Nanoporous Polymer Films with a High Cation Transference Number Stabilize Lithium Metal Anodes in Light-Weight Batteries for Electrified Transportation

Ma, Lin; Fu, Chengyin; Li, Longjun; Mayilvahanan, Karthik S.; Watkins, Tylan; Perdue, Brian R.; Zavadil, Kevin R.; Helms, Brett A.

doi:10.1021/acs.nanolett.8b05101

Nanoporous Polymer Films with a High Cation Transference Number Stabilize Lithium Metal Anodes in Light-Weight Batteries for Electrified Transportation

Journal Article · Tue Jan 22 23:00:00 EST 2019 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.8b05101· OSTI ID:1507408

Ma, Lin ^[1]; Fu, Chengyin ^[1]; Li, Longjun ^[1]; Mayilvahanan, Karthik S. ^[2]; Watkins, Tylan ^[3]; Perdue, Brian R. ^[3]; ^[3]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

To suppress dendrite formation in lithium metal batteries, high cation transference number electrolytes that reduce electrode polarization are highly desirable, but rarely available using conventional liquid electrolytes. Here, we show that liquid electrolytes increase their cation transference numbers (e.g., ~0.2 to >0.70) when confined to a structurally rigid polymer host whose pores are on a similar length scale (0.5–2 nm) as the Debye screening length in the electrolyte, which results in a diffuse electrolyte double layer at the polymer–electrolyte interface that retains counterions and reject co-ions from the electrolyte due to their larger size. Lithium anodes coated with ~1 μm thick overlayers of the polymer host exhibit both a low area-specific resistance and clear dendrite-suppressing character, as evident from their performance in Li–Li and Li–Cu cells as well as in post-mortem analysis of the anode’s morphology after cycling. High areal capacity Li–S cells (4.9 mg cm^–2; 8.2 mAh cm^–2) implementing these high transference number polymer-hosted liquid electrolytes were remarkably stable, considering ~24 μm of lithium was electroreversibly deposited in each cycle at a C-rate of 0.2. In conclusion, we further identified a scalable manufacturing path for these polymer-coated lithium electrodes, which are drop-in components for lithium metal battery manufacturing.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1507408

Alternate ID(s):: OSTI ID: 1634042

Report Number(s):: SAND--2019-3255J; 673712

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 2 Vol. 19; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

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
Poly(dimethylsiloxane) Thin Film as a Stable Interfacial Layer for High-Performance Lithium-Metal Battery Anodes Zhu, Bin; Jin, Yan; Hu, Xiaozhen Advanced Materials, Vol. 29, Issue 2 https://doi.org/10.1002/adma.201603755	journal	October 2016
Engineered Transport in Microporous Materials and Membranes for Clean Energy Technologies Li, Changyi; Meckler, Stephen M.; Smith, Zachary P. Advanced Materials, Vol. 30, Issue 8 https://doi.org/10.1002/adma.201704953	journal	January 2018
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
Review on Li-Sulfur Battery Systems: an Integral Perspective Rosenman, Ariel; Markevich, Elena; Salitra, Gregory Advanced Energy Materials, Vol. 5, Issue 16 https://doi.org/10.1002/aenm.201500212	journal	May 2015
Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors Choi, Nam-Soon; Chen, Zonghai; Freunberger, Stefan A. Angewandte Chemie International Edition, Vol. 51, Issue 40 https://doi.org/10.1002/anie.201201429	journal	September 2012
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
Design Principles of Functional Polymer Separators for High-Energy, Metal-Based Batteries Zhang, Weidong; Tu, Zhengyuan; Qian, Jiawei Small, Vol. 14, Issue 11 https://doi.org/10.1002/smll.201703001	journal	December 2017
Incorporating ionic size in the transport equations for charged nanopores Cervera, Javier; Ramírez, Patricio; Manzanares, José A. Microfluidics and Nanofluidics, Vol. 9, Issue 1 https://doi.org/10.1007/s10404-009-0518-2	journal	October 2009
Steady state current flow in solid binary electrolyte cells Bruce, Peter G.; Vincent, Colin A. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 225, Issue 1-2 https://doi.org/10.1016/0022-0728(87)80001-3	journal	June 1987
Electrochemical measurement of transference numbers in polymer electrolytes Evans, James; Vincent, Colin A.; Bruce, Peter G. Polymer, Vol. 28, Issue 13 https://doi.org/10.1016/0032-3861(87)90394-6	journal	December 1987
Conductivity and transference number measurements on polymer electrolytes Bruce, P. Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/0167-2738(88)90304-9	journal	September 1988
Designing Artificial Solid-Electrolyte Interphases for Single-Ion and High-Efficiency Transport in Batteries Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J. Joule, Vol. 1, Issue 2 https://doi.org/10.1016/j.joule.2017.06.002	journal	October 2017
Atomistic packing model and free volume distribution of a polymer with intrinsic microporosity (PIM-1) Heuchel, Matthias; Fritsch, Detlev; Budd, Peter M. Journal of Membrane Science, Vol. 318, Issue 1-2 https://doi.org/10.1016/j.memsci.2008.02.038	journal	June 2008
Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: Polybenzodioxane PIM-1 Budd, P.; Mckeown, N.; Ghanem, B. Journal of Membrane Science, Vol. 325, Issue 2 https://doi.org/10.1016/j.memsci.2008.09.010	journal	December 2008
Impedance Characteristics of Amine Modified Single Glass Nanopores Feng, Jingyu; Liu, Juan; Wu, Baohua Analytical Chemistry, Vol. 82, Issue 11 https://doi.org/10.1021/ac100440z	journal	June 2010
Hybrid Hairy Nanoparticle Electrolytes Stabilizing Lithium Metal Batteries Choudhury, Snehashis; Agrawal, Akanksha; Wei, Shuya Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00029	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
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
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
Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes Timachova, Ksenia; Watanabe, Hiroshi; Balsara, Nitash P. Macromolecules, Vol. 48, Issue 21 https://doi.org/10.1021/acs.macromol.5b01724	journal	October 2015
Architected Macroporous Polyelectrolytes That Suppress Dendrite Formation during High-Rate Lithium Metal Electrodeposition Li, Longjun; Ma, Lin; Helms, Brett A. Macromolecules, Vol. 51, Issue 19 https://doi.org/10.1021/acs.macromol.8b01188	journal	September 2018
Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries Li, Changyi; Ward, Ashleigh L.; Doris, Sean E. Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b02078	journal	August 2015
Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries that Operate at Ambient Temperature Porcarelli, Luca; Shaplov, Alexander S.; Bella, Federico ACS Energy Letters, Vol. 1, Issue 4 https://doi.org/10.1021/acsenergylett.6b00216	journal	September 2016
Harnessing the Power of Plastics: Nanostructured Polymer Systems in Lithium-Ion Batteries Morris, Melody A.; An, Hyosung; Lutkenhaus, Jodie L. ACS Energy Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acsenergylett.7b00368	journal	August 2017
Performance Metrics Required of Next-Generation Batteries to Make a Practical Electric Semi Truck Sripad, Shashank; Viswanathan, Venkatasubramanian ACS Energy Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsenergylett.7b00432	journal	June 2017
Single-Ion Homopolymer Electrolytes with High Transference Number Prepared by Click Chemistry and Photoinduced Metal-Free Atom-Transfer Radical Polymerization Li, Sipei; Mohamed, Alexander I.; Pande, Vikram ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b00999	journal	November 2017
Interphases in Lithium–Sulfur Batteries: Toward Deployable Devices with Competitive Energy Density and Stability Zhao, Qing; Zheng, Jingxu; Archer, Lynden ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b01001	journal	August 2018
Phase-Field Simulations of Lithium Dendrite Growth with Open-Source Software Hong, Zijian; Viswanathan, Venkatasubramanian ACS Energy Letters, Vol. 3, Issue 7 https://doi.org/10.1021/acsenergylett.8b01009	journal	June 2018
Electrolyte Confinement Alters Lithium Electrodeposition Mistry, Aashutosh; Fear, Conner; Carter, Rachel ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02003	journal	December 2018
Quantifying the Economic Case for Electric Semi-Trucks Sripad, Shashank; Viswanathan, Venkatasubramanian ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02146	journal	December 2018
Performance Metrics Required of Next-Generation Batteries to Electrify Vertical Takeoff and Landing (VTOL) Aircraft Fredericks, William L.; Sripad, Shashank; Bower, Geoffrey C. ACS Energy Letters, Vol. 3, Issue 12 https://doi.org/10.1021/acsenergylett.8b02195	journal	November 2018
High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites Schaefer, Jennifer L.; Yanga, Dennis A.; Archer, Lynden A. Chemistry of Materials, Vol. 25, Issue 6 https://doi.org/10.1021/cm303091j	journal	March 2013
Aprotic and Aqueous Li–O₂ Batteries Lu, Jun; Li, Li; Park, Jin-Bum Chemical Reviews, Vol. 114, Issue 11, p. 5611-5640 https://doi.org/10.1021/cr400573b	journal	April 2014
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
Stabilizing Lithium Metal Anodes by Uniform Li-Ion Flux Distribution in Nanochannel Confinement Liu, Wei; Lin, Dingchang; Pei, Allen Journal of the American Chemical Society, Vol. 138, Issue 47 https://doi.org/10.1021/jacs.6b08730	journal	November 2016
Surface Charge Density Determination of Single Conical Nanopores Based on Normalized Ion Current Rectification Liu, Juan; Kvetny, Maksim; Feng, Jingyu Langmuir, Vol. 28, Issue 2 https://doi.org/10.1021/la203106w	journal	December 2011
Quantification of Steady-State Ion Transport through Single Conical Nanopores and a Nonuniform Distribution of Surface Charges Liu, Juan; Wang, Dengchao; Kvetny, Maksim Langmuir, Vol. 29, Issue 27 https://doi.org/10.1021/la4009009	journal	June 2013
Molecular Simulations of PIM-1-like Polymers of Intrinsic Microporosity Larsen, Gregory S.; Lin, Ping; Hart, Kyle E. Macromolecules, Vol. 44, Issue 17 https://doi.org/10.1021/ma200345v	journal	September 2011
Transference Number Approaching Unity in Nanocomposite Electrolytes Jorne, Jacob Nano Letters, Vol. 6, Issue 12 https://doi.org/10.1021/nl062182m	journal	December 2006
Lithium battery chemistries enabled by solid-state electrolytes Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei Nature Reviews Materials, Vol. 2, Issue 4 https://doi.org/10.1038/natrevmats.2016.103	journal	February 2017
Promise and reality of post-lithium-ion batteries with high energy densities Choi, Jang Wook; Aurbach, Doron Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.13	journal	March 2016
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
Design principles for electrolytes and interfaces for stable lithium-metal batteries Tikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.114	journal	September 2016
Electrolyte additive enabled fast charging and stable cycling lithium metal batteries Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai Nature Energy, Vol. 2, Issue 3 https://doi.org/10.1038/nenergy.2017.12	journal	March 2017
Stable lithium electrodeposition in liquid and nanoporous solid electrolytes Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A. Nature Materials, Vol. 13, Issue 10 https://doi.org/10.1038/nmat4041	journal	August 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
Molecular understanding of polyelectrolyte binders that actively regulate ion transport in sulfur cathodes Li, Longjun; Pascal, Tod A.; Connell, Justin G. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02410-6	journal	December 2017
Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries Albertus, Paul; Babinec, Susan; Litzelman, Scott Nature Energy, Vol. 3, Issue 1 https://doi.org/10.1038/s41560-017-0047-2	journal	December 2017
Performance and cost of materials for lithium-based rechargeable automotive batteries Schmuch, Richard; Wagner, Ralf; Hörpel, Gerhard Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0107-2	journal	April 2018
Batteries and fuel cells for emerging electric vehicle markets Cano, Zachary P.; Banham, Dustin; Ye, Siyu Nature Energy, Vol. 3, Issue 4 https://doi.org/10.1038/s41560-018-0108-1	journal	April 2018
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
History-dependent ion transport through conical nanopipettes and the implications in energy conversion dynamics at nanoscale interfaces Li, Yan; Wang, Dengchao; Kvetny, Maksim M. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC02195A	journal	January 2015
Structure–property study of cross-linked hydrocarbon/poly(ethylene oxide) electrolytes with superior conductivity and dendrite resistance Zheng, Qi; Ma, Lin; Khurana, Rachna Chemical Science, Vol. 7, Issue 11 https://doi.org/10.1039/C6SC01813K	journal	January 2016
Infiltrated porous oxide monoliths as high lithium transference number electrolytes Popovic, Jelena; Hasegawa, George; Moudrakovski, Igor Journal of Materials Chemistry A, Vol. 4, Issue 19 https://doi.org/10.1039/C6TA01826B	journal	January 2016
Understanding and controlling the chemical evolution and polysulfide-blocking ability of lithium–sulfur battery membranes cast from polymers of intrinsic microporosity Doris, Sean E.; Ward, Ashleigh L.; Frischmann, Peter D. Journal of Materials Chemistry A, Vol. 4, Issue 43 https://doi.org/10.1039/C6TA06401A	journal	January 2016
New horizons for inorganic solid state ion conductors Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE01053F	journal	January 2018
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

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High cation transference number
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Nanoporous Polymer Films with a High Cation Transference Number Stabilize Lithium Metal Anodes in Light-Weight Batteries for Electrified Transportation

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