layer or anolyte in the all-solidstate battery (ASSB) configuration.Although introducing the halide into the configuration improved the cycling stability compared to using Na2.9PS-3.9Cl0.1 alone, the capacity retention of 75% after 70 cycles is still severe degradation.A more stable or suitable ASSB cell configuration should be used to demonstrate stability.
• It is unclear why cycling was conducted at 60°C and not at ambient temperature or other temperatures.
• While a higher conducting sodium halide improves its usability, its electrochemical window is similar to other reported halides (chlorides).I do not think that supports the claim that higher voltage solid-state batteries can result.
• I do not think the EXAFS data is reliable if the halide has hydrolyzed, as that degradation will fundamentally alter its properties.Air-sensitive sample transfer is a must.
In addition, there are concerns about the novelty of this manuscript.
• A previous study has already elucidated the effect of Zr4+ aliovalent doping into sodium halide solid-state electrolytes.https://www.nature.com/articles/s41467-021-21488-7.The conclusions in this paper are very similar.
• There is a preprint from 2022 which has shown higher Na conductivity and longer cycling stability than the findings in this manuscript.https://chemrxiv.org/engage/chemrxiv/articledetails/637a89cf20798134fe2e6586 Reviewer #2 (Remarks to the Author): In the manuscript "New Sodium Halide Solid Electrolytes with High Ionic Conductivity for All-Solid-State Batteries", the authors reported a new LaCl3-based solid electrolyte with ionic conductivity of 2.9 × 10^-4 S/cm.When combined with Na2Sn anode and NaCrO2 cathode, the solid-state cell gives an initial capacity of 119 mA h/g at 0.1C.There are quite a few aspects that should be clarified in the manuscript.Some suggestions to further improve the paper: 1 The authors mentioned that "As a result, the bond length of Na-Cl in the 1D channel increases from the original 2.87 Å to 2.91 Å (Fig. 3c), implying that the migration of Na+ ions requiring a lower barrier comparing to NLC (0.04 eV in NLC vs. 0.26 eV in NLZC, Fig. 3d).", which may be not accurate.More explanations about the difference between NLZC and NLZC-La/Na mixing should be given.In actual situations, whether La/Na mixing occurs?If occurs, giving the simulated result about NLZC is reasonable or not? 2 In Table S6 2b site, the occupancy of Na and La is 0.391 and 0.071.But the authors mentioned that "A mixing ratio (0.06) of La/Na at 2b site along the c axis was found from XRD refinement, due to the similar radius of La3+ and Na+ (Table S6)."How can the authors give the numbers?
3 In absorption edge of the Zr K-edge, the comparison of ZrCl4 samples should be considered.The comparison of ZrO2 samples to prove the presence of Zr-Cl coordination is not convincing enough.The XAFS test is capable of avoiding hydrolysis.The fitting results of Zr-O and La-O should be excluded.
4 In Supplementary Figure 12, how to get the oxidation potential of 3.7 V? It seems a clear deviation.
5 In cell tests, why test under 60 ℃?Is it reasonable to test at high temperature when SE conductivity is high enough.Typically, lithium cells could test under room temperature with such ionic conductivity of SE.
6 The stablity of the new SE against NaSn is not good.However, the LaCl3-based Lithium SE is stable with Li metal anode.The authors need give more insightful investigation.

Reviewer #3 (Remarks to the Author):
In this manuscript, the authors report on Na1-xZrxLa1-xCl4 prepared by annealing and subsequent mechanochemical milling method as a halide solid electrolyte material with 0.29 mS cm-1 for all-solid-state Na+ batteries.The structure of Na1-xZrxLa1-xCl4 was characterized using XRD Rietveld refinement and EXAFS.It is interesting that a report about Na halide electrolyte with hexagonal structure is the first time.Besides, the electrochemical performance of Na1-xZrxLa1-xCl4 was also characterized by cyclic voltammetry and half cell tests.Including above issues, the following discussion points should be addressed extensively.
1. Regarding the composition of 'Na0.7Zr0.3La0.7Cl4':Given that ZrCl4 has melting and boiling points of 437 oC and 331 oC, respectively, the annealing protocol, which is performed at 450 oC for 10 h in an Ar furnace, may pose a possibility of ZrCl4 precursor sublimation prior to the intended reaction, potentially altering the nominal compositions.
2. The pivotal role of mechanochemical milling, which enhances conductivity by nearly two orders of magnitude, is broadly, limitedly, and vaguely discussed.Specifically, the claim "To further promote the ionic conductivity, the high temperature sintered samples were ball milled to introduce disordering and defects, thus rising the doping concentration of Zr4+ and further expanding the lattice and diffusion channel (NLZCx-HM)."Warrants a meticulous discussion.Considering that the reported material has rapid 1D Na ion conduction channels along the c axis, introducing disorder might adversely impact the 1D connectivity, which necessitates an extensive and in-depth exploration supplemented by additional data and/or theories.
3. Why does the lattice parameter expand upon although Zr is introduced in the lattice and Na vacancy is formed?The ionic radius of Zr4+ is smaller than that of La3+.

Title: New Sodium Halide Solid Electrolytes with High Ionic Conductivity for All-Solid-State
Batteries REVIEWER 1:

Referee comment:
This review paper summarizes a new halide-based sodium ion conductor Na1-xZrxLa1-xCl4, that has a conductivity in the 10 -4 S/cm range.While the methodology in the paper is quite thorough, there are a few concerns that need to be addressed before it can be recommended for publication.
Author response: We thank the reviewer for the positive comments and carefully revised the relevant content accordingly.

Referee Query 1:
It is unclear why Na2.9PS3.9Cl0.1 was chosen as a barrier layer or anolyte in the all-solid-state battery (ASSB) configuration.Although introducing the halide into the configuration improved the cycling stability compared to using Na2.9PS3.9Cl0.1 alone, the capacity retention of 75% after 70 cycles is still severe degradation.A more stable or suitable ASSB cell configuration should be used to demonstrate stability.
Author response 1: We are sincerely grateful to the referee for their suggestion.The reason we choose Na2.9PS3.9Cl0.1 as a barrier layer instead of Na3PS4 is the higher conductivity of 10 -3 S/cm comparing to Na3PS4 (10 -4 S/cm).However, this electrolyte is incompatible to Na1-xZrxLa1-xCl4 and the interface resistance between Na2.9PS3.9Cl0.1 and Na1-xZrxLa1-xCl4 keeps increasing.After mixing together and hold for 5 days, X-ray photoelectron spectroscopy (XPS) shows significant structural changes, especially in NPSC.In the revised manuscript, Na3PS4 was chosen as the barrier layer and the stability and cycle life are both enhanced.The changes are detailed in the Response Letter and are highlighted in blue font in the revised main text and figure captions: "All solid-state batteries were assembled with homemade NaCrO2 (Supplementary Fig. 20) composite cathode, Na2Sn anode and NLZC0.3-HMSSE, with Na3PS4 serving as a transition layer to isolate the NLZC0.3-HMelectrolyte from the Na2Sn anode (Fig. 5a)." "Enlarged SEM image (Fig. 5b1) and EDS (Supplementary Fig. 22) confirm the tight physical contact between NaCrO2 cathode and NLZC0.3-HMSSE, which should be benefit to the Na + ion diffusion at the interface.The two SSEs layers and Na2Sn anode layer are quite dense with only small amount pores (Fig. 5b2-4).The boundaries between layers are relatively clear, with little mixing between them (Supplementary Fig. 22-25).The total resistance of these ASSBs before cycling is about 400 Ω (Supplementary Fig. 26), which was contributed by NLZC0.3-HM(~150 Ω, Supplementary Fig. 6d), Na3PS4 SSE (~80 Ω, Supplementary Fig. 27), Na2Sn anode side (~20 Ω, Supplementary Fig. 27 and Supplementary Fig. 28a), resistance between NLZC0.3-HM and Na3PS4 (~50 Ω, Supplementary Fig. 28a, b), and interface from NaCrO2 cathode side (~100 Ω, Supplementary Fig. 26 and Supplementary Fig. 28b).Na2.9PS3.9Cl0.1 with higher ionic conductivity (Supplementary Fig. 29) was also selected as a transition layer to reduce the total resistance of ASSB.However, this electrolyte reacts with NLZC0.3-HM and the resistance keeps increasing when co-pressed together (Supplementary Fig. 30).The XPS spectra indicate structural changes with NLZC0.3-HM and NPSC mixing together (Supplementary Fig. 31), especially for NPSC, which causes an increase in resistance (Supplementary Fig. 30).
The ASSB of NaCrO2||NLZC0.3-HM||Na3PS4||Na2Sn was cycled between 2.0 V and 3.4 V, in which range the NLZC0.3-HMSSE is electrochemically stable.When cycling at 0.1 C (30 ℃), the discharge capacity for the first cycle reaches 123 mA h g -1 , with a high columbic efficiency (CE) of 95%, reflecting a highly irreversible reaction in this ASSB.When current density increases, the capacity decreases from 123 mA h g -1 (0.1C) to 119 mA h g -1 (0.2C), 114 mA h g -1 (0.3C), 108 mA h g -1 (0.5C), and 94 mA h g -1 (1C), showing high-capacity retention at high current density (Fig. 5c, d).Compared to other halide SSEs with lower ionic conductivity, the rate performance of ASSB using NLZC0.3-HM is better. 4,46After cycling at 0.3 C for 70 times, the capacity retains 100 mA h g -1 , which is 88% of the initial capacity (Fig. 5e, f).Part of the capacity loss should come from an increase in resistance, which is 780 Ω after 70 cycles at 0.3C (Supplementary Fig. 26).This increase in resistance may originate from Na3PS4/Na2Sn interface, further enhancement in cycle performance can be achieved with other SSE transition layers, such as Na4(B12H12)(B10H10). 46 " Referee Query 2: It is unclear why cycling was conducted at 60°C and not at ambient temperature or other temperatures.
Author response 2: We thank the reviewer for this insightful question.When choosing Na2.9PS3.9Cl0.1 as a barrier layer, the high interfacial resistance between Na2.9PS3.9Cl0.1 and Na1-xZrxLa1-xCl4 makes the ASSB unable to operate at ambient temperature.In the revised manuscript, Na3PS4 was chosen as the barrier layer and the ASSB is operated at ambient temperature.The changes are detailed in the Response Letter and are highlighted in blue font in the revised main text and figure captions: "The ASSB of NaCrO2||NLZC0.3-HM||Na3PS4||Na2Sn was cycled between 2.0 V and 3.4 V, in which range the NLZC0.3-HMSSE is electrochemically stable.When cycling at 0.1 C (30 ℃), the discharge capacity for the first cycle reaches 123 mA h g -1 , with a high columbic efficiency (CE) of 95%, reflecting a highly irreversible reaction in this ASSB.When current density increases, the capacity decreases from 123 mA h g -1 (0.1C) to 119 mA h g -1 (0.2C), 114 mA h g -1 (0.3C), 108 mA h g -1 (0.5C), and 94 mA h g -1 (1C), showing high-capacity retention at high current density (Fig. 5c, d).Compared to other halide SSEs with lower ionic conductivity, the rate performance of ASSB using NLZC0.3-HM is better. 4,46After cycling at 0.3 C for 70 times, the capacity retains 100 mA h g -1 , which is 88% of the initial capacity (Fig. 5e, f).Part of the capacity loss should come from an increase in resistance, which is 780 Ω after 70 cycles at 0.3C (Supplementary Fig. 26).This increase in resistance may originate from Na3PS4/Na2Sn interface, further enhancement in cycle performance can be achieved with other SSE transition layers, such as Na4(B12H12)(B10H10). 46 " Referee Query 3: While a higher conducting sodium halide improves its usability, its electrochemical window is similar to other reported halides (chlorides).I do not think that supports the claim that higher voltage solid-state batteries can result.

Author response 3:
We are sorry about the misunderstanding.High voltage sodium ASSBs we mentioned in the abstract doesn't mean voltage over 4 V vs. Na/Na + but voltage around 3 V vs. Na/Na + , which is incompatible to sulfide SSEs.When using halide SSEs, the low ionic conductivity results in poor rate performance.In this work, the higher ionic conductivity of NLZC0.3-HMimproves the rate performance in ASSBs, compared to the results from literature (Nat.Commun.12, 1256 ( 2021)).To avoid misunderstanding, we deleted high voltage in the revised manuscript: "This work demonstrates the possibility of high ionic conductivity sodium ion halide SSEs, which would promote the development of sodium ASSBs."

Referee Query 4:
I do not think the EXAFS data is reliable if the halide has hydrolyzed, as that degradation will fundamentally alter its properties.Air-sensitive sample transfer is a must.

Author response 4:
We thank the reviewer for this valuable suggestion.The EXAFS was repeated with covering samples with air tight Kapton film and the results show no hydrolyzation.The following discussion was revised as below: "The Zr K-edge and La L3-edge X-ray absorption fine structure (XAFS) was obtained to reveal the local coordination structure of Na0.7La0.7Zr0.3Cl4-HT,Na0.7La0.7Zr0.3Cl4-HMand NaLaCl4-HT.It can be seen that the absorption edge of the Zr K-edge and La L3-edge of three were basically coincide (Supplementary Fig. 14), indicating equal valence with Zr 4+ and La 3+ .From the R-space of Zr K-edge, the main peak at about 2 Å could be recognized as Zr-Cl coordination from Na0.7La0.7Zr0.3Cl4-HTand Na0.7La0.7Zr0.3Cl4-HM(Supplementary Fig. 15).Similarly, the R-space curve of La L3-edge also show a significant difference in the position of the main peaks compare with La2O3 (Supplementary Fig. 16), which could be recognized as La-Cl coordination of NaLaCl4, Na0.7La0.7Zr0.3Cl4-HTand Na0.7La0.7Zr0.3Cl4-HM.As a result, Zr-Cl bond and La-Cl bond lengths are different obviously.""As shown in Fig. 4, EXAFS fitting is performed to quantitatively compare the Zr-Cl and La-Cl coordination structures in Na0.7La0.7Zr0.3Cl4and the results are summarized in Supplementary Tab.12. NaLaCl4, NLZC0.3-HT and NLZC0.3-HMhave similar bond length of La-Cl and the coordination numbers of La, which proves that the doping of the Zr element and ball milling process does not change its structure, which is consistent with the XRD results (Supplementary Fig. 1).It can be confirmed that the bond length of Zr-Cl is about 2.48 Å while it is 2.94 Å for La-Cl."Extended Data Figure 1 LaCl3 based Na + ion SSE with higher ionic conductivity and lower activation energy."When cycling at 0.1 C (30 ℃), the discharge capacity for the first cycle reaches 123 mA h g -1 , with a high columbic efficiency (CE) of 95%, reflecting a highly irreversible reaction in this ASSB.
Author response: Aliovalent doping is quite common in enhancing ionic conductivity of SSEs.
Zr 4+ doping has a different affect in the LaCl3-based SSE, which is changing the distributions of Na + ions.More importantly, Zr 4+ doping is the tool to enhance the ionic conductivity but not the key point in this work.
• There is a preprint from 2022 which has shown higher Na conductivity and longer cycling stability than the findings in this manuscript.https://chemrxiv.org/engage/chemrxiv/articledetails/637a89cf20798134fe2e6586 Author response: Thanks for sharing this work, which we didn't notice before.We have cited this work and compared the rate performance in the revised manuscript.

REVIWER 2:
Referee comment: In the manuscript "New Sodium Halide Solid Electrolytes with High Ionic Conductivity for All-Solid-State Batteries", the authors reported a new LaCl3-based solid electrolyte with ionic conductivity of 2.9 × 10 -4 S/cm.When combined with Na2Sn anode and NaCrO2 cathode, the solidstate cell gives an initial capacity of 119 mA h/g at 0.1C.There are quite a few aspects that should be clarified in the manuscript.Some suggestions to further improve the paper: Author response: We thank the reviewer for the detailed suggestions, which helps to improve the quality of our work.

Referee Query 1:
The authors mentioned that "As a result, the bond length of Na-Cl in the 1D channel increases from the original 2.87 Å to 2.91 Å (Fig. 3c), implying that the migration of Na + ions requiring a lower barrier comparing to NLC (0.04 eV in NLC vs. 0.26 eV in NLZC, Fig. 3d).", which may be not accurate.More explanations about the difference between NLZC and NLZC-La/Na mixing should be given.In actual situations, whether La/Na mixing occurs?If occurs, giving the simulated result about NLZC is reasonable or not?
Author response 1: Thank you very much for the reviewer's correction of this point of view.Our explanation about the relationship between Na-Cl bond length and activation energy is too simple, makes this not convincing.We added more explanations in the revised manuscript: "The longer Na-Cl bond broadens the diffusion bottleneck in the 1D channel, lowers the site energy of Na + ions at the bottleneck, thereby lowering their migration activation energy and increasing the Na + ion conductivity.The AIMD simulations imply that the migration of Na + ions in NLZC requiring a lower barrier comparing to NLC (0.04 eV in NLC vs. 0.26 eV in NLZC, Fig. 3d)." The La/Na mixing was confirmed with XRD refinement.More importantly, this is reasonable since La 3+ (1.032 Å) has a similar size to Na + (1.02 Å) and this La 3+ /Na + mixing at 2c site is confirmed already (Z.Anorg.Allg.Chem.620, 444-450 (1994)).The blocking of 1D ion conduction is also found in other materials, such as LiFePO4 (Chem.Mater.17, 5085-5092 ( 2005)), so this La 3+ /Na + mixing should be considered when conducting theoretical simulations.
Energy is considered when introducing La 3+ at 2b site.The model with the lowest energy was selected to calculate Na + ion conductivity.Meanwhile, the thermodynamic stability of this optimized model was also investigated.Ion mixing generally increases the entropy in solids, making it relatively stable at high temperatures.AIMD results show that the mixed material can still maintain stability at 500K, which is one of the reasons for the mixing of materials obtained in the experiment.More explanations are added in the revised manuscript: "The NLZC-La/Namixing structure was constructed with energy as the criterion (Supplementary Fig. 11).The thermodynamic stability of the constructed model was also investigated (Supplementary Fig. 12).
The comparison of results shows that when the NLZC is at 400K, the structural frame with LaCl3 as the premise has greater distortion, which means it is more unstable, while the NLZC-La/Namixing still keeps the structure relatively stable under 500K, indicating that the mixing makes the material more stable." Referee Query 2: In Table S6 2b site, the occupancy of Na and La is 0.391 and 0.071.But the authors mentioned that "A mixing ratio (0.06) of La/Na at 2b site along the c axis was found from XRD refinement, due to the similar radius of La 3+ and Na + (Table S6)."How can the authors give the numbers?
edge and La L3-edge X-ray absorption fine structure (XAFS) was obtained to reveal the local coordination structure of Na0.7La0.7Zr0.3Cl4-HT,Na0.7La0.7Zr0.3Cl4-HMand NaLaCl4-HT.It can be seen that the absorption edge of the Zr K-edge and La L3-edge of three were basically coincide (Supplementary Fig. 14), indicating equal valence with Zr 4+ and La 3+ .From the R-space of Zr Kedge, the main peak at about 2 Å could be recognized as Zr-Cl coordination from Na0.7La0.7Zr0.3Cl4-HTand Na0.7La0.7Zr0.3Cl4-HM(Supplementary Fig. 15).Similarly, the R-space curve of La L3-edge also show a significant difference in the position of the main peaks compare with La2O3 (Supplementary Fig. 16), which could be recognized as La-Cl coordination of NaLaCl4, Na0.7La0.7Zr0.3Cl4-HTand Na0.7La0.7Zr0.3Cl4-HM.As a result, Zr-Cl bond and La-Cl bond lengths are different obviously." "As shown in Fig. 4, EXAFS fitting is performed to quantitatively compare the Zr-Cl and La-Cl coordination structures in Na0.7La0.7Zr0.3Cl4and the results are summarized in Supplementary Tab.12. NaLaCl4, NLZC0.3-HT and NLZC0.3-HMhave similar bond length of La-Cl and the coordination numbers of La, which proves that the doping of the Zr element and ball milling process does not change its structure, which is consistent with the XRD results (Supplementary Fig. 1).It can be confirmed that the bond length of Zr-Cl is about 2.48 Å while it is 2.94 Å for La-Cl."Supplementary Figure 14 (a)La L3-edge and (b)Zr K-edge XANES spectra for the Na0.7La0.7Zr0.3Cl4and NaLaCl4 and distribution of Na ions at different sites.As a result, the ion migration activation energy and ionic conductivity can be changed.The structure change with ball milling was further investigated with XAFS and synchrotron XRD.According to the synchrotron XRD, ball milling increased the number of Na + ions at 2b site and also the lattice parameter a, which increases the charge carrier concentration and size of diffusion bottleneck, both are benefit to the ion migration.However, Ball milling did not excessively increase the disorder of the electrolyte, and the LaCl3 framework structure was well maintained.Therefore, the adverse effect on conductivity is relatively small.
Relevant figures and contents are added: "Synchrotron XRD of NaLaCl4-HT and NaLaCl4-HM were carried out to figure out the changes in fine structure and the reason for volume expansion.
The refinement results shown in Supplementary Fig. 6 and Supplementary Tab. 9 reveal a small amount of Na + at the 2b site (0.16) in NaLaCl4-HT, which means this site is small and metastable for Na + occupying.Excess Na exists in the form of unknown impurities (Supplementary Fig. 6).
During the ball milling process, the high energy causes more Na + to occupy the 2b site (0.251), resulting in disappearance of impurities and lattice expansion (Supplementary Fig. 7 and Supplementary Tab.10).On the contrary, the expansion of the lattice makes the Na + at the 2b site more stable.Zr 4+ doping at La 3+ site can also stabilize Na + at 2b site and more Na + occupies 2b site (0.461) in Na0.7La0.7Zr0.3Cl4-HT(Supplementary Fig. 8 and Supplementary Tab.11), leading to an increase of lattice parameter a (7.583Å).Furthermore, there is no significant change in the framework, such as significant decrease in orderliness or even to totally amorphous (Supplementary Fig. 6 and 7).This may be related to the strong bond energy of M-Cl, which keeps its main structure unchanged."current density increases, the capacity decreases from 123 mA h g -1 (0.1C) to 119 mA h g -1 (0.2C), 114 mA h g -1 (0.3C), 108 mA h g -1 (0.5C), and 94 mA h g -1 (1C), showing high-capacity retention at high current density (Fig. 5c, d).Compared to other halide SSEs with lower ionic conductivity, the rate performance of ASSB using NLZC0.3-HM is better. 4,46After cycling at 0.3 C for 70 times, the capacity retains 100 mA h g -1 , which is 88% of the initial capacity (Fig. 5e, f).Part of the capacity loss should come from an increase in resistance, which is 780 Ω after 70 cycles at 0.3C (Supplementary Fig. 26).This increase in resistance may originate from Na3PS4/Na2Sn interface, further enhancement in cycle performance can be achieved with other SSE transition layers, such as Na4(B12H12)(B10H10). 46 " Referee Query 5: Cyclic voltammetry for oxidative and reductive stability should be measured separately at room temperature and 60 o C.

Author response 5:
We are sincerely grateful to the referee for this suggestion.In order to display the electrochemical stability window of NLZC more clearly, linear scanning voltammetry (LSV) was conducted.We have added the following discussion in revised manuscript: "Linear scanning voltammetry (LSV) of NLZC0.3-HM-SuperP||NLZC0.3-HM||Na3PS4||Na2Snreveals that the electrochemical stable window of NLZC0.3-HM is from 1.33 V to 3.80 V vs. Na2Sn at 30 ℃ and from 1.44 V to 3.79 V vs. Na2Sn at 60 ℃ (Supplementary Fig. 17), which is consistent with the theoretical results of sodium halide SSEs. 4 "

Table 12
Fitting results from EXAFS

Table 12
Fitting results from EXAFS