A new halospinel superionic conductor for high-voltage all solid state lithium batteries
Abstract
We report a new Li-superionic chloride, Li2Sc2/3Cl4, that crystallizes in a disordered spinel structure, and exhibits an ionic conductivity of 1.5 mS cm–1 with a low activation energy barrier for Li+ ion diffusion of 0.34 eV. Here, this material is the first spinel-type superionic halide. Structural elucidation via powder neutron diffraction reveals a significantly disordered Li+-ion distribution over available tetrahedral and octahedral sites within the lattice, forming an infinitely 3D connected Li+ ion diffusion pathway comprised of face-sharing octahedra and tetrahedra. Due to the high oxidative stability of Li2Sc2/3Cl4, all solid state lithium batteries employing Li2Sc2/3Cl4 and high voltage cathodes (LiCoO2, LiNi0.6Mn0.2Co0.2O2 or high-Ni LiNi0.85Mn0.1Co0.05O2) – without any coating – exhibit excellent electrochemical performance up to 4.6 V in terms of capacity retention and cycle life.
- Authors:
-
- University of Waterloo, ON (Canada)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- BASF SE, Ludwigshafen (Germany)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1657953
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 7; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Zhou, Laidong, Kwok, Chun Yuen, Shyamsunder, Abhinandan, Zhang, Qiang, Wu, Xiaohan, and Nazar, Linda F. A new halospinel superionic conductor for high-voltage all solid state lithium batteries. United States: N. p., 2020.
Web. doi:10.1039/D0EE01017K.
Zhou, Laidong, Kwok, Chun Yuen, Shyamsunder, Abhinandan, Zhang, Qiang, Wu, Xiaohan, & Nazar, Linda F. A new halospinel superionic conductor for high-voltage all solid state lithium batteries. United States. https://doi.org/10.1039/D0EE01017K
Zhou, Laidong, Kwok, Chun Yuen, Shyamsunder, Abhinandan, Zhang, Qiang, Wu, Xiaohan, and Nazar, Linda F. 2020.
"A new halospinel superionic conductor for high-voltage all solid state lithium batteries". United States. https://doi.org/10.1039/D0EE01017K. https://www.osti.gov/servlets/purl/1657953.
@article{osti_1657953,
title = {A new halospinel superionic conductor for high-voltage all solid state lithium batteries},
author = {Zhou, Laidong and Kwok, Chun Yuen and Shyamsunder, Abhinandan and Zhang, Qiang and Wu, Xiaohan and Nazar, Linda F.},
abstractNote = {We report a new Li-superionic chloride, Li2Sc2/3Cl4, that crystallizes in a disordered spinel structure, and exhibits an ionic conductivity of 1.5 mS cm–1 with a low activation energy barrier for Li+ ion diffusion of 0.34 eV. Here, this material is the first spinel-type superionic halide. Structural elucidation via powder neutron diffraction reveals a significantly disordered Li+-ion distribution over available tetrahedral and octahedral sites within the lattice, forming an infinitely 3D connected Li+ ion diffusion pathway comprised of face-sharing octahedra and tetrahedra. Due to the high oxidative stability of Li2Sc2/3Cl4, all solid state lithium batteries employing Li2Sc2/3Cl4 and high voltage cathodes (LiCoO2, LiNi0.6Mn0.2Co0.2O2 or high-Ni LiNi0.85Mn0.1Co0.05O2) – without any coating – exhibit excellent electrochemical performance up to 4.6 V in terms of capacity retention and cycle life.},
doi = {10.1039/D0EE01017K},
url = {https://www.osti.gov/biblio/1657953},
journal = {Energy & Environmental Science},
issn = {1754-5692},
number = 7,
volume = 13,
place = {United States},
year = {Wed Jun 10 00:00:00 EDT 2020},
month = {Wed Jun 10 00:00:00 EDT 2020}
}
Web of Science
Works referenced in this record:
High-Voltage Superionic Halide Solid Electrolytes for All-Solid-State Li-Ion Batteries
journal, January 2020
- Park, Kern-Ho; Kaup, Kavish; Assoud, Abdeljalil
- ACS Energy Letters, Vol. 5, Issue 2
Pressure effects on sulfide electrolytes for all solid-state batteries
journal, January 2020
- Doux, Jean-Marie; Yang, Yangyuchen; Tan, Darren H. S.
- Journal of Materials Chemistry A, Vol. 8, Issue 10
High-Throughput Screening of Solid-State Li-Ion Conductors Using Lattice-Dynamics Descriptors
journal, June 2019
- Muy, Sokseiha; Voss, Johannes; Schlem, Roman
- iScience, Vol. 16
New horizons for inorganic solid state ion conductors
journal, January 2018
- Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina
- Energy & Environmental Science, Vol. 11, Issue 8
Interfacial Processes and Influence of Composite Cathode Microstructure Controlling the Performance of All-Solid-State Lithium Batteries
journal, May 2017
- Zhang, Wenbo; Weber, Dominik A.; Weigand, Harald
- ACS Applied Materials & Interfaces, Vol. 9, Issue 21
A bird's-eye view of Li-stuffed garnet-type Li 7 La 3 Zr 2 O 12 ceramic electrolytes for advanced all-solid-state Li batteries
journal, January 2019
- Samson, Alfred Junio; Hofstetter, Kyle; Bag, Sourav
- Energy & Environmental Science, Vol. 12, Issue 10
Benchmarking the performance of all-solid-state lithium batteries
journal, March 2020
- Randau, Simon; Weber, Dominik A.; Kötz, Olaf
- Nature Energy, Vol. 5, Issue 3
Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces
journal, November 2019
- Chen, Rusong; Li, Qinghao; Yu, Xiqian
- Chemical Reviews, Vol. 120, Issue 14
Insights into the Performance Limits of the Li 7 P 3 S 11 Superionic Conductor: A Combined First-Principles and Experimental Study
journal, March 2016
- Chu, Iek-Heng; Nguyen, Han; Hy, Sunny
- ACS Applied Materials & Interfaces, Vol. 8, Issue 12
Revealing Nanoscale Solid–Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries
journal, October 2019
- Banerjee, Abhik; Tang, Hanmei; Wang, Xuefeng
- ACS Applied Materials & Interfaces, Vol. 11, Issue 46
Some chlorides with the inverse spinel structure
journal, October 1975
- van Loon, C. J. J.; de Jong, J.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 31, Issue 10
A solid future for battery development
journal, September 2016
- Janek, Jürgen; Zeier, Wolfgang G.
- Nature Energy, Vol. 1, Issue 9
High magnesium mobility in ternary spinel chalcogenides
journal, November 2017
- Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan
- Nature Communications, Vol. 8, Issue 1
Beyond Doping and Coating: Prospective Strategies for Stable High-Capacity Layered Ni-Rich Cathodes
journal, March 2020
- Sun, H. Hohyun; Ryu, Hoon-Hee; Kim, Un-Hyuck
- ACS Energy Letters, Vol. 5, Issue 4
An Entropically Stabilized Fast-Ion Conductor: Li 3.25 [Si 0.25 P 0.75 ]S 4
journal, September 2019
- Zhou, Laidong; Assoud, Abdeljalil; Shyamsunder, Abhinandan
- Chemistry of Materials, Vol. 31, Issue 19
Kristallstrukturen von MgCr2O4-Typ Li2VCl4 und Spinell-Typ Li2MgCl4 und Li2CdCl4
journal, May 1994
- Partik, M.; Schneider, M.; Lutz, H. D.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 620, Issue 5
Thermodynamics of Antisite Defects in Layered NMC Cathodes: Systematic Insights from High-Precision Powder Diffraction Analyses
journal, December 2019
- Yin, Liang; Li, Zhuo; Mattei, Gerard S.
- Chemistry of Materials, Vol. 32, Issue 3
Solid Halide Electrolytes with High Lithium-Ion Conductivity for Application in 4 V Class Bulk-Type All-Solid-State Batteries
journal, September 2018
- Asano, Tetsuya; Sakai, Akihiro; Ouchi, Satoru
- Advanced Materials, Vol. 30, Issue 44
A lithium superionic conductor
journal, July 2011
- Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro
- Nature Materials, Vol. 10, Issue 9, p. 682-686
From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries
journal, March 2020
- Tan, Darren H. S.; Banerjee, Abhik; Chen, Zheng
- Nature Nanotechnology, Vol. 15, Issue 3
Air-stable Li 3 InCl 6 electrolyte with high voltage compatibility for all-solid-state batteries
journal, January 2019
- Li, Xiaona; Liang, Jianwen; Luo, Jing
- Energy & Environmental Science, Vol. 12, Issue 9
Stabilized Behavior of LiNi 0.85 Co 0.10 Mn 0.05 O 2 Cathode Materials Induced by Their Treatment with SO 2
journal, March 2020
- Susai, Francis Amalraj; Sclar, Hadar; Maiti, Sandipan
- ACS Applied Energy Materials, Vol. 3, Issue 4
High-power all-solid-state batteries using sulfide superionic conductors
journal, March 2016
- Kato, Yuki; Hori, Satoshi; Saito, Toshiya
- Nature Energy, Vol. 1, Issue 4
Elucidating Reversible Electrochemical Redox of Li 6 PS 5 Cl Solid Electrolyte
journal, August 2019
- Tan, Darren H. S.; Wu, Erik A.; Nguyen, Han
- ACS Energy Letters, Vol. 4, Issue 10
Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li 3 MCl 6 (M = Y, Er) Superionic Conductors
journal, December 2019
- Schlem, Roman; Muy, Sokseiha; Prinz, Nils
- Advanced Energy Materials, Vol. 10, Issue 6
Degradation Mechanisms at the Li 10 GeP 2 S 12 /LiCoO 2 Cathode Interface in an All-Solid-State Lithium-Ion Battery
journal, June 2018
- Zhang, Wenbo; Richter, Felix H.; Culver, Sean P.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 26
High Active Material Loading in All‐Solid‐State Battery Electrode via Particle Size Optimization
journal, November 2019
- Shi, Tan; Tu, Qingsong; Tian, Yaosen
- Advanced Energy Materials, Vol. 10, Issue 1
Li 3 BO 3 –Li 2 CO 3 : Rationally Designed Buffering Phase for Sulfide All-Solid-State Li-Ion Batteries
journal, October 2018
- Jung, Sung Hoo; Oh, Kyungbae; Nam, Young Jin
- Chemistry of Materials, Vol. 30, Issue 22
Impact of Cathode Material Particle Size on the Capacity of Bulk-Type All-Solid-State Batteries
journal, March 2018
- Strauss, Florian; Bartsch, Timo; de Biasi, Lea
- ACS Energy Letters, Vol. 3, Issue 4
Enhanced Cycling Performance of Ni-Rich Positive Electrodes (NMC) in Li-Ion Batteries by Reducing Electrolyte Free-Solvent Activity
journal, June 2019
- Tatara, Ryoichi; Yu, Yang; Karayaylali, Pinar
- ACS Applied Materials & Interfaces, Vol. 11, Issue 38
Interface Stability in Solid-State Batteries
journal, December 2015
- Richards, William D.; Miara, Lincoln J.; Wang, Yan
- Chemistry of Materials, Vol. 28, Issue 1
Stabilizing Effect of a Hybrid Surface Coating on a Ni-Rich NCM Cathode Material in All-Solid-State Batteries
journal, November 2019
- Kim, A-Young; Strauss, Florian; Bartsch, Timo
- Chemistry of Materials, Vol. 31, Issue 23
Microstructural Modeling of Composite Cathodes for All-Solid-State Batteries
journal, December 2018
- Bielefeld, Anja; Weber, Dominik A.; Janek, Jürgen
- The Journal of Physical Chemistry C, Vol. 123, Issue 3
Tuning mobility and stability of lithium ion conductors based on lattice dynamics
journal, January 2018
- Muy, Sokseiha; Bachman, John C.; Giordano, Livia
- Energy & Environmental Science, Vol. 11, Issue 4
Stack Pressure Considerations for Room‐Temperature All‐Solid‐State Lithium Metal Batteries
journal, November 2019
- Doux, Jean‐Marie; Nguyen, Han; Tan, Darren H. S.
- Advanced Energy Materials, Vol. 10, Issue 1
New Family of Argyrodite Thioantimonate Lithium Superionic Conductors
journal, October 2019
- Zhou, Laidong; Assoud, Abdeljalil; Zhang, Qiang
- Journal of the American Chemical Society, Vol. 141, Issue 48
Chloride spinels: A new group of solid lithium electrolytes
journal, January 1981
- Lutz, H. D.; Schmidt, W.; Haeuseler, H.
- Journal of Physics and Chemistry of Solids, Vol. 42, Issue 4
Solvent-Engineered Design of Argyrodite Li 6 PS 5 X (X = Cl, Br, I) Solid Electrolytes with High Ionic Conductivity
journal, November 2018
- Zhou, Laidong; Park, Kern-Ho; Sun, Xiaoqi
- ACS Energy Letters, Vol. 4, Issue 1
Solution-Processable Glass LiI-Li 4 SnS 4 Superionic Conductors for All-Solid-State Li-Ion Batteries
journal, December 2015
- Park, Kern Ho; Oh, Dae Yang; Choi, Young Eun
- Advanced Materials, Vol. 28, Issue 9
Neue schnelle Ionenleiter vom Typ MI3MIIICl6 (MI = Li, Na, Ag; MIII = In, Y)
journal, July 1992
- Steiner, H. -J.; Lutz, H. D.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 613, Issue 7
Structure, ionic motion and conductivity in some solid-solutions of the LiClMCl2 systems (M=Mg,V,Mn)
journal, December 1983
- Cros, C.; Hanebali, L.; Latie, L.
- Solid State Ionics, Vol. 9-10
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction
journal, December 2015
- Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis
- Chemical Reviews, Vol. 116, Issue 1
Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017
- Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
- Nature Reviews Materials, Vol. 2, Issue 4
Inducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li 6+ x P 1– x Ge x S 5 I for All-Solid-State Batteries
journal, October 2018
- Kraft, Marvin A.; Ohno, Saneyuki; Zinkevich, Tatiana
- Journal of the American Chemical Society, Vol. 140, Issue 47
Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12”
journal, January 2011
- Buschmann, Henrik; Dölle, Janis; Berendts, Stefan
- Physical Chemistry Chemical Physics, Vol. 13, Issue 43
Understanding interface stability in solid-state batteries
journal, December 2019
- Xiao, Yihan; Wang, Yan; Bo, Shou-Hang
- Nature Reviews Materials, Vol. 5, Issue 2