Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes

Chen, Lin; Chen, Kan -Sheng; Chen, Xinjie; Ramirez, Giovanni; Huang, Zhennan; Geise, Natalie R.; Steinrück, Hans -Georg; Fisher, Brandon L.; Shahbazian-Yassar, Reza; Toney, Michael F.; Hersam, Mark C.; Elam, Jeffrey W.

doi:10.1021/acsami.8b04573

Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes

Journal Article · Mon Jul 09 00:00:00 EDT 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b04573· OSTI ID:1476140

Chen, Lin ^[1]; Chen, Kan -Sheng ^[2]; Chen, Xinjie ^[2]; Ramirez, Giovanni ^[3]; Huang, Zhennan ^[4]; Geise, Natalie R. ^[5]; Steinrück, Hans -Georg ^[6]; Fisher, Brandon L. ^[1]; Shahbazian-Yassar, Reza ^[4]; ^[6]; ^[2]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Bruker Nano Surfaces, San Jose, CA (United States)
Univ. of Illinois at Chicago, Chicago, IL (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

Lithium metal anodes can largely enhance the energy density of rechargeable batteries because of the high theoretical capacity and the high negative potential. However, the problem of lithium dendrite formation and low Coulombic efficiency (CE) during electrochemical cycling must be solved before lithium anodes can be widely deployed. Herein, a new atomic layer deposition (ALD) chemistry to realize the low-temperature synthesis of homogeneous and stoichiometric lithium fluoride (LiF) is reported, which then for the first time, as far as we know, is deposited directly onto lithium metal. The LiF preparation is performed at 150 °C yielding 0.8 Å/cycle. The LiF films are found to be crystalline, highly conformal, and stoichiometric with purity levels >99%. Nanoindentation measurements demonstrate the LiF achieving a shear modulus of 58 GPa, 7 times higher than the sufficient value to resist lithium dendrites. When used as the protective coating on lithium, it enables a stable Coulombic efficiency as high as 99.5% for over 170 cycles, about 4 times longer than that of bare lithium anodes. The remarkable battery performance is attributed to the nanosized LiF that serves two critical functions simultaneously: (1) the high dielectric value creates a uniform current distribution for excellent lithium stripping/plating and ultrahigh mechanical strength to suppress lithium dendrites; (2) the great stability and electrolyte isolation by the pure LiF on lithium prevents parasitic reactions for a much improved CE. Here, this new ALD chemistry for conformal LiF not only offers a promising avenue to implement lithium metal anodes for high-capacity batteries but also paves the way for future studies to investigate failure and evolution mechanisms of solid electrolyte interphase (SEI) using our LiF on anodes such as graphite, silicon, and lithium.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 1476140

Alternate ID(s):: OSTI ID: 1493895

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 32 Vol. 10; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Phosphorous Pentasulfide as a Novel Additive for High-Performance Lithium-Sulfur Batteries Lin, Zhan; Liu, Zengcai; Fu, Wujun Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200696	journal	June 2012
Ultra-Uniform SnO _x /Carbon Nanohybrids toward Advanced Lithium-Ion Battery Anodes Zhou, Xiaosi; Dai, Zhihui; Liu, Shuhu Advanced Materials, Vol. 26, Issue 23 https://doi.org/10.1002/adma.201400173	journal	March 2014
An Artificial Solid Electrolyte Interphase Layer for Stable Lithium Metal Anodes Li, Nian-Wu; Yin, Ya-Xia; Yang, Chun-Peng Advanced Materials, Vol. 28, Issue 9 https://doi.org/10.1002/adma.201504526	journal	December 2015
Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries Cheng, Xin-Bing; Hou, Ting-Zheng; Zhang, Rui Advanced Materials, Vol. 28, Issue 15 https://doi.org/10.1002/adma.201506124	journal	February 2016
An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes Liu, Yayuan; Lin, Dingchang; Yuen, Pak Yan Advanced Materials, Vol. 29, Issue 10 https://doi.org/10.1002/adma.201605531	journal	December 2016
A Review of Solid Electrolyte Interphases on Lithium Metal Anode Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Advanced Science, Vol. 3, Issue 3 https://doi.org/10.1002/advs.201500213	journal	November 2015
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
Stable Cycling of Lithium Metal Batteries Using High Transference Number Electrolytes Lu, Yingying; Tikekar, Mukul; Mohanty, Ritesh Advanced Energy Materials, Vol. 5, Issue 9 https://doi.org/10.1002/aenm.201402073	journal	February 2015
Defect Chemistry: Composition, Transport, and Reactions in the Solid State; Part I: Thermodynamics Maier, Joachim Angewandte Chemie International Edition in English, Vol. 32, Issue 3 https://doi.org/10.1002/anie.199303133	journal	March 1993
Atomic Layer Deposition of Li _x Al _y S Solid-State Electrolytes for Stabilizing Lithium-Metal Anodes Cao, Yanqiang; Meng, Xiangbo; Elam, Jeffrey W. ChemElectroChem, Vol. 3, Issue 6 https://doi.org/10.1002/celc.201600139	journal	April 2016
Atomic Layer Deposition of LiF Thin Films from Lithd and TiF ₄ Precursors Mäntymäki, Miia; Hämäläinen, Jani; Puukilainen, Esa Chemical Vapor Deposition, Vol. 19, Issue 4-6 https://doi.org/10.1002/cvde.201207026	journal	May 2013
Influence of OH− ions on infrared absorption and ionic conductivity in lithium fluoride crystals Stoebe, Thomas G. Journal of Physics and Chemistry of Solids, Vol. 28, Issue 8 https://doi.org/10.1016/0022-3697(67)90266-1	journal	August 1967
Composition, depth profiles and lateral distribution of materials in the SEI built on HOPG-TOF SIMS and XPS studies Peled, E.; Bar Tow, D.; Merson, A. Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00505-5	journal	July 2001
Long lifespan lithium metal anodes enabled by Al2O3 sputter coating Wang, Liping; Zhang, Lei; Wang, Qingji Energy Storage Materials, Vol. 10 https://doi.org/10.1016/j.ensm.2017.08.001	journal	January 2018
A simple composite protective layer coating that enhances the cycling stability of lithium metal batteries Lee, Hongkyung; Lee, Dong Jin; Kim, Yun-Jung Journal of Power Sources, Vol. 284 https://doi.org/10.1016/j.jpowsour.2015.03.004	journal	June 2015
Improved Cycle Life and Stability of Lithium Metal Anodes through Ultrathin Atomic Layer Deposition Surface Treatments Kazyak, Eric; Wood, Kevin N.; Dasgupta, Neil P. Chemistry of Materials, Vol. 27, Issue 18 https://doi.org/10.1021/acs.chemmater.5b02789	journal	September 2015
Elastic Properties of the Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03854	journal	December 2015
Interface Stability in Solid-State Batteries Richards, William D.; Miara, Lincoln J.; Wang, Yan Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04082	journal	December 2015
Atomic Layer Deposition of Metal Fluorides Using HF–Pyridine as the Fluorine Precursor Lee, Younghee; Sun, Huaxing; Young, Matthias J. Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.5b04360	journal	March 2016
Stable Artificial Solid Electrolyte Interphases for Lithium Batteries Ma, Lin; Kim, Mun Sek; Archer, Lynden A. Chemistry of Materials, Vol. 29, Issue 10 https://doi.org/10.1021/acs.chemmater.6b03687	journal	May 2017
Mixing Behavior in Small Molecule:Fullerene Organic Photovoltaics Oosterhout, Stefan D.; Savikhin, Victoria; Zhang, Junxiang Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00067	journal	March 2017
Poly(ethyl α-cyanoacrylate)-Based Artificial Solid Electrolyte Interphase Layer for Enhanced Interface Stability of Li Metal Anodes Hu, Zhenglin; Zhang, Shu; Dong, Shanmu Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.7b00091	journal	May 2017
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00115	journal	July 2017
Attainable Gravimetric and Volumetric Energy Density of Li–S and Li Ion Battery Cells with Solid Separator-Protected Li Metal Anodes McCloskey, Bryan D. The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b01814	journal	October 2015
Tribochemistry of Carbon Films in Oxygen and Humid Environments: Oxidative Wear and Galvanic Corrosion Alazizi, Ala; Draskovics, Andrew; Ramirez, Giovanni Langmuir, Vol. 32, Issue 8 https://doi.org/10.1021/acs.langmuir.5b04207	journal	February 2016
Conformal Lithium Fluoride Protection Layer on Three-Dimensional Lithium by Nonhazardous Gaseous Reagent Freon Lin, Dingchang; Liu, Yayuan; Chen, Wei Nano Letters, Vol. 17, Issue 6 https://doi.org/10.1021/acs.nanolett.7b01020	journal	May 2017
First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF Yildirim, Handan; Kinaci, Alper; Chan, Maria K. Y. ACS Applied Materials & Interfaces, Vol. 7, Issue 34 https://doi.org/10.1021/acsami.5b02904	journal	August 2015
Dual-Phase Lithium Metal Anode Containing a Polysulfide-Induced Solid Electrolyte Interphase and Nanostructured Graphene Framework for Lithium–Sulfur Batteries Cheng, Xin-Bing; Peng, Hong-Jie; Huang, Jia-Qi ACS Nano, Vol. 9, Issue 6 https://doi.org/10.1021/acsnano.5b01990	journal	May 2015
Next-Generation Lithium Metal Anode Engineering via Atomic Layer Deposition Kozen, Alexander C.; Lin, Chuan-Fu; Pearse, Alexander J. ACS Nano, Vol. 9, Issue 6 https://doi.org/10.1021/acsnano.5b02166	journal	May 2015
Atomic Layer Deposition of Stable LiAlF ₄ Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling Xie, Jin; Sendek, Austin D.; Cubuk, Ekin D. ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.7b02561	journal	July 2017
Atomic Layer Deposition of LiF Thin Films from Lithd, Mg(thd) ₂ , and TiF ₄ Precursors Mäntymäki, Miia; Hämäläinen, Jani; Puukilainen, Esa Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm400046w	journal	April 2013
Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism Ding, Fei; Xu, Wu; Graff, Gordon L. Journal of the American Chemical Society, Vol. 135, Issue 11, p. 4450-4456 https://doi.org/10.1021/ja312241y	journal	March 2013
Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries Khurana, Rachna; Schaefer, Jennifer L.; Archer, Lynden A. Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja502133j	journal	May 2014
Lithium Metal Anodes with an Adaptive “Solid-Liquid” Interfacial Protective Layer Liu, Kai; Pei, Allen; Lee, Hye Ryoung Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.6b13314	journal	March 2017
Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode Yan, Kai; Lee, Hyun-Wook; Gao, Teng Nano Letters, Vol. 14, Issue 10 https://doi.org/10.1021/nl503125u	journal	September 2014
Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu Nano Letters, Vol. 14, Issue 12 https://doi.org/10.1021/nl5039117	journal	November 2014
Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries Suo, Liumin; Hu, Yong-Sheng; Li, Hong Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2513	journal	February 2013
Defect-induced plating of lithium metal within porous graphene networks Mukherjee, Rahul; Thomas, Abhay V.; Datta, Dibakar Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4710	journal	April 2014
High rate and stable cycling of lithium metal anode Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7362	journal	February 2015
Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries Bouchet, Renaud; Maria, Sébastien; Meziane, Rachid Nature Materials, Vol. 12, Issue 5 https://doi.org/10.1038/nmat3602	journal	March 2013
Interconnected hollow carbon nanospheres for stable lithium metal anodes Zheng, Guangyuan; Lee, Seok Woo; Liang, Zheng Nature Nanotechnology, Vol. 9, Issue 8 https://doi.org/10.1038/nnano.2014.152	journal	July 2014
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
Lithium metal anodes for rechargeable batteries Xu, Wu; Wang, Jiulin; Ding, Fei Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE40795K	journal	January 2014
Enhanced electrochemical properties of a LiNiO ₂ -based cathode material by removing lithium residues with (NH ₄ ) ₂ HPO ₄ Xiong, Xunhui; Ding, Dong; Bu, Yunfei J. Mater. Chem. A, Vol. 2, Issue 30 https://doi.org/10.1039/C4TA01282H	journal	January 2014
Bottom-up, hard template and scalable approaches toward designing nanostructured Li ₂ S for high performance lithium sulfur batteries Chen, Lin; Liu, Yuzi; Dietz-Rago, Nancy Nanoscale, Vol. 7, Issue 43 https://doi.org/10.1039/C5NR04478B	journal	January 2015
Lithium transport through lithium-ion battery cathode coatings Xu, Shenzhen; Jacobs, Ryan M.; Nguyen, Ha M. Journal of Materials Chemistry A, Vol. 3, Issue 33 https://doi.org/10.1039/C5TA01664A	journal	January 2015
New insights into the electrode mechanism of lithium sulfur batteries via air-free post-test analysis Chen, Lin; Dietz Rago, Nancy L.; Bloom, Ira D. Chemical Communications, Vol. 52, Issue 64 https://doi.org/10.1039/C6CC04401H	journal	January 2016
Lithium metal protected by atomic layer deposition metal oxide for high performance anodes Chen, Lin; Connell, Justin G.; Nie, Anmin Journal of Materials Chemistry A, Vol. 5, Issue 24 https://doi.org/10.1039/C7TA03116E	journal	January 2017
Nanostructured metal oxide-based materials as advanced anodes for lithium-ion batteries Wu, Hao Bin; Chen, Jun Song; Hng, Huey Hoon Nanoscale, Vol. 4, Issue 8, p. 2526-2542 https://doi.org/10.1039/c2nr11966h	journal	January 2012
Synthesis and characterization of nano- and microcrystalline cubes of pure and Ag-doped LiF Alharbi, Najlaa D.; Salah, Numan; Habib, Sami S. Journal of Physics D: Applied Physics, Vol. 46, Issue 3 https://doi.org/10.1088/0022-3727/46/3/035305	journal	December 2012
Unit-cell dimensions of lithium fluoride made from Li ⁶ and Li ⁷ Thewlis, J. Acta Crystallographica, Vol. 8, Issue 1 https://doi.org/10.1107/S0365110X55000091	journal	January 1955
What is the Young's Modulus of Silicon? Hopcroft, Matthew A.; Nix, William D.; Kenny, Thomas W. Journal of Microelectromechanical Systems, Vol. 19, Issue 2 https://doi.org/10.1109/JMEMS.2009.2039697	journal	April 2010
Dendrite Growth in Lithium/Polymer Systems Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 150, Issue 10 https://doi.org/10.1149/1.1606686	journal	January 2003
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces Monroe, Charles; Newman, John Journal of The Electrochemical Society, Vol. 152, Issue 2 https://doi.org/10.1149/1.1850854	journal	January 2005
Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode Harry, Katherine J.; Higa, Kenneth; Srinivasan, Venkat Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.0191610jes	journal	January 2016
Mechanical and Thermal Properties of Certain Optical Crystalline Materials* Combes, Lewis S.; Ballard, Stanley S.; McCarthy, Kathryn A. Journal of the Optical Society of America, Vol. 41, Issue 4 https://doi.org/10.1364/JOSA.41.000215	journal	January 1951
ALD for clean energy conversion, utilization, and storage Elam, Jeffrey W.; Dasgupta, Neil P.; Prinz, Fritz B. MRS Bulletin, Vol. 36, Issue 11, p. 899-906 https://doi.org/10.1557/mrs.2011.265	journal	November 2011

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
atomic layer deposition
high shear modulus
lithium fluoride
lithium metal anode
new chemistry

Novel ALD Chemistry Enabled Low-Temperature Synthesis of Lithium Fluoride Coatings for Durable Lithium Anodes

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