DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries

Abstract

Solid-state batteries (SSBs) could significantly improve the safety and energy density over conventional liquid cells. One key enabling technology is the use of solid electrolytes. NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a very attractive solid-state electrolyte for the cathode side due to its high oxidation potential and high ionic conductivity. The usage, however, is limited by its large interfacial resistance against most of the cathode materials as well as the thermodynamic instability during high temperature sintering needed to achieve high mass density. Here we construct thin, percolative, and mixed conductive interphases through in situ low-melting-point liquid sintering. These mixed conductive interphases drastically improve the kinetics, leading to high-loading solid LATP/LiCoO2 cathodes achieving capacity loading of up to ~6 mA h cm–2. The technique is also applicable to Ni-rich cathode materials, achieving up to ~10 mAh cm–2, which can lead to more than 400 W h kg–1 cells in SSBs. Furthermore, our composite cathodes show a ten-times and three-times area capacity improvement over the state-of-the-art cathodes using oxide and sulfide SSEs, respectively.

Authors:
 [1];  [2];  [3];  [4];  [2];  [5];  [2];  [3];  [2];  [4];  [4]; ORCiD logo [3];  [4];  [6];  [2];  [7];  [2]
  1. Univ. of Washington, Seattle, WA (United States); Nanjing Forestry Univ. (China); Xiamen Univ. (China)
  2. Univ. of Washington, Seattle, WA (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Xiamen Univ. (China)
  5. Shanghai Univ. (China)
  6. Southern Univ. of Science and Technology, Shenzhen (China)
  7. Univ. of Washington, Seattle, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1827882
Report Number(s):
PNNL-SA-164550
Journal ID: ISSN 1754-5692
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 14; Journal Issue: 9; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Han, Xiang, Wang, Shanyu, Xu, Yaobin, Zhong, Guiming, Zhou, Yang, Liu, Bo, Jiang, Xiaoyu, Wang, Xiang, Li, Yun, Zhang, Ziqi, Chen, Songyan, Wang, Chongmin, Yang, Yong, Zheng, Wenqing, Wang, Junlan, Liu, Jun, and Yang, Jihui. All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries. United States: N. p., 2021. Web. doi:10.1039/d1ee01494c.
Han, Xiang, Wang, Shanyu, Xu, Yaobin, Zhong, Guiming, Zhou, Yang, Liu, Bo, Jiang, Xiaoyu, Wang, Xiang, Li, Yun, Zhang, Ziqi, Chen, Songyan, Wang, Chongmin, Yang, Yong, Zheng, Wenqing, Wang, Junlan, Liu, Jun, & Yang, Jihui. All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries. United States. https://doi.org/10.1039/d1ee01494c
Han, Xiang, Wang, Shanyu, Xu, Yaobin, Zhong, Guiming, Zhou, Yang, Liu, Bo, Jiang, Xiaoyu, Wang, Xiang, Li, Yun, Zhang, Ziqi, Chen, Songyan, Wang, Chongmin, Yang, Yong, Zheng, Wenqing, Wang, Junlan, Liu, Jun, and Yang, Jihui. Wed . "All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries". United States. https://doi.org/10.1039/d1ee01494c. https://www.osti.gov/servlets/purl/1827882.
@article{osti_1827882,
title = {All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries},
author = {Han, Xiang and Wang, Shanyu and Xu, Yaobin and Zhong, Guiming and Zhou, Yang and Liu, Bo and Jiang, Xiaoyu and Wang, Xiang and Li, Yun and Zhang, Ziqi and Chen, Songyan and Wang, Chongmin and Yang, Yong and Zheng, Wenqing and Wang, Junlan and Liu, Jun and Yang, Jihui},
abstractNote = {Solid-state batteries (SSBs) could significantly improve the safety and energy density over conventional liquid cells. One key enabling technology is the use of solid electrolytes. NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a very attractive solid-state electrolyte for the cathode side due to its high oxidation potential and high ionic conductivity. The usage, however, is limited by its large interfacial resistance against most of the cathode materials as well as the thermodynamic instability during high temperature sintering needed to achieve high mass density. Here we construct thin, percolative, and mixed conductive interphases through in situ low-melting-point liquid sintering. These mixed conductive interphases drastically improve the kinetics, leading to high-loading solid LATP/LiCoO2 cathodes achieving capacity loading of up to ~6 mA h cm–2. The technique is also applicable to Ni-rich cathode materials, achieving up to ~10 mAh cm–2, which can lead to more than 400 W h kg–1 cells in SSBs. Furthermore, our composite cathodes show a ten-times and three-times area capacity improvement over the state-of-the-art cathodes using oxide and sulfide SSEs, respectively.},
doi = {10.1039/d1ee01494c},
journal = {Energy & Environmental Science},
number = 9,
volume = 14,
place = {United States},
year = {Wed Jul 21 00:00:00 EDT 2021},
month = {Wed Jul 21 00:00:00 EDT 2021}
}

Works referenced in this record:

Negating interfacial impedance in garnet-based solid-state Li metal batteries
journal, December 2016

  • Han, Xiaogang; Gong, Yunhui; Fu, Kun (Kelvin)
  • Nature Materials, Vol. 16, Issue 5
  • DOI: 10.1038/nmat4821

All-Solid-State Li-Ion Battery Using Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 As Electrolyte Without Polymer Interfacial Adhesion
journal, May 2018

  • Meesala, Yedukondalu; Chen, Chen-Yu; Jena, Anirudha
  • The Journal of Physical Chemistry C, Vol. 122, Issue 26
  • DOI: 10.1021/acs.jpcc.8b03971

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Li 3 N-Modified Garnet Electrolyte for All-Solid-State Lithium Metal Batteries Operated at 40 °C
journal, October 2018


Projector augmented-wave method
journal, December 1994


A review of lithium and non-lithium based solid state batteries
journal, May 2015


Co-sinterable lithium garnet-type oxide electrolyte with cathode for all-solid-state lithium ion battery
journal, November 2014


Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries
journal, January 2020

  • Li, Xiaona; Liang, Jianwen; Yang, Xiaofei
  • Energy & Environmental Science, Vol. 13, Issue 5
  • DOI: 10.1039/C9EE03828K

High ion conductive Sb2O5-doped β-Li3PS4 with excellent stability against Li for all-solid-state lithium batteries
journal, June 2018


Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
journal, October 2015

  • Zhu, Yizhou; He, Xingfeng; Mo, Yifei
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 42
  • DOI: 10.1021/acsami.5b07517

Influence of B2O3 addition on the ionic conductivity of Li1.5Al0.5Ge1.5(PO4)3 glass ceramics
journal, November 2013


Flexible Composite Solid Electrolyte Facilitating Highly Stable “Soft Contacting” Li-Electrolyte Interface for Solid State Lithium-Ion Batteries
journal, September 2017

  • Yang, Luyi; Wang, Zijian; Feng, Yancong
  • Advanced Energy Materials, Vol. 7, Issue 22
  • DOI: 10.1002/aenm.201701437

Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries
journal, March 2017

  • Wu, Jian-Fang; Pang, Wei Kong; Peterson, Vanessa K.
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 14
  • DOI: 10.1021/acsami.7b00614

Mechanochemical synthesis and crystallization of Li<sub>3</sub>BO<sub>3</sub>–Li<sub>2</sub>CO<sub>3</sub> glass electrolytes
journal, January 2016

  • Nagao, Kenji; Hayashi, Akitoshi; Tatsumisago, Masahiro
  • Journal of the Ceramic Society of Japan, Vol. 124, Issue 9
  • DOI: 10.2109/jcersj2.16114

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


A lithium superionic conductor
journal, July 2011

  • Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro
  • Nature Materials, Vol. 10, Issue 9, p. 682-686
  • DOI: 10.1038/nmat3066

High-power all-solid-state batteries using sulfide superionic conductors
journal, March 2016


Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface
journal, October 2017


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
  • DOI: 10.1021/acsami.8b05132

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Interphase Engineering Enabled All-Ceramic Lithium Battery
journal, March 2018


Investigation on the interface between Li10GeP2S12 electrolyte and carbon conductive agents in all-solid-state lithium battery
journal, May 2018


Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density
journal, January 2018

  • Wang, Longlong; Chen, Bingbing; Ma, Jun
  • Chemical Society Reviews, Vol. 47, Issue 17
  • DOI: 10.1039/C8CS00322J

Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li 4 SiO 4 –Li 3 PO 4 Solid Electrolytes
journal, July 2015

  • Deng, Yue; Eames, Christopher; Chotard, Jean-Noël
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b04444

High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes
journal, March 2018

  • Chen, Shuru; Zheng, Jianming; Mei, Donghai
  • Advanced Materials, Vol. 30, Issue 21
  • DOI: 10.1002/adma.201706102

Separating electronic and ionic conductivity in mix-conducting layered lithium transition-metal oxides
journal, July 2018


Transient Behavior of the Metal Interface in Lithium Metal-Garnet Batteries
journal, October 2017

  • Fu, Kun Kelvin; Gong, Yunhui; Fu, Zhezhen
  • Angewandte Chemie International Edition, Vol. 56, Issue 47
  • DOI: 10.1002/anie.201708637

All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing
journal, September 2013


A solid future for battery development
journal, September 2016


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Growth and ionic conductivity of γ-Li3PO4
journal, September 2001

  • Ivanov-Shitz, A. K.; Kireev, V. V.; Mel’nikov, O. K.
  • Crystallography Reports, Vol. 46, Issue 5
  • DOI: 10.1134/1.1405880

Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode
journal, September 2018


A High-Performance and Durable Poly(ethylene oxide)-Based Composite Solid Electrolyte for All Solid-State Lithium Battery
journal, April 2018

  • Ban, Xiaoyao; Zhang, Wenqiang; Chen, Ning
  • The Journal of Physical Chemistry C, Vol. 122, Issue 18
  • DOI: 10.1021/acs.jpcc.8b02556

Garnet Electrolyte with an Ultralow Interfacial Resistance for Li-Metal Batteries
journal, April 2018

  • Li, Yutao; Chen, Xi; Dolocan, Andrei
  • Journal of the American Chemical Society, Vol. 140, Issue 20
  • DOI: 10.1021/jacs.8b03106

Lithium Insertion into Titanium Phosphates, Silicates, and Sulfates
journal, December 2002

  • Patoux, Sébastien; Masquelier, Christian
  • Chemistry of Materials, Vol. 14, Issue 12
  • DOI: 10.1021/cm0201798

Drawing a Soft Interface: An Effective Interfacial Modification Strategy for Garnet-Type Solid-State Li Batteries
journal, May 2018


Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries
journal, February 2018


Electrochemical and interfacial behavior of all solid state batteries using Li10SnP2S12 solid electrolyte
journal, August 2018


Compatibility study of oxide and olivine cathode materials with lithium aluminum titanium phosphate
journal, September 2017


Doping of Co3O4 with lithium by a solid-state reaction in air I. Oxidation degree and coordination of cations
journal, July 1990


Mitigating the Interfacial Degradation in Cathodes for High-Performance Oxide-Based Solid-State Lithium Batteries
journal, January 2019

  • Wang, Dawei; Sun, Qian; Luo, Jing
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 5
  • DOI: 10.1021/acsami.8b17881

Spark Plasma Sintering of LiTi2(PO4)3-Based Solid Electrolytes
journal, July 2005


Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems
journal, January 2016

  • Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J.
  • Journal of Materials Chemistry A, Vol. 4, Issue 40
  • DOI: 10.1039/C6TA05439K

Recent progress on solid-state hybrid electrolytes for solid-state lithium batteries
journal, September 2019


Use of B2O3 to improve Li+-ion transport in LiTi2(PO4)3-based ceramics
journal, January 2012


Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017


Constructing double buffer layers to boost electrochemical performances of NCA cathode for ASSLB
journal, March 2019