Designing a hybrid electrode toward high energy density with a staged Li+ and PF6- deintercalation/intercalation mechanism
Abstract
Existing lithium-ion battery technology is struggling to meet our increasing requirements for high energy density, long lifetime, and low-cost energy storage. Here, a hybrid electrode design is developed by a straightforward reengineering of commercial electrode materials, which has revolutionized the “rocking chair” mechanism by unlocking the role of anions in the electrolyte. Our proof-of-concept hybrid LiFePO4(LFP)/graphite electrode works with a staged deintercalation/intercalation mechanism of Li+cations and PF6-anions in a broadened voltage range, which was thoroughly studied byex situX-ray diffraction,ex situRaman spectroscopy, andoperandoneutron powder diffraction. Introducing graphite into the hybrid electrode accelerates its conductivity, facilitating the rapid extraction/insertion of Li+from/into the LFP phase in 2.5 to 4.0 V. This charge/discharge process, in turn, triggers the in situ formation of the cathode/electrolyte interphase (CEI) layer, reinforcing the structural integrity of the whole electrode at high voltage. Consequently, this hybrid LFP/graphite-20% electrode displays a high capacity and long-term cycling stability over 3,500 cycles at 10 C, superior to LFP and graphite cathodes. Importantly, the broadened voltage range and high capacity of the hybrid electrode enhance its energy density, which is leveraged further in a full-cell configuration.
- Authors:
-
- Univ. of Wollongong, NSW (Australia)
- Univ. of Wollongong, NSW (Australia); Fudan Univ., Shanghai (China)
- Univ. of Wollongong, NSW (Australia); Australian Nuclear Science and Technology Organisation (ANSTO), Kirrawee, NSW (Australia)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Wollongong, NSW (Australia); Zhengzhou Univ. (China)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Australian Research Council; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1632117
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Volume: 117; Journal Issue: 6; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Li-ion battery; hybrid electrode; intercalation
Citation Formats
Hao, Junnan, Yang, Fuhua, Zhang, Shilin, He, Hanna, Xia, Guanglin, Liu, Yajie, Didier, Christophe, Liu, Tongchao, Pang, Wei Kong, Peterson, Vanessa K., Lu, Jun, and Guo, Zaiping. Designing a hybrid electrode toward high energy density with a staged Li+ and PF6- deintercalation/intercalation mechanism. United States: N. p., 2020.
Web. doi:10.1073/pnas.1918442117.
Hao, Junnan, Yang, Fuhua, Zhang, Shilin, He, Hanna, Xia, Guanglin, Liu, Yajie, Didier, Christophe, Liu, Tongchao, Pang, Wei Kong, Peterson, Vanessa K., Lu, Jun, & Guo, Zaiping. Designing a hybrid electrode toward high energy density with a staged Li+ and PF6- deintercalation/intercalation mechanism. United States. https://doi.org/10.1073/pnas.1918442117
Hao, Junnan, Yang, Fuhua, Zhang, Shilin, He, Hanna, Xia, Guanglin, Liu, Yajie, Didier, Christophe, Liu, Tongchao, Pang, Wei Kong, Peterson, Vanessa K., Lu, Jun, and Guo, Zaiping. Wed .
"Designing a hybrid electrode toward high energy density with a staged Li+ and PF6- deintercalation/intercalation mechanism". United States. https://doi.org/10.1073/pnas.1918442117. https://www.osti.gov/servlets/purl/1632117.
@article{osti_1632117,
title = {Designing a hybrid electrode toward high energy density with a staged Li+ and PF6- deintercalation/intercalation mechanism},
author = {Hao, Junnan and Yang, Fuhua and Zhang, Shilin and He, Hanna and Xia, Guanglin and Liu, Yajie and Didier, Christophe and Liu, Tongchao and Pang, Wei Kong and Peterson, Vanessa K. and Lu, Jun and Guo, Zaiping},
abstractNote = {Existing lithium-ion battery technology is struggling to meet our increasing requirements for high energy density, long lifetime, and low-cost energy storage. Here, a hybrid electrode design is developed by a straightforward reengineering of commercial electrode materials, which has revolutionized the “rocking chair” mechanism by unlocking the role of anions in the electrolyte. Our proof-of-concept hybrid LiFePO4(LFP)/graphite electrode works with a staged deintercalation/intercalation mechanism of Li+cations and PF6-anions in a broadened voltage range, which was thoroughly studied byex situX-ray diffraction,ex situRaman spectroscopy, andoperandoneutron powder diffraction. Introducing graphite into the hybrid electrode accelerates its conductivity, facilitating the rapid extraction/insertion of Li+from/into the LFP phase in 2.5 to 4.0 V. This charge/discharge process, in turn, triggers the in situ formation of the cathode/electrolyte interphase (CEI) layer, reinforcing the structural integrity of the whole electrode at high voltage. Consequently, this hybrid LFP/graphite-20% electrode displays a high capacity and long-term cycling stability over 3,500 cycles at 10 C, superior to LFP and graphite cathodes. Importantly, the broadened voltage range and high capacity of the hybrid electrode enhance its energy density, which is leveraged further in a full-cell configuration.},
doi = {10.1073/pnas.1918442117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 117,
place = {United States},
year = {Wed Jan 29 00:00:00 EST 2020},
month = {Wed Jan 29 00:00:00 EST 2020}
}
Web of Science
Works referenced in this record:
Reversible Anion Storage in a Metal-Organic Framework for Dual-Ion Battery Systems
journal, January 2019
- Dühnen, Simon; Nölle, Roman; Wrogemann, Jens
- Journal of The Electrochemical Society, Vol. 166, Issue 3
The cathode–electrolyte interface in the Li-ion battery
journal, November 2004
- Edström, K.; Gustafsson, T.; Thomas, J. O.
- Electrochimica Acta, Vol. 50, Issue 2-3
Soft Carbon as Anode for High-Performance Sodium-Based Dual Ion Full Battery
journal, March 2017
- Fan, Ling; Liu, Qian; Chen, Suhua
- Advanced Energy Materials, Vol. 7, Issue 14
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
Optimized LiFePO[sub 4] for Lithium Battery Cathodes
journal, January 2001
- Yamada, A.; Chung, S. C.; Hinokuma, K.
- Journal of The Electrochemical Society, Vol. 148, Issue 3
Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007
- Ferrari, Andrea C.
- Solid State Communications, Vol. 143, Issue 1-2, p. 47-57
Wombat: The high-intensity powder diffractometer at the OPAL reactor
journal, November 2006
- Studer, Andrew J.; Hagen, Mark E.; Noakes, Terrence J.
- Physica B: Condensed Matter, Vol. 385-386
Performance and cost of materials for lithium-based rechargeable automotive batteries
journal, April 2018
- Schmuch, Richard; Wagner, Ralf; Hörpel, Gerhard
- Nature Energy, Vol. 3, Issue 4
An operando X-ray diffraction study of chloroaluminate anion-graphite intercalation in aluminum batteries
journal, May 2018
- Pan, Chun-Jern; Yuan, Chunze; Zhu, Guanzhou
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 22
Unlocking the energy capabilities of micron-sized LiFePO4
journal, August 2015
- Guo, Limin; Zhang, Yelong; Wang, Jiawei
- Nature Communications, Vol. 6, Issue 1
Study of the Cathode–Electrolyte Interface of LiMn[sub 1.5]Ni[sub 0.5]O[sub 4] Synthesized by a Sol–Gel Method for Li-Ion Batteries
journal, January 2010
- Duncan, Hugues; Abu-Lebdeh, Yaser; Davidson, Isobel J.
- Journal of The Electrochemical Society, Vol. 157, Issue 4
Aqueous Li-ion battery enabled by halogen conversion–intercalation chemistry in graphite
journal, May 2019
- Yang, Chongyin; Chen, Ji; Ji, Xiao
- Nature, Vol. 569, Issue 7755
Heterostructure Manipulation via in Situ Localized Phase Transformation for High-Rate and Highly Durable Lithium Ion Storage
journal, September 2018
- Hao, Junnan; Zhang, Jian; Xia, Guanglin
- ACS Nano, Vol. 12, Issue 10
Ab-initio simulations of materials using VASP: Density-functional theory and beyond
journal, October 2008
- Hafner, Jürgen
- Journal of Computational Chemistry, Vol. 29, Issue 13
Surface Characterization of Electrodes from High Power Lithium-Ion Batteries
journal, January 2002
- Andersson, A. M.; Abraham, D. P.; Haasch, R.
- Journal of The Electrochemical Society, Vol. 149, Issue 10
Perspective on Performance, Cost, and Technical Challenges for Practical Dual-Ion Batteries
journal, December 2018
- Placke, Tobias; Heckmann, Andreas; Schmuch, Richard
- Joule, Vol. 2, Issue 12
Highly Improved Cycling Stability of Anion De-/Intercalation in the Graphite Cathode for Dual-Ion Batteries
journal, November 2018
- Li, Wen-Hao; Ning, Qiu-Li; Xi, Xiao-Tong
- Advanced Materials, Vol. 31, Issue 4
SiO 2 -Enhanced Structural Stability and Strong Adhesion with a New Binder of Konjac Glucomannan Enables Stable Cycling of Silicon Anodes for Lithium-Ion Batteries
journal, June 2018
- Guo, Songtao; Li, Heng; Li, Yaqian
- Advanced Energy Materials, Vol. 8, Issue 24
Fast Diffusivity of PF 6 – Anions in Graphitic Carbon for a Dual-Carbon Rechargeable Battery with Superior Rate Property
journal, September 2016
- Miyoshi, Seiji; Akbay, Taner; Kurihara, Takuya
- The Journal of Physical Chemistry C, Vol. 120, Issue 40
An Outlook on Lithium Ion Battery Technology
journal, September 2017
- Manthiram, Arumugam
- ACS Central Science, Vol. 3, Issue 10
Lithium Nitrate Solvation Chemistry in Carbonate Electrolyte Sustains High-Voltage Lithium Metal Batteries
journal, September 2018
- Yan, Chong; Yao, Yu-Xing; Chen, Xiang
- Angewandte Chemie International Edition, Vol. 57, Issue 43
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
Ultrafast all-climate aluminum-graphene battery with quarter-million cycle life
journal, December 2017
- Chen, Hao; Xu, Hanyan; Wang, Siyao
- Science Advances, Vol. 3, Issue 12
Energy and Capacity Projections for Practical Dual-Graphite Cells
journal, January 2000
- Dahn, J. R.; Seel, J. A.
- Journal of The Electrochemical Society, Vol. 147, Issue 3
A custom battery for operando neutron powder diffraction studies of electrode structure
journal, January 2015
- Pang, Wei Kong; Peterson, Vanessa K.
- Journal of Applied Crystallography, Vol. 48, Issue 1
Analysis and visualisation of neutron-scattering data
journal, December 1996
- Richard, D.; Ferrand, M.; Kearley, G. J.
- Journal of Neutron Research, Vol. 4, Issue 1
Electrochemical Intercalation of PF 6 into Graphite
journal, January 2000
- Seel, J. A.; Dahn, J. R.
- Journal of The Electrochemical Society, Vol. 147, Issue 3, p. 892-898
Carbon-Coated Porous Aluminum Foil Anode for High-Rate, Long-Term Cycling Stability, and High Energy Density Dual-Ion Batteries
journal, September 2016
- Tong, Xuefeng; Zhang, Fan; Ji, Bifa
- Advanced Materials, Vol. 28, Issue 45
A Review on the Features and Progress of Dual-Ion Batteries
journal, March 2018
- Wang, Meng; Tang, Yongbing
- Advanced Energy Materials, Vol. 8, Issue 19
X-ray diffraction patterns of graphite and turbostratic carbon
journal, July 2007
- Li, Z. Q.; Lu, C. J.; Xia, Z. P.
- Carbon, Vol. 45, Issue 8
Recent progress and perspectives on dual-ion batteries
journal, July 2019
- Hao, Junnan; Li, Xiaolong; Song, Xiaohe
- EnergyChem, Vol. 1, Issue 1
A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework
journal, October 2015
- Aubrey, Michael L.; Long, Jeffrey R.
- Journal of the American Chemical Society, Vol. 137, Issue 42
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014
- Larcher, D.; Tarascon, J-M.
- Nature Chemistry, Vol. 7, Issue 1
Li-ion battery materials: present and future
journal, June 2015
- Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae
- Materials Today, Vol. 18, Issue 5
An In Situ Interface Reinforcement Strategy Achieving Long Cycle Performance of Dual‐Ion Batteries
journal, February 2019
- Han, Xiaoqi; Xu, Gaojie; Zhang, Zhonghua
- Advanced Energy Materials, Vol. 9, Issue 16
Optimization of electrochemical properties of LiFePO4/C prepared by an aqueous solution method using sucrose
journal, January 2010
- Kadoma, Yoshihiro; Kim, Jung-Min; Abiko, Katsutoshi
- Electrochimica Acta, Vol. 55, Issue 3
Investigation of SEI Layer Formation in Conversion Iron Fluoride Cathodes by Combined STEM/EELS and XPS
journal, April 2015
- Sina, M.; Thorpe, R.; Rangan, S.
- The Journal of Physical Chemistry C, Vol. 119, Issue 18
The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013
- Goodenough, John B.; Park, Kyu-Sung
- Journal of the American Chemical Society, Vol. 135, Issue 4
Fast charging of lithium-ion batteries at all temperatures
journal, June 2018
- Yang, Xiao-Guang; Zhang, Guangsheng; Ge, Shanhai
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 28
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997
- Padhi, A. K.
- Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
First-principles study of Li ion diffusion in
journal, March 2004
- Ouyang, Chuying; Shi, Siqi; Wang, Zhaoxiang
- Physical Review B, Vol. 69, Issue 10
Yolk–Shell Structured FeP@C Nanoboxes as Advanced Anode Materials for Rechargeable Lithium‐/Potassium‐Ion Batteries
journal, February 2019
- Yang, Fuhua; Gao, Hong; Hao, Junnan
- Advanced Functional Materials, Vol. 29, Issue 16
Atomic-Scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO 4 Olivine-Type Battery Material
journal, October 2005
- Islam, M. Saiful; Driscoll, Daniel J.; Fisher, Craig A. J.
- Chemistry of Materials, Vol. 17, Issue 20
A Novel Aluminum-Graphite Dual-Ion Battery
journal, March 2016
- Zhang, Xiaolong; Tang, Yongbing; Zhang, Fan
- Advanced Energy Materials, Vol. 6, Issue 11
Lithium Nitrate Solvation Chemistry in Carbonate Electrolyte Sustains High-Voltage Lithium Metal Batteries
journal, September 2018
- Yan, Chong; Yao, Yu-Xing; Chen, Xiang
- Angewandte Chemie, Vol. 130, Issue 43