Emerging Potassium Metal Anodes: Perspectives on Control of the Electrochemical Interfaces
Abstract
Potassium metal acts as the anode in emerging potassium metal batteries (KMBs). It further serves as the counter-electrode for potassium ion battery (KIB) half-cells, with its reliable performance being critical for assessing the working electrode material. This first-of-its-kind critical review focuses on the dual challenge of controlling the potassium metal-substrate and the potassium metal-electrolyte interface so as to prevent dendrites. The discussion begins with a comparison of the physical and chemical properties of K metal anodes versus the much oft studied Li and Na metal anodes. Based on established descriptions for root causes of dendrites, the problem should be less severe for K than for Li or Na, while in fact the opposite is observed. The key reason that the K metal surface rapidly becomes dendritic in common electrolytes is its unstable solid electrolyte interphase (SEI). An unstable SEI layer is defined as being non self-passivating. No SEI is perfectly stable during cycling, and all SEI structures are heterogenous both vertically and horizontally relative to the electrolyte interface. The difference between a "stable" and an "unstable" SEI may be viewed as the relative degree to which during cycling it thickens and becomes further heterogeneous. The unstable SEI on K metalmore »
- Authors:
-
- Univ. of Texas, Austin, TX (United States)
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1631281
- Grant/Contract Number:
- SC0018074
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Accounts of Chemical Research
- Additional Journal Information:
- Journal Volume: 53; Journal Issue: 6; Journal ID: ISSN 0001-4842
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; potassium metal battery (PMB, KMB); potassium sulfur battery; lithium metal battery (LMB); sodium metal battery (SMB, NMB); lithium sulfur battery, potassium ion battery (KIB, PIB).
Citation Formats
Liu, Pengcheng, and Mitlin, David. Emerging Potassium Metal Anodes: Perspectives on Control of the Electrochemical Interfaces. United States: N. p., 2020.
Web. doi:10.1021/acs.accounts.0c00099.
Liu, Pengcheng, & Mitlin, David. Emerging Potassium Metal Anodes: Perspectives on Control of the Electrochemical Interfaces. United States. https://doi.org/10.1021/acs.accounts.0c00099
Liu, Pengcheng, and Mitlin, David. Thu .
"Emerging Potassium Metal Anodes: Perspectives on Control of the Electrochemical Interfaces". United States. https://doi.org/10.1021/acs.accounts.0c00099. https://www.osti.gov/servlets/purl/1631281.
@article{osti_1631281,
title = {Emerging Potassium Metal Anodes: Perspectives on Control of the Electrochemical Interfaces},
author = {Liu, Pengcheng and Mitlin, David},
abstractNote = {Potassium metal acts as the anode in emerging potassium metal batteries (KMBs). It further serves as the counter-electrode for potassium ion battery (KIB) half-cells, with its reliable performance being critical for assessing the working electrode material. This first-of-its-kind critical review focuses on the dual challenge of controlling the potassium metal-substrate and the potassium metal-electrolyte interface so as to prevent dendrites. The discussion begins with a comparison of the physical and chemical properties of K metal anodes versus the much oft studied Li and Na metal anodes. Based on established descriptions for root causes of dendrites, the problem should be less severe for K than for Li or Na, while in fact the opposite is observed. The key reason that the K metal surface rapidly becomes dendritic in common electrolytes is its unstable solid electrolyte interphase (SEI). An unstable SEI layer is defined as being non self-passivating. No SEI is perfectly stable during cycling, and all SEI structures are heterogenous both vertically and horizontally relative to the electrolyte interface. The difference between a "stable" and an "unstable" SEI may be viewed as the relative degree to which during cycling it thickens and becomes further heterogeneous. The unstable SEI on K metal leads to a number of interrelated problems, such as low cycling Coulombic efficiency (CE), a severe impedance rise, large overpotentials, and possibly electrical shorting; all of which have been reported to occur as early as in the first ten plating/stripping cycles. Many of the traditional "interface fixes" employed for Li and Na metal anodes, such as various artificial SEIs, surface membranes, barrier layers, the secondary separators, etc. have not been attempted or optimized for the case of K. This is an important area for further exploration, with an understanding that success may come harder than with Li due to K-based SEI reactivity with both ether and ester solvents. The second critical problem with K metal anodes is that they do not thermally or electrochemically wet a standard (untreated) Cu foil current collector. Published experimental and modeling research directly highlights the weak bonding between the K atoms and a Cu surface. Existing surface treatment approaches that achieve improved K wetting are discussed, along with the general design rules for future studies. Also discussed are geometry-based methods to tune nucleation, as well dual approaches where nucleation and SEI structure are tuned through complementary schemes to achieve extended half-cell and full battery stability. We hypothesize that K metal never achieves a planar wetting morphology even at cycle one making the dendrites "baked-in". We propose that classical thin films growth models, Frank van der Merwe (F-M), Volmer Weber (V-W), and Stranski-Krastanov (S-K) can be employed to describe early stage plating behavior. It is demonstrated that island-like V-W growth is the applicable description for the natural plating behavior of K on pristine Cu. Moving forward, there are three inter-related thrusts to be pursued: First, K salt - based electrolyte formulations have to mature and become further tailored to handle the increased reactivity of a metal rather than an ion anode. Second, the K-based SEI structure needs to be further understood and ultimately tuned to be less reactive. Third, the energetics of the K metal - current collector interface must be controlled to promote planar wetting/dewetting throughout cycling.},
doi = {10.1021/acs.accounts.0c00099},
journal = {Accounts of Chemical Research},
number = 6,
volume = 53,
place = {United States},
year = {Thu May 28 00:00:00 EDT 2020},
month = {Thu May 28 00:00:00 EDT 2020}
}
Web of Science
Works referenced in this record:
How we made the Li-ion rechargeable battery
journal, March 2018
- Goodenough, John B.
- Nature Electronics, Vol. 1, Issue 3
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
A cost and resource analysis of sodium-ion batteries
journal, March 2018
- Vaalma, Christoph; Buchholz, Daniel; Weil, Marcel
- Nature Reviews Materials, Vol. 3, Issue 4
Research Development on K-Ion Batteries
journal, January 2020
- Hosaka, Tomooki; Kubota, Kei; Hameed, A. Shahul
- Chemical Reviews, Vol. 120, Issue 14
Approaching high-performance potassium-ion batteries via advanced design strategies and engineering
journal, May 2019
- Zhang, Wenchao; Liu, Yajie; Guo, Zaiping
- Science Advances, Vol. 5, Issue 5
Review of Emerging Potassium–Sulfur Batteries
journal, April 2020
- Ding, Jia; Zhang, Hao; Fan, Wenjie
- Advanced Materials, Vol. 32, Issue 23
Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors
journal, November 2015
- Komaba, Shinichi; Hasegawa, Tatsuya; Dahbi, Mouad
- Electrochemistry Communications, Vol. 60
Towards K-Ion and Na-Ion Batteries as “Beyond Li-Ion”
journal, February 2018
- Kubota, Kei; Dahbi, Mouad; Hosaka, Tomooki
- The Chemical Record, Vol. 18, Issue 4
Dendrite‐Free Potassium Metal Anodes in a Carbonate Electrolyte
journal, November 2019
- Liu, Pengcheng; Wang, Yixian; Gu, Qilin
- Advanced Materials, Vol. 32, Issue 7
Sulfur‐Grafted Hollow Carbon Spheres for Potassium‐Ion Battery Anodes
journal, June 2019
- Ding, Jia; Zhang, Hanlei; Zhou, Hui
- Advanced Materials
Cathode Materials for Potassium-Ion Batteries: Current Status and Perspective
journal, October 2018
- Zhang, Qing; Wang, Zhijie; Zhang, Shilin
- Electrochemical Energy Reviews, Vol. 1, Issue 4
Reviving the lithium metal anode for high-energy batteries
journal, March 2017
- Lin, Dingchang; Liu, Yayuan; Cui, Yi
- Nature Nanotechnology, Vol. 12, Issue 3
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review
journal, July 2017
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Chemical Reviews, Vol. 117, Issue 15
Sodium Metal Anodes: Emerging Solutions to Dendrite Growth
journal, April 2019
- Lee, Byeongyong; Paek, Eunsu; Mitlin, David
- Chemical Reviews, Vol. 119, Issue 8
Recent developments and insights into the understanding of Na metal anodes for Na-metal batteries
journal, January 2018
- Zhao, Yang; Adair, Keegan R.; Sun, Xueliang
- Energy & Environmental Science, Vol. 11, Issue 10
Natural SEI-Inspired Dual-Protective Layers via Atomic/Molecular Layer Deposition for Long-Life Metallic Lithium Anode
journal, November 2019
- Zhao, Yang; Amirmaleki, Maedeh; Sun, Qian
- Matter, Vol. 1, Issue 5
Electrochemical aspects of the generation of ramified metallic electrodeposits
journal, December 1990
- Chazalviel, J. -N.
- Physical Review A, Vol. 42, Issue 12
Microscopic properties of lithium, sodium, and magnesium battery anode materials related to possible dendrite growth
journal, November 2014
- Jäckle, Markus; Groß, Axel
- The Journal of Chemical Physics, Vol. 141, Issue 17
Dendrite Growth in Lithium/Polymer Systems
journal, January 2003
- Monroe, Charles; Newman, John
- Journal of The Electrochemical Society, Vol. 150, Issue 10
Pathways for practical high-energy long-cycling lithium metal batteries
journal, February 2019
- Liu, Jun; Bao, Zhenan; Cui, Yi
- Nature Energy, Vol. 4, Issue 3
Dendritic growth mechanisms in lithium/polymer cells
journal, September 1999
- Brissot, C.; Rosso, M.; Chazalviel, J. -N.
- Journal of Power Sources, Vol. 81-82
Solvation and Dynamics of Sodium and Potassium in Ethylene Carbonate from ab Initio Molecular Dynamics Simulations
journal, September 2017
- Pham, Tuan Anh; Kweon, Kyoung E.; Samanta, Amit
- The Journal of Physical Chemistry C, Vol. 121, Issue 40
Artificial Solid‐Electrolyte Interphase Enabled High‐Capacity and Stable Cycling Potassium Metal Batteries
journal, September 2019
- Wang, Huwei; Hu, Junyang; Dong, Jiahui
- Advanced Energy Materials, Vol. 9, Issue 43
A 4 V Class Potassium Metal Battery with Extremely Low Overpotential
journal, July 2019
- Ye, Minghui; Hwang, Jang-Yeon; Sun, Yang-Kook
- ACS Nano, Vol. 13, Issue 8
Li 2 O-Reinforced Cu Nanoclusters as Porous Structure for Dendrite-Free and Long-Lifespan Lithium Metal Anode
journal, September 2016
- Zhang, Zhenggang; Xu, Xiaoyue; Wang, Shuwei
- ACS Applied Materials & Interfaces, Vol. 8, Issue 40
Chemical Dealloying Derived 3D Porous Current Collector for Li Metal Anodes
journal, May 2016
- Yun, Qinbai; He, Yan-Bing; Lv, Wei
- Advanced Materials, Vol. 28, Issue 32
Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode
journal, March 2016
- Liu, Yayuan; Lin, Dingchang; Liang, Zheng
- Nature Communications, Vol. 7, Issue 1
Covalently Connected Carbon Nanostructures for Current Collectors in Both the Cathode and Anode of Li-S Batteries
journal, September 2016
- Jin, Song; Xin, Sen; Wang, Linjun
- Advanced Materials, Vol. 28, Issue 41
Electrochemical Alloying of Lithium in Organic Electrolytes
journal, January 1971
- Dey, A. N.
- Journal of The Electrochemical Society, Vol. 118, Issue 10
Film forming reaction at the lithium/electrolyte interface
journal, January 1983
- Peled, E.
- Journal of Power Sources, Vol. 9, Issue 3
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
Intermolecular Chemistry in Solid Polymer Electrolytes for High‐Energy‐Density Lithium Batteries
journal, July 2019
- Zhou, Qian; Ma, Jun; Dong, Shanmu
- Advanced Materials, Vol. 31, Issue 50
Room-Temperature Potassium–Sulfur Batteries Enabled by Microporous Carbon Stabilized Small-Molecule Sulfur Cathodes
journal, January 2019
- Xiong, Peixun; Han, Xinpeng; Zhao, Xinxin
- ACS Nano
Electrode–electrolyte interfaces in lithium-based batteries
journal, January 2018
- Yu, Xingwen; Manthiram, Arumugam
- Energy & Environmental Science, Vol. 11, Issue 3
Review—SEI: Past, Present and Future
journal, January 2017
- Peled, E.; Menkin, S.
- Journal of The Electrochemical Society, Vol. 164, Issue 7
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures
journal, January 1996
- Aurbach, D.
- Journal of The Electrochemical Society, Vol. 143, Issue 12
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy
journal, October 2017
- Li, Yuzhang; Li, Yanbin; Pei, Allen
- Science, Vol. 358, Issue 6362
New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM
journal, November 2017
- Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith
- Nano Letters, Vol. 17, Issue 12
Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries
journal, August 2018
- Zachman, Michael J.; Tu, Zhengyuan; Choudhury, Snehashis
- Nature, Vol. 560, Issue 7718
Potassium Metal as Reliable Reference Electrodes of Nonaqueous Potassium Cells
journal, May 2019
- Hosaka, Tomooki; Muratsubaki, Shotaro; Kubota, Kei
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 12
Reversible Dendrite-Free Potassium Plating and Stripping Electrochemistry for Potassium Secondary Batteries
journal, July 2017
- Xiao, Neng; McCulloch, William D.; Wu, Yiying
- Journal of the American Chemical Society, Vol. 139, Issue 28
Original growth mechanism for ultra-stable dendrite-free potassium metal electrode
journal, August 2019
- Li, Yuqian; Zhang, Liyuan; Liu, Sufu
- Nano Energy, Vol. 62
Pristine or Highly Defective? Understanding the Role of Graphene Structure for Stable Lithium Metal Plating
journal, November 2018
- Liu, Wei; Xia, Yuting; Wang, Wenwu
- Advanced Energy Materials, Vol. 9, Issue 3
Understanding High-Energy-Density Sn4P3 Anodes for Potassium-Ion Batteries
journal, August 2018
- Zhang, Wenchao; Pang, Wei Kong; Sencadas, Vitor
- Joule, Vol. 2, Issue 8
Simultaneous Stabilization of Potassium Metal and Superoxide in K-O 2 Batteries on the Basis of Electrolyte Reactivity
journal, June 2018
- Xiao, Neng; Gourdin, Gerald; Wu, Yiying
- Angewandte Chemie International Edition, Vol. 57, Issue 34
Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes
journal, April 2018
- Gu, Yu; Wang, Wei-Wei; Li, Yi-Juan
- Nature Communications, Vol. 9, Issue 1
Capillary Encapsulation of Metallic Potassium in Aligned Carbon Nanotubes for Use as Stable Potassium Metal Anodes
journal, June 2019
- Qin, Lei; Lei, Yu; Wang, Huwei
- Advanced Energy Materials, Vol. 9, Issue 29
3D Vertically Aligned Li Metal Anodes with Ultrahigh Cycling Currents and Capacities of 10 mA cm −2 /20 mAh cm −2 Realized by Selective Nucleation within Microchannel Walls
journal, January 2020
- Gao, Xuejie; Yang, Xiaofei; Adair, Keegan
- Advanced Energy Materials, Vol. 10, Issue 7
Addressing Interfacial Issues in Liquid-Based and Solid-State Batteries by Atomic and Molecular Layer Deposition
journal, December 2018
- Zhao, Yang; Zheng, Kelly; Sun, Xueliang
- Joule, Vol. 2, Issue 12
Self-heating–induced healing of lithium dendrites
journal, March 2018
- Li, Lu; Basu, Swastik; Wang, Yiping
- Science, Vol. 359, Issue 6383
Encapsulation of Metallic Na in an Electrically Conductive Host with Porous Channels as a Highly Stable Na Metal Anode
journal, May 2017
- Luo, Wei; Zhang, Ying; Xu, Shaomao
- Nano Letters, Vol. 17, Issue 6
Nip the Sodium Dendrites in the Bud on Planar Doped Graphene in Liquid/Gel Electrolytes
journal, January 2019
- Hu, Xiaofei; Joo, Paul Hyunggyu; Wang, Huan
- Advanced Functional Materials, Vol. 29, Issue 9
Nucleation and Early Stage Growth of Li Electrodeposits
journal, September 2019
- Biswal, Prayag; Stalin, Sanjuna; Kludze, Atsu
- Nano Letters, Vol. 19, Issue 11
MXene‐Based Dendrite‐Free Potassium Metal Batteries
journal, November 2019
- Tang, Xiao; Zhou, Dong; Li, Peng
- Advanced Materials, Vol. 32, Issue 4
Directional Flow-Aided Sonochemistry Yields Graphene with Tunable Defects to Provide Fundamental Insight on Sodium Metal Plating Behavior
journal, November 2018
- Liu, Wei; Li, Peiyu; Wang, Wenwu
- ACS Nano, Vol. 12, Issue 12
Role of Nitrogen-Doped Graphene for Improved High-Capacity Potassium Ion Battery Anodes
journal, October 2016
- Share, Keith; Cohn, Adam P.; Carter, Rachel
- ACS Nano, Vol. 10, Issue 10
Island growth in electrodeposition
journal, October 2011
- Guo, Lian; Oskam, Gerko; Radisic, Aleksandar
- Journal of Physics D: Applied Physics, Vol. 44, Issue 44
Electrodeposition stability of metal electrodes
journal, July 2019
- Hao, Feng; Verma, Ankit; Mukherjee, Partha P.
- Energy Storage Materials, Vol. 20
Liquid K-Na Alloy Anode Enables Dendrite-Free Potassium Batteries
journal, September 2016
- Xue, Leigang; Gao, Hongcai; Zhou, Weidong
- Advanced Materials, Vol. 28, Issue 43
Cathode Dependence of Liquid-Alloy Na–K Anodes
journal, February 2018
- Xue, Leigang; Gao, Hongcai; Li, Yutao
- Journal of the American Chemical Society, Vol. 140, Issue 9
A Liquid‐Metal‐Enabled Versatile Organic Alkali‐Ion Battery
journal, January 2019
- Ding, Yu; Guo, Xuelin; Qian, Yumin
- Advanced Materials, Vol. 31, Issue 11
A functional SrF 2 coated separator enabling a robust and dendrite-free solid electrolyte interphase on a lithium metal anode
journal, January 2019
- Li, Xing; Liu, Yang; Pan, Yong
- Journal of Materials Chemistry A, Vol. 7, Issue 37
In situ healing of dendrites in a potassium metal battery
journal, March 2020
- Hundekar, Prateek; Basu, Swastik; Fan, Xiulin
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 11
An Intrinsically Non‐flammable Electrolyte for High‐Performance Potassium Batteries
journal, January 2020
- Liu, Sailin; Mao, Jianfeng; Zhang, Qing
- Angewandte Chemie International Edition, Vol. 59, Issue 9
Electrolyte Chemistry Enables Simultaneous Stabilization of Potassium Metal and Alloying Anode for Potassium‐Ion Batteries
journal, November 2019
- Wang, Hua; Yu, Dandan; Wang, Xiao
- Angewandte Chemie International Edition, Vol. 58, Issue 46
P2‐K 0.75 [Ni 1/3 Mn 2/3 ]O 2 Cathode Material for High Power and Long Life Potassium‐Ion Batteries
journal, January 2020
- Jo, Jae Hyeon; Choi, Ji Ung; Park, Yun Ji
- Advanced Energy Materials, Vol. 10, Issue 7
Encapsulation of SeS 2 into Nitrogen-Doped Free-Standing Carbon Nanofiber Film Enabling Long Cycle Life and High Energy Density K-SeS 2 Battery
journal, March 2019
- Yao, Yu; Xu, Rui; Chen, Minglong
- ACS Nano, Vol. 13, Issue 4
A new energy storage system: Rechargeable potassium-selenium battery
journal, May 2017
- Liu, Yajie; Tai, Zhixin; Zhang, Qing
- Nano Energy, Vol. 35
A high-rate and long-life organic–oxygen battery
journal, February 2019
- Cong, Guangtao; Wang, Wanwan; Lai, Nien-Chu
- Nature Materials, Vol. 18, Issue 4
A Low-Overpotential Potassium–Oxygen Battery Based on Potassium Superoxide
journal, February 2013
- Ren, Xiaodi; Wu, Yiying
- Journal of the American Chemical Society, Vol. 135, Issue 8, p. 2923-2926
Potassium Superoxide: A Unique Alternative for Metal–Air Batteries
journal, August 2018
- Xiao, Neng; Ren, Xiaodi; McCulloch, William D.
- Accounts of Chemical Research, Vol. 51, Issue 9
Understanding Side Reactions in K–O 2 Batteries for Improved Cycle Life
journal, October 2014
- Ren, Xiaodi; Lau, Kah Chun; Yu, Mingzhe
- ACS Applied Materials & Interfaces, Vol. 6, Issue 21
Dendrite-Free Potassium–Oxygen Battery Based on a Liquid Alloy Anode
journal, March 2017
- Yu, Wei; Lau, Kah Chun; Lei, Yu
- ACS Applied Materials & Interfaces, Vol. 9, Issue 37
Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries
journal, December 2017
- Albertus, Paul; Babinec, Susan; Litzelman, Scott
- Nature Energy, Vol. 3, Issue 1
Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery
journal, January 2020
- Zhou, Yufan; Su, Mao; Yu, Xiaofei
- Nature Nanotechnology, Vol. 15, Issue 3
Machine Learning Interatomic Potentials as Emerging Tools for Materials Science
journal, September 2019
- Deringer, Volker L.; Caro, Miguel A.; Csányi, Gábor
- Advanced Materials, Vol. 31, Issue 46