A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Erik A Wu^#¹, Swastika Banerjee^#¹, Hanmei Tang^#¹, Peter M Richardson², Jean-Marie Doux¹, Ji Qi¹, Zhuoying Zhu¹, Antonin Grenier³, Yixuan Li¹, Enyue Zhao¹, Grayson Deysher⁴, Elias Sebti², Han Nguyen⁵, Ryan Stephens⁶, Guy Verbist⁷, Karena W Chapman³, Raphaële J Clément⁸, Abhik Banerjee^{9

10}, Ying Shirley Meng^{11

12}, Shyue Ping Ong^{13

14}

Affiliations

¹ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA.
² Materials Department, University of California Santa Barbara, Santa Barbara, CA, USA.
³ Department of Chemistry, Stony Brook University, Stony Brook, New York, NY, USA.
⁴ Department of Materials Science and Engineering, University of California San Diego, La Jolla, San Diego, CA, USA.
⁵ Department of Chemistry & Biochemistry, University of California San Diego, La Jolla, San Diego, CA, USA.
⁶ Shell International Exploration & Production Inc., Houston, TX, USA.
⁷ Shell Global Solutions International BV, The Hague, Netherlands.
⁸ Materials Department, University of California Santa Barbara, Santa Barbara, CA, USA. rclement@ucsb.edu.
⁹ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA. abhik.banerjee@tcgcrest.org.
¹⁰ Research Institute for Sustainable Energy (RISE), TCG Centres for Research and Education in Science and Technology (TCG CREST), Sector V, Salt Lake, Kolkata, India. abhik.banerjee@tcgcrest.org.
¹¹ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA. shmeng@ucsd.edu.
¹² Sustainable Power & Energy Center (SPEC), University of California San Diego, La Jolla, San Diego, CA, USA. shmeng@ucsd.edu.
¹³ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA. ongsp@eng.ucsd.edu.
¹⁴ Sustainable Power & Energy Center (SPEC), University of California San Diego, La Jolla, San Diego, CA, USA. ongsp@eng.ucsd.edu.

^# Contributed equally.

PMID: 33623048
PMCID: PMC7902639
DOI: 10.1038/s41467-021-21488-7

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Erik A Wu et al. Nat Commun. 2021.

. 2021 Feb 23;12(1):1256.

doi: 10.1038/s41467-021-21488-7.

Authors

Affiliations

¹ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA.
² Materials Department, University of California Santa Barbara, Santa Barbara, CA, USA.
³ Department of Chemistry, Stony Brook University, Stony Brook, New York, NY, USA.
⁴ Department of Materials Science and Engineering, University of California San Diego, La Jolla, San Diego, CA, USA.
⁵ Department of Chemistry & Biochemistry, University of California San Diego, La Jolla, San Diego, CA, USA.
⁶ Shell International Exploration & Production Inc., Houston, TX, USA.
⁷ Shell Global Solutions International BV, The Hague, Netherlands.
⁸ Materials Department, University of California Santa Barbara, Santa Barbara, CA, USA. rclement@ucsb.edu.
⁹ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA. abhik.banerjee@tcgcrest.org.
¹⁰ Research Institute for Sustainable Energy (RISE), TCG Centres for Research and Education in Science and Technology (TCG CREST), Sector V, Salt Lake, Kolkata, India. abhik.banerjee@tcgcrest.org.
¹¹ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA. shmeng@ucsd.edu.
¹² Sustainable Power & Energy Center (SPEC), University of California San Diego, La Jolla, San Diego, CA, USA. shmeng@ucsd.edu.
¹³ Department of NanoEngineering, University of California San Diego, La Jolla, San Diego, CA, USA. ongsp@eng.ucsd.edu.
¹⁴ Sustainable Power & Energy Center (SPEC), University of California San Diego, La Jolla, San Diego, CA, USA. ongsp@eng.ucsd.edu.

^# Contributed equally.

PMID: 33623048
PMCID: PMC7902639
DOI: 10.1038/s41467-021-21488-7

Abstract

Rechargeable solid-state sodium-ion batteries (SSSBs) hold great promise for safer and more energy-dense energy storage. However, the poor electrochemical stability between current sulfide-based solid electrolytes and high-voltage oxide cathodes has limited their long-term cycling performance and practicality. Here, we report the discovery of the ion conductor Na_3-xY_1-xZr_xCl₆ (NYZC) that is both electrochemically stable (up to 3.8 V vs. Na/Na⁺) and chemically compatible with oxide cathodes. Its high ionic conductivity of 6.6 × 10^-5 S cm^-1 at ambient temperature, several orders of magnitude higher than oxide coatings, is attributed to abundant Na vacancies and cooperative MCl₆ rotation, resulting in an extremely low interfacial impedance. A SSSB comprising a NaCrO₂ + NYZC composite cathode, Na₃PS₄ electrolyte, and Na-Sn anode exhibits an exceptional first-cycle Coulombic efficiency of 97.1% at room temperature and can cycle over 1000 cycles with 89.3% capacity retention at 40 °C. These findings highlight the immense potential of halides for SSSB applications.

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Conflict of interest statement

R.S. and G.V. are employees of Shell International Exploration and Production Inc., USA and Shell Global Solutions International BV, Netherlands, respectively. A patent was filed for this work through the UCSD Office of Innovation and Commercialization. The remaining authors declare no competing interests.

Figures

**Fig. 1. Effect of Zr dopants on properties of Na₃YCl₆.**
a Crystal structure of Na₃YCl₆. b Stability of Na_3-xY_1-xZr_xCl₆ after incorporating Zr⁴⁺ into Na₃YCl₆. Each square marker indicates a symmetrically distinct ordering of Na and Y/Zr. c Electrochemical stability window of Na_3-xY_1-xZr_xCl₆ (0 ≤ x ≤ 1), with the window of Na₃PS₄ (NPS) shown as a reference. d Arrhenius plot for Na_3-xY_1-xZr_xCl₆ from AIMD simulations (at x = 0.375, 0.5, and 0.75; solid lines and markers) and ML-IAP MD simulations (at x = 0.75; dashed lines and open markers). AIMD simulations were carried out at T = 600–1000 K at 100 K intervals, using a supercell of 150 atoms for up to 200 ps, while the ML-IAP MD simulations were carried out at T = 350 K–650 K using a supercell of 592 atoms for up to 10 ns.

**Fig. 2. Experimental Characterization of Na_3-xY_1-xZr_xCl₆.**
a XRD of the Na_3-xY_1-xZr_xCl₆ compositions, obtained in x = 0.125 increments. Asterisks indicate the presence of new peaks. b The corresponding room temperature conductivity values. c Arrhenius plot of Na_2.25Y_0.25Zr_0.75Cl₆ from experimental measurements. The activation energy (low-temperature regime) and room temperature conductivity values are consistent with the MTP results.

**Fig. 3. ²³Na single-pulse solid-state NMR spectra.**
a Spectra collected on Na_3-xY_1-xZr_xCl₆ (x = 0, 0.25, 0.5, 0.75 and 1); the data were acquired at 18.8 T and at a MAS rate of 12 kHz and at a set temperature of 298 K. b Schematic of the Na0 and Na1 local environments in Na₃YCl₆.

**Fig. 4. Effect of octahedra rotation on Na⁺ diffusivity.**
Plots of the probability density (isosurface value = 5 × 10⁻⁴) of a Na⁺ in Na₃YCl₆, b Na⁺ in Na_2.25Y_0.25Z_0.75Cl₆, c Cl⁻ in Na₃YCl₆ and d Cl⁻ in Na_2.25Y_0.25Z_0.75Cl₆, over 100 ps of AIMD simulations at 600 K. The motion of Na⁺ and Cl⁻ in Na₃YCl₆ are relatively localized, while macroscopic Na⁺ diffusion with (Zr/Y)Cl₆ octahedral rotation are observed in Na_2.25Y_0.25Z_0.75Cl₆. e Na⁺ diffusivity at 800 K (D_800K, in cm²/s) for varying Zr content in Na_3−xY_1−xZr_xCl₆, compared with a selective dynamics simulation with Cl⁻ ions frozen in space, which shows negligible Na⁺ diffusivity.

**Fig. 5. Electrochemical performance of the NYZC0.75 SSSBs.**
a Cell schematic. Voltage profile and specific capacity as a function of cycle number of this cell configuration, respectively, running at: b–c 20 °C and C/10, d–e 20 °C and C/10 for the first 5 cycles and subsequent cycling at C/2, f–g 40 °C and C/10 for the first 5 cycles and subsequent cycling at C/2, and h–i 40 °C and 1 C. In each case, the NYZC0.75 cells exhibit long-term cycling stability, with 89.3% capacity retention at 1000 cycles for the 40 °C 1 C cell.

**Fig. 6. Comparison of SSSB performance metrics.**
a Gravimetric energy density (per mass of active material) plotted as a function of cycle number. b Capacity retention as a function of cycle number^,,–. The cycling performance comparison highlights the compatibility and stability of the NaCrO₂ + Na_2.25Y_0.25Zr_0.75Cl₆ + VGCF composite cathode.

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A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Affiliations

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Authors

Affiliations

Abstract

Conflict of interest statement

Figures

References

LinkOut - more resources

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