Lithium Growth on Alloying Substrates and Effect on Volumetric Expansion

Merrill, Laura Christine; Craig, Robert Lee; Cummings, Damion P.; Deitz, Julia Irene

doi:10.3390/batteries11070249

Lithium Growth on Alloying Substrates and Effect on Volumetric Expansion

Journal Article · Sun Jun 29 00:00:00 EDT 2025 · Batteries

DOI:https://doi.org/10.3390/batteries11070249· OSTI ID:2585652

^[1]; Craig, Robert Lee ^[1]; Cummings, Damion P. ^[1]; ^[1]

Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

The widespread implementation of next-generation Li metal anodes is limited, in part, due to the formation of dendritic and/or mossy electrodeposits during cycling. These morphologies can lead to battery failure due to the formation of short circuits and significant volumetric expansion at the anode. One strategy to control the electrodeposition of Li metal is to use lithiophilic materials at the anode. Here, we evaluate the impact of Ag and Au on the early stages of Li metal electrodeposition and cycling. The alloying substrates decrease the voltage for Li reduction and improve Li wetting/adhesion. We probe volumetric expansion directly through dilatometry measurements and find that the degree of volumetric expansion is less when lithium is cycled on an alloying substrate compared to a non-alloying substrate (Cu). Dilatometry experiments reveal that Au has the least amount of volumetric expansion and coin cell cycling experiments indicate that Ag yields more stable cycling compared to Au or Cu. The evaluation of in situ cross-sectional images of cycled coin cells shows that Ag has the lowest volumetric expansion in a coin cell format.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2585652

Report Number(s):: SAND--2025-08011J; 1765561

Journal Information:: Batteries, Journal Name: Batteries Journal Issue: 7 Vol. 11; ISSN 2313-0105

Publisher:: MDPI AGCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Towards High-Safe Lithium Metal Anodes: Suppressing Lithium Dendrites via Tuning Surface Energy Wang, Dong; Zhang, Wei; Zheng, Weitao Advanced Science, Vol. 4, Issue 1 https://doi.org/10.1002/advs.201600168	journal	July 2016
Enhanced Stability of Li Metal Anodes by Synergetic Control of Nucleation and the Solid Electrolyte Interphase Peng, Zhe; Song, Junhua; Huai, Liyuan Advanced Energy Materials, Vol. 9, Issue 42 https://doi.org/10.1002/aenm.201901764	journal	September 2019
Marginal Magnesium Doping for High‐Performance Lithium Metal Batteries Choi, Seung Ho; Lee, Seung Jong; Yoo, Dong‐Joo Advanced Energy Materials, Vol. 9, Issue 41 https://doi.org/10.1002/aenm.201902278	journal	September 2019
Fast‐Charging and Ultrahigh‐Capacity Lithium Metal Anode Enabled by Surface Alloying Xu, Tianhui; Gao, Peng; Li, Peirong Advanced Energy Materials, Vol. 10, Issue 8 https://doi.org/10.1002/aenm.201902343	journal	January 2020
Review of Emerging Concepts in SEI Analysis and Artificial SEI Membranes for Lithium, Sodium, and Potassium Metal Battery Anodes Liu, Wei; Liu, Pengcheng; Mitlin, David Advanced Energy Materials, Vol. 10, Issue 43 https://doi.org/10.1002/aenm.202002297	journal	October 2020
Porous Lithiophilic Li–Si Alloy‐Type Interfacial Framework via Self‐Discharge Mechanism for Stable Lithium Metal Anode with Superior Rate Park, Jung Been; Choi, Changhoon; Yu, Seungho Advanced Energy Materials, Vol. 11, Issue 37 https://doi.org/10.1002/aenm.202101544	journal	August 2021
Electroless Formation of Hybrid Lithium Anodes for Fast Interfacial Ion Transport Choudhury, Snehashis; Tu, Zhengyuan; Stalin, Sanjuna Angewandte Chemie International Edition, Vol. 56, Issue 42 https://doi.org/10.1002/anie.201707754	journal	September 2017
Artificial Solid‐Electrolyte Interphase for Lithium Metal Batteries Kang, Danmiao; Xiao, Muye; Lemmon, John P. Batteries & Supercaps, Vol. 4, Issue 3 https://doi.org/10.1002/batt.202000225	journal	December 2020
Li‐containing alloys beneficial for stabilizing lithium anode: A review Gu, Xingxing; Dong, Jing; Lai, Chao Engineering Reports, Vol. 3, Issue 1 https://doi.org/10.1002/eng2.12339	journal	December 2020
Sustaining Surface Lithiophilicity of Ultrathin Li‐Alloy Coating Layers on Current Collector for Zero‐Excess Li‐Metal Batteries Seo, Jiyeon; Lim, Jihye; Chang, Hongjun Small, Vol. 20, Issue 47 https://doi.org/10.1002/smll.202402988	journal	July 2024
Study of lithium metal-based electrodes by electrochemical dilatometry Fatahine, Mohamed; Guay, Daniel; Roué, Lionel Journal of Applied Electrochemistry, Vol. 52, Issue 1 https://doi.org/10.1007/s10800-021-01626-1	journal	October 2021
Thickness dependence of high volumetric energy density lithium ion battery based on Sn–Zn eutectic alloy foil anode Zhang, Xin; Gong, Yangjie; Xu, Chunyi Ionics, Vol. 28, Issue 6 https://doi.org/10.1007/s11581-022-04550-2	journal	April 2022
Electrochemical properties of Li–Mg alloy electrodes for lithium batteries Shi, Zhong; Liu, Meilin; Naik, Devang Journal of Power Sources, Vol. 92, Issue 1-2 https://doi.org/10.1016/S0378-7753(00)00521-8	journal	January 2001
Lithium metal stripping/plating mechanisms studies: A metallurgical approach Gireaud, L.; Grugeon, S.; Laruelle, S. Electrochemistry Communications, Vol. 8, Issue 10, p. 1639-1649 https://doi.org/10.1016/j.elecom.2006.07.037	journal	October 2006
Lithiation and Delithiation Mechanisms of Gold Thin Film Model Anodes for Lithium Ion Batteries: Electrochemical Characterization Bach, P.; Stratmann, M.; Valencia-Jaime, I. Electrochimica Acta, Vol. 164 https://doi.org/10.1016/j.electacta.2015.02.184	journal	May 2015
A novel dual-protection interface based on gallium-lithium alloy enables dendrite-free lithium metal anodes Zhou, Ying; Zhang, Jiaming; Zhao, Kai Energy Storage Materials, Vol. 39 https://doi.org/10.1016/j.ensm.2021.04.042	journal	August 2021
Fast cycling of “anode-less”, redox-mediated Li-S flow batteries Meyerson, Melissa L.; Maraschky, Adam M.; Watt, John Journal of Energy Storage, Vol. 72 https://doi.org/10.1016/j.est.2023.108767	journal	November 2023
Cryogenic electron microscopy reveals that applied pressure promotes short circuits in Li batteries Harrison, Katharine L.; Merrill, Laura C.; Long, Daniel Martin iScience, Vol. 24, Issue 12 https://doi.org/10.1016/j.isci.2021.103394	journal	December 2021
Silver: high performance anode for thin film lithium ion batteries Taillades, G.; Sarradin, J. Journal of Power Sources, Vol. 125, Issue 2 https://doi.org/10.1016/j.jpowsour.2003.07.004	journal	January 2004
Lithium plating induced volume expansion overshoot of lithium-ion batteries: Experimental analysis and modeling Wang, Shan; Ren, Dongsheng; Xu, Chengshan Journal of Power Sources, Vol. 593 https://doi.org/10.1016/j.jpowsour.2023.233946	journal	February 2024
Stack pressure on lithium-ion pouch cells: A comparative study of constant pressure and fixed displacement devices Schommer, Adriano; Corzo, Miguel Orozco; Henshall, Paul Journal of Power Sources, Vol. 629 https://doi.org/10.1016/j.jpowsour.2024.236019	journal	February 2025
Sputter coating of lithium metal electrodes with lithiophilic metals for homogeneous and reversible lithium electrodeposition and electrodissolution Stan, Marian Cristian; Becking, Jens; Kolesnikov, Aleksei Materials Today, Vol. 39 https://doi.org/10.1016/j.mattod.2020.04.002	journal	October 2020
Intraparticle alloying-plating reaction for high-performing lithium metal batteries with low volume expansion Chen, Zidong; Luo, Yiteng; Yang, Dongsheng Materials Today, Vol. 86 https://doi.org/10.1016/j.mattod.2025.03.012	journal	July 2025
Entrapping lithium deposition in lithiophilic reservoir constructed by vertically aligned ZnO nanosheets for dendrite-free Li metal anodes Zhao, Fei; Zhou, Xufeng; Deng, Wei Nano Energy, Vol. 62 https://doi.org/10.1016/j.nanoen.2019.04.087	journal	August 2019
Stable lithium metal anode enabled by lithium metal partial alloying Qiu, Hailong; Tang, Tianyu; Asif, Muhammad Nano Energy, Vol. 65 https://doi.org/10.1016/j.nanoen.2019.103989	journal	November 2019
Nanoscale Protection Layers To Mitigate Degradation in High-Energy Electrochemical Energy Storage Systems Lin, Chuan-Fu; Qi, Yue; Gregorczyk, Keith Accounts of Chemical Research, Vol. 51, Issue 1 https://doi.org/10.1021/acs.accounts.7b00524	journal	January 2018
Role of Lithiophilic Metal Sites in Lithium Metal Anodes Chen, Xiao-Ru; Chen, Xiang; Yan, Chong Energy & Fuels, Vol. 35, Issue 15 https://doi.org/10.1021/acs.energyfuels.1c01602	journal	July 2021
Progress, Challenges, and Perspectives on Alloy-Based Anode Materials for Lithium Ion Battery: A Mini-Review Gopinadh, Sumol V.; Phanendra, Peddinti V. R. L.; V., Anoopkumar Energy & Fuels, Vol. 38, Issue 18 https://doi.org/10.1021/acs.energyfuels.4c03023	journal	August 2024
Role of Coatings as Artificial Solid Electrolyte Interphases on Lithium Metal Self-Discharge Merrill, Laura C.; Long, Daniel M.; Small, Kathryn A. The Journal of Physical Chemistry C, Vol. 126, Issue 41 https://doi.org/10.1021/acs.jpcc.2c05385	journal	October 2022
Chemical Energy Release Driven Lithiophilic Layer on 1 m ² Commercial Brass Mesh toward Highly Stable Lithium Metal Batteries Huang, Shaobo; Zhang, Wenfeng; Ming, Hai Nano Letters, Vol. 19, Issue 3 https://doi.org/10.1021/acs.nanolett.8b04919	journal	January 2019
Uncovering the Relationship between Aging and Cycling on Lithium Metal Battery Self-Discharge Merrill, Laura C.; Rosenberg, Samantha G.; Jungjohann, Katherine L. ACS Applied Energy Materials, Vol. 4, Issue 8 https://doi.org/10.1021/acsaem.1c00874	journal	August 2021
Engineering Lithiophilic Silver Sponge Integrated with Ion-Conductive PVDF/LiF Protective Layer for Dendrite-Free and High-Performance Lithium Metal Batteries Liu, Hong-Jun; Qu, Jin; Chang, Yu ACS Applied Energy Materials, Vol. 6, Issue 1 https://doi.org/10.1021/acsaem.2c03528	journal	December 2022
Solubility-Dependent Protective Effects of Binary Alloys for Lithium Anode Xu, Yan; Zhao, Shuyang; Zhou, Guangmin ACS Applied Energy Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsaem.9b02125	journal	February 2020
High-Throughput Exploration of Lithium-Alloy Protection Layers for High-Performance Lithium-Metal Batteries Manandhar, Kedar; Ren, Yaoyu; Stasak, Drew ACS Applied Energy Materials, Vol. 3, Issue 3 https://doi.org/10.1021/acsaem.9b02252	journal	February 2020
Three-Dimensional Ordered Macro/Mesoporous Cu/Zn as a Lithiophilic Current Collector for Dendrite-Free Lithium Metal Anode Zhang, Duo; Dai, Alvin; Fan, Binfeng ACS Applied Materials & Interfaces, Vol. 12, Issue 28 https://doi.org/10.1021/acsami.0c09503	journal	June 2020
Electrochemical Lithiation/Delithiation of ZnO in 3D-Structured Electrodes: Elucidating the Mechanism and the Solid Electrolyte Interphase Formation Kreissl, Julian J. A.; Petit, Jan; Oppermann, Raika ACS Applied Materials & Interfaces, Vol. 13, Issue 30 https://doi.org/10.1021/acsami.1c06135	journal	July 2021
Effects of Applied Interfacial Pressure on Li-Metal Cycling Performance and Morphology in 4 M LiFSI in DME Harrison, Katharine L.; Goriparti, Subrahmanyam; Merrill, Laura C. ACS Applied Materials & Interfaces, Vol. 13, Issue 27 https://doi.org/10.1021/acsami.1c06488	journal	June 2021
One-Pot Preparation of Lithium Compensation Layer, Lithiophilic Layer, and Artificial Solid Electrolyte Interphase for Lean-Lithium Metal Anode Li, Cheng; Li, Yan; Yu, Yongkun ACS Applied Materials & Interfaces, Vol. 14, Issue 17 https://doi.org/10.1021/acsami.2c01716	journal	April 2022
Cryogenic Laser Ablation Reveals Short-Circuit Mechanism in Lithium Metal Batteries Jungjohann, Katherine L.; Gannon, Renae N.; Goriparti, Subrahmanyam ACS Energy Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsenergylett.1c00509	journal	May 2021
Phase Diagram Determined Lithium Plating/Stripping Behaviors on Lithiophilic Substrates Zhang, Simeng; Yang, Gaojing; Liu, Zepeng ACS Energy Letters, Vol. 6, Issue 11 https://doi.org/10.1021/acsenergylett.1c02127	journal	November 2021
Tuning Lithiophilic Sites of Ag-Embedded N-Doped Carbon Hollow Spheres via Intentional Blocking Strategy for Ultrastable Li Metal Anode in Rechargeable Batteries Kim, Minjun; Lee, Seunghak; Park, Dohyub ACS Sustainable Chemistry & Engineering, Vol. 11, Issue 5 https://doi.org/10.1021/acssuschemeng.2c05918	journal	January 2023
Solid–Solution-Based Metal Alloy Phase for Highly Reversible Lithium Metal Anode Jin, Song; Ye, Yadong; Niu, Yijie Journal of the American Chemical Society, Vol. 142, Issue 19 https://doi.org/10.1021/jacs.0c01811	journal	April 2020
Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth Yan, Kai; Lu, Zhenda; Lee, Hyun-Wook Nature Energy, Vol. 1, Issue 3, Article No. 16010 https://doi.org/10.1038/nenergy.2016.10	journal	February 2016
Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization Cao, Xia; Ren, Xiaodi; Zou, Lianfeng Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0464-5	journal	September 2019
Best practices in lithium battery cell preparation and evaluation Dai, Fang; Cai, Mei Communications Materials, Vol. 3, Issue 1 https://doi.org/10.1038/s43246-022-00286-8	journal	September 2022
Regulating electrodeposition morphology of lithium: towards commercially relevant secondary Li metal batteries Zheng, Jingxu; Kim, Mun Sek; Tu, Zhengyuan Chemical Society Reviews, Vol. 49, Issue 9 https://doi.org/10.1039/C9CS00883G	journal	January 2020
A study of lithium insertion into electrodes with thin gold films Kulova, T. L.; Skundin, A. M.; Kozhevin, V. M. Russian Journal of Electrochemistry, Vol. 46, Issue 8 https://doi.org/10.1134/S1023193510080033	journal	August 2010
Understanding Li Plating and Stripping Behavior in Zero-Excess Li Metal Batteries Using Operando Dilatometry Lohrberg, Oliver; Maletti, Sebastian; Heubner, Christian Journal of The Electrochemical Society, Vol. 169, Issue 3 https://doi.org/10.1149/1945-7111/ac5cf1	journal	March 2022
Editors’ Choice—Methods—Pressure Control Apparatus for Lithium Metal Batteries Lu, Bingyu; Bao, Wurigumula; Yao, Weiliang Journal of The Electrochemical Society, Vol. 169, Issue 7 https://doi.org/10.1149/1945-7111/ac834c	journal	July 2022
Miniaturization of Reference Electrodes for Solid-State Lithium-Ion Batteries Hertle, Jonas; Walther, Felix; Mogwitz, Boris Journal of The Electrochemical Society, Vol. 170, Issue 4 https://doi.org/10.1149/1945-7111/accb6f	journal	April 2023
Evaluation of Lithium Metal Anode Volumetric Expansion through Laser Plasma Focused Ion Beam Cross-Sectional Imaging Merrill, Laura C.; Gannon, Renae N.; Jungjohann, Katherine L. Journal of The Electrochemical Society, Vol. 170, Issue 8 https://doi.org/10.1149/1945-7111/acf162	journal	August 2023
Interfacial pressure improves calendar aging of lithium metal anodes Bassett, Kimberly L.; Small, Kathryn A.; Long, Daniel M. Frontiers in Batteries and Electrochemistry, Vol. 2 https://doi.org/10.3389/fbael.2023.1292639	journal	October 2023
Unlocking the Potential of Li–Ag Alloys: Phase Selection and Practical Application Huang, Yuping; Chen, Shiwei; Yang, Yu Energy Material Advances, Vol. 5 https://doi.org/10.34133/energymatadv.0108	journal	January 2024

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Lithium Growth on Alloying Substrates and Effect on Volumetric Expansion

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