Control of nanoparticle dispersion, SEI composition, and electrode morphology enables long cycle life in high silicon content nanoparticle-based composite anodes for lithium-ion batteries

Schulze, Maxwell C.; Urias, Fernando; Dutta, Nikita S.; Huey, Zoey; Coyle, Jaclyn; Teeter, Glenn; Doeren, Ryan; Tremolet de Villers, Bertrand J.; Han, Sang-Don; Neale, Nathan R.; Carroll, G. Michael

doi:10.1039/D2TA08935A

Title: Control of nanoparticle dispersion, SEI composition, and electrode morphology enables long cycle life in high silicon content nanoparticle-based composite anodes for lithium-ion batteries

Journal Article · Tue Mar 07 00:00:00 EST 2023 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/D2TA08935A· OSTI ID:1924591

^[1]; Urias, Fernando ^[1];

^[1];

^[1]; Coyle, Jaclyn ^[1]; Teeter, Glenn ^[1]; Doeren, Ryan ^[1];

^[1];

^[1]

National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, USA

Striking a balance between high theoretical capacity, earth abundance, and compatibility with existing manufacturing infrastructure, silicon is one of the few materials that meet the requirements for a next-generation anode for rechargeable lithium-ion batteries. Due to complications with extreme volume changes during charging/discharging and reactive interfacial chemistries, the cycle life of silicon-based composite anodes is unacceptable for broad use. Developing a majority silicon composite anode formulation that overcomes these challenges and is compatible with current industrial manufacturing practices requires materials and chemical engineering solutions that account for both electrode morphology and interfacial chemistry. Here, we synthesize surface-functionalized silicon nanocrystals that enable a highly dispersed and homogeneous slurry that can easily be integrated into a standard electrode fabrication process. We use this formulation to fabricate a 76 wt% silicon composite electrode. We show that the contents and the morphology of the silicon electrolyte interphase – a determining factor for the cycle life of silicon-based anodes – can be controlled with a post-synthetic thermal curing procedure. The curing process removes the organic surface functional groups used initially to enable dispersion in the slurry. Removing the organic surface coating reduces the cell impedance, improves the silicon utilization for lithium storage, and boosts the coulombic efficiency to values > 99.9% when electrochemically cycled. When paired with a capacity-matched lithium nickel manganese cobalt oxide LiNi_0.8Mn_0.1Co_0.1O₂ cathode, the cell retains 72% of its capacity after 1000 charge/discharge cycles while delivering an initial anode specific capacity of nearly 1000 mA h g^-1 and an areal capacity of 2.55 mA h cm^-2.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1924591

Alternate ID(s):: OSTI ID: 1959951

Report Number(s):: NREL/JA-5900-82857; JMCAET

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Vol. 11 Journal Issue: 10; ISSN 2050-7488

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

References (58)

Conveying Advanced Li-ion Battery Materials into Practice The Impact of Electrode Slurry Preparation Skills Kraytsberg, Alexander; Ein-Eli, Yair Advanced Energy Materials, Vol. 6, Issue 21 https://doi.org/10.1002/aenm.201600655	journal	July 2016
Intrinsic Properties of Individual Inorganic Silicon–Electrolyte Interphase Constituents Han, Sang-Don; Wood, Kevin N.; Stetson, Caleb ACS Applied Materials & Interfaces, Vol. 11, Issue 50 https://doi.org/10.1021/acsami.9b18252	journal	November 2019
Chemistry of Electrolyte Reduction on Lithium Silicide Xu, Yun; Wood, Kevin; Coyle, Jaclyn The Journal of Physical Chemistry C, Vol. 123, Issue 21 https://doi.org/10.1021/acs.jpcc.9b02611	journal	May 2019
Evolution of solid electrolyte interphase and active material in the silicon wafer model system Stetson, Caleb; Yin, Yanli; Norman, Andrew Journal of Power Sources, Vol. 482 https://doi.org/10.1016/j.jpowsour.2020.228946	journal	January 2021
Enhanced Interfacial Stability of Si Anodes for Li-Ion Batteries via Surface SiO ₂ Coating Schnabel, Manuel; Arca, Elisabetta; Ha, Yeyoung ACS Applied Energy Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsaem.0c01337	journal	August 2020
Probing the Evolution of Surface Chemistry at the Silicon–Electrolyte Interphase via In Situ Surface-Enhanced Raman Spectroscopy Ha, Yeyoung; Tremolet de Villers, Bertrand J.; Li, Zhifei The Journal of Physical Chemistry Letters, Vol. 11, Issue 1 https://doi.org/10.1021/acs.jpclett.9b03284	journal	December 2019
Silicon-Based Anodes for Lithium-Ion Batteries: From Fundamentals to Practical Applications Feng, Kun; Li, Matthew; Liu, Wenwen Small, Vol. 14, Issue 8 https://doi.org/10.1002/smll.201702737	journal	January 2018
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
Electrochemical Reaction of Lithium with Nanostructured Silicon Anodes: A Study by In-Situ Synchrotron X-Ray Diffraction and Electron Energy-Loss Spectroscopy Wang, Feng; Wu, Lijun; Key, Baris Advanced Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1002/aenm.201300394	journal	August 2013
Mechanical studies of the solid electrolyte interphase on anodes in lithium and lithium ion batteries McBrayer, Josefine D.; Apblett, Christopher A.; Harrison, Katharine L. Nanotechnology, Vol. 32, Issue 50 https://doi.org/10.1088/1361-6528/ac17fe	journal	September 2021
Half-Cell Cumulative Efficiency Forecasts Full-Cell Capacity Retention in Lithium-Ion Batteries Schulze, Maxwell C.; Neale, Nathan R. ACS Energy Letters, Vol. 6, Issue 3 https://doi.org/10.1021/acsenergylett.1c00173	journal	February 2021
Poly(ethylene oxide)-based electrolytes for lithium-ion batteries Xue, Zhigang; He, Dan; Xie, Xiaolin Journal of Materials Chemistry A, Vol. 3, Issue 38 https://doi.org/10.1039/C5TA03471J	journal	January 2015
Review on Polymer-Based Composite Electrolytes for Lithium Batteries Yao, Penghui; Yu, Haobin; Ding, Zhiyu Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00522	journal	August 2019
A review of the multiscale mechanics of silicon electrodes in high-capacity lithium-ion batteries Wang, Haoran; Lu, Shao-Hao; Wang, Xueju Journal of Physics D: Applied Physics, Vol. 55, Issue 6 https://doi.org/10.1088/1361-6463/ac2d64	journal	October 2021
Intrinsic chemical reactivity of solid-electrolyte interphase components in silicon–lithium alloy anode batteries probed by FTIR spectroscopy Pekarek, Ryan T.; Affolter, Alec; Baranowski, Lauryn L. Journal of Materials Chemistry A, Vol. 8, Issue 16 https://doi.org/10.1039/C9TA13535A	journal	January 2020
Thermal characterization of poly(acrylic acid) Maurer, J. J.; Eustace, D. J.; Ratcliffe, C. T. Macromolecules, Vol. 20, Issue 1 https://doi.org/10.1021/ma00167a035	journal	January 1987
Critical Review on Low‐Temperature Li‐Ion/Metal Batteries Zhang, Nan; Deng, Tao; Zhang, Shuoqing Advanced Materials, Vol. 34, Issue 15 https://doi.org/10.1002/adma.202107899	journal	February 2022
25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries McDowell, Matthew T.; Lee, Seok Woo; Nix, William D. Advanced Materials, Vol. 25, Issue 36 https://doi.org/10.1002/adma.201301795	journal	August 2013
Silicon-Based Nanomaterials for Lithium-Ion Batteries: A Review Su, Xin; Wu, Qingliu; Li, Juchuan Advanced Energy Materials, Vol. 4, Issue 1 https://doi.org/10.1002/aenm.201300882	journal	October 2013
Impacts of lean electrolyte on cycle life for rechargeable Li metal batteries Nagpure, Shrikant C.; Tanim, Tanvir R.; Dufek, Eric J. Journal of Power Sources, Vol. 407 https://doi.org/10.1016/j.jpowsour.2018.10.060	journal	December 2018
Silicon based lithium-ion battery anodes: A chronicle perspective review Zuo, Xiuxia; Zhu, Jin; Müller-Buschbaum, Peter Nano Energy, Vol. 31 https://doi.org/10.1016/j.nanoen.2016.11.013	journal	January 2017
Temperature-Dependent Solubility of Solid Electrolyte Interphase on Silicon Electrodes Stetson, Caleb; Yin, Yanli; Jiang, Chun-Sheng ACS Energy Letters, Vol. 4, Issue 12 https://doi.org/10.1021/acsenergylett.9b02082	journal	October 2019
Suppressing Auger Recombination in Multiply Excited Colloidal Silicon Nanocrystals with Ligand-Induced Hole Traps Carroll, Gerard Michael; Limpens, Rens; Pach, Gregory F. The Journal of Physical Chemistry C, Vol. 125, Issue 4 https://doi.org/10.1021/acs.jpcc.0c11388	journal	January 2021
Tailoring the Surface of Silicon Nanoparticles for Enhanced Chemical and Electrochemical Stability for Li-Ion Batteries Jiang, Sisi; Hu, Bin; Sahore, Ritu ACS Applied Energy Materials, Vol. 2, Issue 9 https://doi.org/10.1021/acsaem.9b01601	journal	August 2019
Hydrophobic versus Hydrophilic Interfacial Coatings on Silicon Nanoparticles Teach Us How to Design the Solid Electrolyte Interphase in Silicon-Based Li-Ion Battery Anodes Schulze, Maxwell C.; Carroll, Gerard Michael; Martin, Trevor R. ACS Applied Energy Materials, Vol. 4, Issue 2 https://doi.org/10.1021/acsaem.0c02817	journal	February 2021
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Microscopic Observation of Solid Electrolyte Interphase Bilayer Inversion on Silicon Oxide Stetson, Caleb; Schnabel, Manuel; Li, Zhifei ACS Energy Letters, Vol. 5, Issue 12 https://doi.org/10.1021/acsenergylett.0c02081	journal	October 2020
Nanoscale silicon as anode for Li-ion batteries: The fundamentals, promises, and challenges Gu, Meng; He, Yang; Zheng, Jianming Nano Energy, Vol. 17 https://doi.org/10.1016/j.nanoen.2015.08.025	journal	October 2015
Electrochemically-driven solid-state amorphization in lithium-silicon alloys and implications for lithium storage Limthongkul, Pimpa; Jang, Young-Il; Dudney, Nancy J. Acta Materialia, Vol. 51, Issue 4 https://doi.org/10.1016/S1359-6454(02)00514-1	journal	February 2003
Effect of Water Concentration in LiPF ₆ -Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes Ha, Yeyoung; Stetson, Caleb; Harvey, Steven P. ACS Applied Materials & Interfaces, Vol. 12, Issue 44 https://doi.org/10.1021/acsami.0c12884	journal	October 2020
Impact of Silicon/Graphite Composite Electrode Porosity on the Cycle Life of 18650 Lithium-Ion Cell Profatilova, Irina; De Vito, Eric; Genies, Sylvie ACS Applied Energy Materials, Vol. 3, Issue 12 https://doi.org/10.1021/acsaem.0c01999	journal	December 2020
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Calendar aging of silicon-containing batteries McBrayer, Josefine D.; Rodrigues, Marco-Tulio F.; Schulze, Maxwell C. Nature Energy, Vol. 6, Issue 9 https://doi.org/10.1038/s41560-021-00883-w	journal	September 2021
Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries Wang, Aiping; Kadam, Sanket; Li, Hong npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-018-0064-0	journal	March 2018
Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]∕Carbon Cells with a New Electrolyte Composition Guyomard, D. Journal of The Electrochemical Society, Vol. 140, Issue 11 https://doi.org/10.1149/1.2220987	journal	January 1993
Evaluating the roles of electrolyte components on the passivation of silicon anodes Malkowski, Thomas F.; Yang, Zhenzhen; Sacci, Robert L. Journal of Power Sources, Vol. 523 https://doi.org/10.1016/j.jpowsour.2022.231021	journal	March 2022
Nonpassivated Silicon Anode Surface Yin, Yanli; Arca, Elisabetta; Wang, Luning ACS Applied Materials & Interfaces, Vol. 12, Issue 23 https://doi.org/10.1021/acsami.0c03799	journal	May 2020
Advances of polymer binders for silicon‐based anodes in high energy density lithium‐ion batteries Zhao, Yu‐Ming; Yue, Feng‐Shu; Li, Shi‐Cheng InfoMat, Vol. 3, Issue 5 https://doi.org/10.1002/inf2.12185	journal	March 2021
Identifying the Structural Basis for the Increased Stability of the Solid Electrolyte Interphase Formed on Silicon with the Additive Fluoroethylene Carbonate Jin, Yanting; Kneusels, Nis-Julian H.; Magusin, Pieter C. M. M. Journal of the American Chemical Society, Vol. 139, Issue 42 https://doi.org/10.1021/jacs.7b06834	journal	October 2017
Silicon‐Based Lithium Ion Battery Systems: State‐of‐the‐Art from Half and Full Cell Viewpoint Guo, Junpo; Dong, Dongqi; Wang, Jun Advanced Functional Materials, Vol. 31, Issue 34 https://doi.org/10.1002/adfm.202102546	journal	June 2021
Recent progress of silicon composites as anode materials for secondary batteries Wang, Jingjing; Xu, Tingting; Huang, Xiao RSC Advances, Vol. 6, Issue 90 https://doi.org/10.1039/C6RA08971B	journal	January 2016
Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy Yang, Guang; Sacci, Robert L.; Ivanov, Ilia N. Journal of The Electrochemical Society, Vol. 166, Issue 2 https://doi.org/10.1149/2.0391902jes	journal	January 2019
Frontiers in Theoretical Analysis of Solid Electrolyte Interphase Formation Mechanism Takenaka, Norio; Bouibes, Amine; Yamada, Yuki Advanced Materials, Vol. 33, Issue 37 https://doi.org/10.1002/adma.202100574	journal	August 2021
Organometallic Chemistry on Silicon and Germanium Surfaces Buriak, Jillian M. Chemical Reviews, Vol. 102, Issue 5 https://doi.org/10.1021/cr000064s	journal	May 2002
Developing high safety Li-metal anodes for future high-energy Li-metal batteries: strategies and perspectives Liu, Dai-Huo; Bai, Zhengyu; Li, Matthew Chemical Society Reviews, Vol. 49, Issue 15 https://doi.org/10.1039/C9CS00636B	journal	January 2020
Development of carbon conductive additives for advanced lithium ion batteries Spahr, Michael E.; Goers, Dietrich; Leone, Antonio Journal of Power Sources, Vol. 196, Issue 7 https://doi.org/10.1016/j.jpowsour.2010.07.002	journal	April 2011
Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands Carroll, Gerard M.; Limpens, Rens; Neale, Nathan R. Nano Letters, Vol. 18, Issue 5 https://doi.org/10.1021/acs.nanolett.8b00680	journal	April 2018
Size-Dependent Fracture of Silicon Nanoparticles During Lithiation Liu, Xiao Hua; Zhong, Li; Huang, Shan ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn204476h	journal	January 2012
Effect of Porosity, Thickness and Tortuosity on Capacity Fade of Anode Suthar, Bharatkumar; Northrop, Paul W. C.; Rife, Derek Journal of The Electrochemical Society, Vol. 162, Issue 9 https://doi.org/10.1149/2.0061509jes	journal	January 2015
Alloy Negative Electrodes for Li-Ion Batteries Obrovac, M. N.; Chevrier, V. L. Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500207g	journal	October 2014
Intrinsic Chemical Reactivity of Silicon Electrode Materials: Gas Evolution Seitzinger, Claire L.; Sacci, Robert L.; Coyle, Jaclyn E. Chemistry of Materials, Vol. 32, Issue 7 https://doi.org/10.1021/acs.chemmater.0c00308	journal	March 2020
Challenges and Recent Progress in the Development of Si Anodes for Lithium-Ion Battery Jin, Yan; Zhu, Bin; Lu, Zhenda Advanced Energy Materials, Vol. 7, Issue 23 https://doi.org/10.1002/aenm.201700715	journal	September 2017
Key functional groups defining the formation of Si anode solid-electrolyte interphase towards high energy density Li-ion batteries Shin, Jaewook; Kim, Tae-Hee; Lee, Yongju Energy Storage Materials, Vol. 25 https://doi.org/10.1016/j.ensm.2019.09.009	journal	March 2020
Investigating the Chemical Reactivity of Lithium Silicate Model SEI Layers Coyle, Jaclyn E.; Brumbach, Michael T.; Veith, Gabriel M. The Journal of Physical Chemistry C, Vol. 124, Issue 15 https://doi.org/10.1021/acs.jpcc.0c01057	journal	March 2020
Review—SEI: Past, Present and Future Peled, E.; Menkin, S. Journal of The Electrochemical Society, Vol. 164, Issue 7 https://doi.org/10.1149/2.1441707jes	journal	January 2017
Recent Research Progress of Silicon‐Based Anode Materials for Lithium‐Ion Batteries Du, Aimin; Li, Hang; Chen, Xinwen ChemistrySelect, Vol. 7, Issue 19 https://doi.org/10.1002/slct.202201269	journal	May 2022
Silyl Radical Abstraction in the Functionalization of Plasma-Synthesized Silicon Nanocrystals Wheeler, Lance M.; Anderson, Nicholas C.; Palomaki, Peter K. B. Chemistry of Materials, Vol. 27, Issue 19, p. 6869-6878 https://doi.org/10.1021/acs.chemmater.5b03309	journal	September 2015
The interplay between solid electrolyte interface (SEI) and dendritic lithium growth Wu, Bingbin; Lochala, Joshua; Taverne, Tyler Nano Energy, Vol. 40 https://doi.org/10.1016/j.nanoen.2017.08.005	journal	October 2017

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Title: Control of nanoparticle dispersion, SEI composition, and electrode morphology enables long cycle life in high silicon content nanoparticle-based composite anodes for lithium-ion batteries

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