Solvent‐Phobic and Ionophilic Carboxylated Polythiophene Layer for Fluoride‐Rich Cathode Electrolyte Interphase

Ren, Haoze; Sun, Zeyuan; Wang, Meng; Sun, Mengting; Li, Han; Pace, Alexis; Takeuchi, Esther S.; Marschilok, Amy C.; Yan, Shan; Takeuchi, Kenneth J.; Reichmanis, Elsa

doi:10.1002/aenm.202406019

Solvent‐Phobic and Ionophilic Carboxylated Polythiophene Layer for Fluoride‐Rich Cathode Electrolyte Interphase

Journal Article · Fri Mar 21 00:00:00 EDT 2025 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202406019· OSTI ID:2536738

^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[2]; ^[3]; ^[3]; ^[4]; ^[3]; ^[1]

Department of Chemical and Bimolecular Engineering Lehigh University Bethlehem PA 18015 USA
Institute of Sustainability, Environment and Energy Stony Brook University Stony Brook New York 11794 USA
Institute of Sustainability, Environment and Energy Stony Brook University Stony Brook New York 11794 USA, Interdisciplinary Science Department Brookhaven National Laboratory Upton, New York 11973 USA, Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook New York 11794 USA, Department of Chemistry Stony Brook University Stony Brook New York 11794 USA
Institute of Sustainability, Environment and Energy Stony Brook University Stony Brook New York 11794 USA, Interdisciplinary Science Department Brookhaven National Laboratory Upton, New York 11973 USA

Abstract

One focal area of contemporary organic mixed ionic‐electronic conductor (OMIEC) research relates to utilization of dual‐conductive properties to enhance the ion/electron transfer kinetics for energy storage applications. Insight regarding OMIEC response toward the electrolyte anion and solvent used in lithium‐ion batteries (LIBs), however, is limited. Here, for the first time, the solvent‐phobic and ionophilic (SP‐IP) properties of the OMIEC, poly[3‐(potassium‐4‐butanoate)thiophene‐2,5‐diyl] (P3KBT), are revealed through comprehensive evaluation and characterization. The solvent‐phobic characteristics arise from the cooperation of dispersive interaction, polar interaction, and hydrogen‐bonding between P3KBT and electrolyte solvent. The ionophilic nature is driven by electrostatic interactions between P3KBT side chain carboxylate groups and LiPF ₆ , and the reversible electrochemical doping/de‐doping of the polythiophene backbone with PF ₆ ^⁻ . The SP‐IP properties induce formation of a LiF‐ rich , Li ₂ CO ₃ ‐ limited cathode electrolyte interphase (CEI) layer when a P3KBT coating layer is applied to the active material surface, significantly improving half‐cell life to over 1500 cycles at 2C.

View Journal Article

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0012673; AC02-76SF00515

OSTI ID:: 2536738

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials; ISSN 1614-6832

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (66)

Decomposition of Trace Li ₂ CO ₃ During Charging Leads to Cathode Interface Degradation with the Solid Electrolyte LLZO Delluva, Alexander A.; Kulberg‐Savercool, Jonas; Holewinski, Adam Advanced Functional Materials, Vol. 31, Issue 34 https://doi.org/10.1002/adfm.202103716	journal	July 2021
Ion Pair Uptake in Ion Gel Devices Based on Organic Mixed Ionic–Electronic Conductors Quill, Tyler J.; LeCroy, Garrett; Melianas, Armantas Advanced Functional Materials, Vol. 31, Issue 47 https://doi.org/10.1002/adfm.202104301	journal	August 2021
Enhancement‐Mode PEDOT:PSS Organic Electrochemical Transistors Using Molecular De‐Doping Keene, Scott T.; Pol, Tom P. A.; Zakhidov, Dante Advanced Materials, Vol. 32, Issue 19 https://doi.org/10.1002/adma.202000270	journal	March 2020
Mixed Ionic–Electronic Conduction, a Multifunctional Property in Organic Conductors Tan, Siew Ting Melissa; Gumyusenge, Aristide; Quill, Tyler James Advanced Materials, Vol. 34, Issue 21 https://doi.org/10.1002/adma.202110406	journal	April 2022
Fluorinating All Interfaces Enables Super‐Stable Solid‐State Lithium Batteries by In Situ Conversion of Detrimental Surface Li₂CO₃ Guo, Yong; Pan, Siyuan; Yi, Xuerui Advanced Materials, Vol. 36, Issue 13 https://doi.org/10.1002/adma.202308493	journal	December 2023
Observing Ion Motion in Conjugated Polyelectrolytes with Kelvin Probe Force Microscopy Collins, Samuel D.; Mikhnenko, Oleksandr V.; Nguyen, Thanh Luan Advanced Electronic Materials, Vol. 3, Issue 3 https://doi.org/10.1002/aelm.201700005	journal	February 2017
Self-Assembled Nanocomposite of Silicon Nanoparticles Encapsulated in Graphene through Electrostatic Attraction for Lithium-Ion Batteries Zhou, Xiaosi; Yin, Ya-Xia; Wan, Li-Jun Advanced Energy Materials, Vol. 2, Issue 9 https://doi.org/10.1002/aenm.201200158	journal	April 2012
Regulating Mass Transport Behavior for High‐Performance Lithium Metal Batteries and Fast‐Charging Lithium‐Ion Batteries Li, Guoxing Advanced Energy Materials, Vol. 11, Issue 7 https://doi.org/10.1002/aenm.202002891	journal	January 2021
Temperature‐Responsive Formation Cycling Enabling LiF‐Rich Cathode‐Electrolyte Interphase Hong, Luxi; Zhang, Yi; Mei, Pan Angewandte Chemie International Edition, Vol. 63, Issue 41 https://doi.org/10.1002/anie.202409069	journal	September 2024
Understanding the Cathode–Electrolyte Interphase in Lithium‐Ion Batteries No authors listed Energy Technology, Vol. 10, Issue 9 https://doi.org/10.1002/ente.202200421	journal	July 2022
Facile synthesis of high-performance LiFePO4-reduced graphene oxide composites using ball milling Kuk, Youngsu; Hwang, Jieun; Nam, Dongho Ionics, Vol. 26, Issue 6 https://doi.org/10.1007/s11581-019-03395-6	journal	January 2020
Changes in surface chemistry of activated carbons by wet oxidation Moreno-Castilla, C.; López-Ramón, M. V.; Carrasco-Marı́n, F. Carbon, Vol. 38, Issue 14 https://doi.org/10.1016/S0008-6223(00)00048-8	journal	January 2000
Natural and synthetic superhydrophobic surfaces: A review of the fundamentals, structures, and applications Sotoudeh, Freshteh; Mousavi, S. Mahmood; Karimi, Nader Alexandria Engineering Journal, Vol. 68 https://doi.org/10.1016/j.aej.2023.01.058	journal	April 2023
Improving the deconvolution and interpretation of XPS spectra from chars by ab initio calculations Smith, Matthew; Scudiero, Louis; Espinal, Juan Carbon, Vol. 110 https://doi.org/10.1016/j.carbon.2016.09.012	journal	December 2016
Molecular design of highly Li-ion conductive cathode-electrolyte interface enabling excellent rate performance for lithium-ion batteries Wu, Xiaolong; Xue, Yejuan; Li, Zezhuo Chemical Engineering Journal, Vol. 493 https://doi.org/10.1016/j.cej.2024.152512	journal	August 2024
Experimental studies of contact angle hysteresis phenomena on polymer surfaces — Toward the understanding and control of wettability for different applications Grundke, K.; Pöschel, K.; Synytska, A. Advances in Colloid and Interface Science, Vol. 222 https://doi.org/10.1016/j.cis.2014.10.012	journal	August 2015
Solid electrolytes reinforced by infinite coordination polymer nano-network for dendrite-free lithium metal batteries Wu, Xiaoxue; Zheng, Yongjian; Li, Wenbo Energy Storage Materials, Vol. 41 https://doi.org/10.1016/j.ensm.2021.06.009	journal	October 2021
A quasi-solid state polymer electrolyte for high-rate and long-life sodium-metal batteries Vineeth, S. K.; Soni, Chhail Bihari Journal of Energy Storage, Vol. 73 https://doi.org/10.1016/j.est.2023.108780	journal	December 2023
The effect of different binders on electrochemical properties of LiNi1/3Mn1/3Co1/3O2 cathode material in lithium ion batteries Xu, Jiantie; Chou, Shu-Lei; Gu, Qin-fen Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.10.033	journal	March 2013
Manipulating cation-anion coordination in fire-retardant electrolytes to enable high-areal-capacity fluoride conversion batteries Chen, Keyi; Qiu, Wujie; Lei, Meng Matter, Vol. 7, Issue 11 https://doi.org/10.1016/j.matt.2024.07.007	journal	November 2024
Water repellent/wetting characteristics of various bio-inspired morphologies and fluid drag reduction testing research Luo, Yuehao; Song, Wen; Wang, Xudong Micron, Vol. 82 https://doi.org/10.1016/j.micron.2015.12.004	journal	March 2016
Mixed conductivity of polythiophene-based ionic polymers under controlled conditions Merkle, R.; Gutbrod, P.; Reinold, P. Polymer, Vol. 132 https://doi.org/10.1016/j.polymer.2017.10.064	journal	December 2017
The significance of aqueous binders in lithium-ion batteries Lingappan, Niranjanmurthi; Kong, Lingxi; Pecht, Michael Renewable and Sustainable Energy Reviews, Vol. 147 https://doi.org/10.1016/j.rser.2021.111227	journal	September 2021
Drag reduction of Newtonian fluid in a circular pipe with a highly water-repellent wall Watanabe, Keizo; Udagawa, Yanuar; Udagawa, Hiroshi Journal of Fluid Mechanics, Vol. 381 https://doi.org/10.1017/S0022112098003747	journal	February 1999
Li ⁺ and Oxidant Addition To Control Ionic and Electronic Conduction in Ionic Liquid-Functionalized Conjugated Polymers Rawlings, Dakota; Lee, Dongwook; Kim, Jeongmin Chemistry of Materials, Vol. 33, Issue 16 https://doi.org/10.1021/acs.chemmater.1c01811	journal	August 2021
Impact of Side Chain Chemistry on Lithium Transport in Mixed Ion–Electron-Conducting Polymers Pace, Gordon; Nordness, Oscar; Asham, Kareem Chemistry of Materials, Vol. 34, Issue 10 https://doi.org/10.1021/acs.chemmater.2c00592	journal	May 2022
Mixed Ion–Electron-Conducting Polymer Complexes as High-Rate Battery Binders Pace, Gordon; Zele, Alexandra; Nguyen, Phong Chemistry of Materials, Vol. 35, Issue 19 https://doi.org/10.1021/acs.chemmater.3c01587	journal	September 2023
Carboxyl-Alkyl Functionalized Conjugated Polyelectrolytes for High Performance Organic Electrochemical Transistors Sun, Zeyuan; Khau, Brian; Dong, Hao Chemistry of Materials, Vol. 35, Issue 21, p. 9299-9312 https://doi.org/10.1021/acs.chemmater.3c02103	journal	November 2023
Recent Advances in the Application of Magnetite (Fe₃O₄) in Lithium-Ion Batteries: Synthesis, Electrochemical Performance, and Characterization Techniques Ren, Haoze; Li, Han; Barry, Patrick Chemistry of Materials, Vol. 36, Issue 19 https://doi.org/10.1021/acs.chemmater.4c02013	journal	September 2024
Electron/Ion Transport Enhancer in High Capacity Li-Ion Battery Anodes Kwon, Yo Han; Minnici, Krysten; Huie, Matthew M. Chemistry of Materials, Vol. 28, Issue 18 https://doi.org/10.1021/acs.chemmater.6b02982	journal	September 2016
Polythiophene: From Fundamental Perspectives to Applications Kaloni, Thaneshwor P.; Giesbrecht, Patrick K.; Schreckenbach, Georg Chemistry of Materials, Vol. 29, Issue 24 https://doi.org/10.1021/acs.chemmater.7b03035	journal	November 2017
Controlling the Doping Mechanism in Poly(3-hexylthiophene) Thin-Film Transistors with Polymeric Ionic Liquid Dielectrics Rawlings, Dakota; Thomas, Elayne M.; Segalman, Rachel A. Chemistry of Materials, Vol. 31, Issue 21 https://doi.org/10.1021/acs.chemmater.9b02803	journal	October 2019
Electron and Ion Transport in Lithium and Lithium-Ion Battery Negative and Positive Composite Electrodes Quilty, Calvin D.; Wu, Daren; Li, Wenzao Chemical Reviews, Vol. 123, Issue 4 https://doi.org/10.1021/acs.chemrev.2c00214	journal	February 2023
Understanding the Role of Polymer Interactions within Binders in Composite Lithium-Ion Anodes Gonzalez, Miguel A.; Freer, W. Henry; Wang, Meng The Journal of Physical Chemistry C, Vol. 126, Issue 46, p. 19603-19617 https://doi.org/10.1021/acs.jpcc.2c06139	journal	November 2022
Stress-Relieving Carboxylated Polythiophene/Single-Walled Carbon Nanotube Conductive Layer for Stable Silicon Microparticle Anodes in Lithium-Ion Batteries Gueon, Donghee; Ren, Haoze; Sun, Zeyuan ACS Applied Energy Materials, Vol. 7, Issue 17 https://doi.org/10.1021/acsaem.4c01132	journal	August 2024
XPS on Li-Battery-Related Compounds: Analysis of Inorganic SEI Phases and a Methodology for Charge Correction Wood, Kevin N.; Teeter, Glenn ACS Applied Energy Materials, Vol. 1, Issue 9 https://doi.org/10.1021/acsaem.8b00406	journal	August 2018
Tuning Conjugated Polymers for Binder Applications in High-Capacity Magnetite Anodes Minnici, Krysten; Kwon, Yo Han; Housel, Lisa M. ACS Applied Energy Materials, Vol. 2, Issue 10 https://doi.org/10.1021/acsaem.9b01580	journal	September 2019
Toward Uniformly Dispersed Battery Electrode Composite Materials: Characteristics and Performance Kwon, Yo Han; Huie, Matthew M.; Choi, Dalsu ACS Applied Materials & Interfaces, Vol. 8, Issue 5 https://doi.org/10.1021/acsami.5b11938	journal	January 2016
Carboxylated Poly(thiophene) Binders for High-Performance Magnetite Anodes: Impact of Cation Structure Minnici, Krysten; Kwon, Yo Han; O’Neil, Johnathan ACS Applied Materials & Interfaces, Vol. 11, Issue 47 https://doi.org/10.1021/acsami.9b11513	journal	November 2019
A Coacervate-Based Mixed-Conducting Binder for High-Power, High-Energy Batteries Pace, Gordon T.; Le, My Linh; Clément, Raphaële J. ACS Energy Letters, Vol. 8, Issue 6 https://doi.org/10.1021/acsenergylett.3c00829	journal	May 2023
Beyond Composition: Surface Reactivity and Structural Arrangement of the Cathode–Electrolyte Interphase Hestenes, Julia C.; Marbella, Lauren E. ACS Energy Letters, Vol. 8, Issue 11 https://doi.org/10.1021/acsenergylett.3c01529	journal	October 2023
Percolation, Tie-Molecules, and the Microstructural Determinants of Charge Transport in Semicrystalline Conjugated Polymers Mollinger, Sonya A.; Krajina, Brad A.; Noriega, Rodrigo ACS Macro Letters, Vol. 4, Issue 7 https://doi.org/10.1021/acsmacrolett.5b00314	journal	June 2015
Constructing LiF-Dominated Interphases with Polymer Interwoven Outer Layer Enables Long-Term Cycling of Si Anodes Yang, Yaozong; Wang, Jie; Li, Zhaolin ACS Nano, Vol. 18, Issue 10, p. 7666-7676 https://doi.org/10.1021/acsnano.4c00998	journal	February 2024
Carbon Nanotube Web with Carboxylated Polythiophene “Assist” for High-Performance Battery Electrodes Kwon, Yo Han; Park, Jung Jin; Housel, Lisa M. ACS Nano, Vol. 12, Issue 4 https://doi.org/10.1021/acsnano.7b08918	journal	January 2018
The Nature of In-Plane Skeleton Raman Modes of P3HT and Their Correlation to the Degree of Molecular Order in P3HT:PCBM Blend Thin Films Tsoi, Wing C.; James, David T.; Kim, Jong Soo Journal of the American Chemical Society, Vol. 133, Issue 25 https://doi.org/10.1021/ja2013104	journal	June 2011
Both Resilience and Adhesivity Define Solid Electrolyte Interphases for a High Performance Anode Zhai, Yue; Zhong, Zitong; Kuang, Nannan Journal of the American Chemical Society, Vol. 146, Issue 22 https://doi.org/10.1021/jacs.4c02115	journal	May 2024
SWNT Anchored with Carboxylated Polythiophene “Links” on High-Capacity Li-Ion Battery Anode Materials Kwon, Yo Han; Minnici, Krysten; Park, Jung Jin Journal of the American Chemical Society, Vol. 140, Issue 17 https://doi.org/10.1021/jacs.8b00693	journal	March 2018
Polymer entanglements Wool, Richard P. Macromolecules, Vol. 26, Issue 7 https://doi.org/10.1021/ma00059a012	journal	March 1993
Organic electrochemical transistors Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto Nature Reviews Materials, Vol. 3, Issue 2 https://doi.org/10.1038/natrevmats.2017.86	journal	January 2018
High-rate lithiation-induced reactivation of mesoporous hollow spheres for long-lived lithium-ion batteries Sun, Hongtao; Xin, Guoqing; Hu, Tao Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5526	journal	July 2014
A general relationship between disorder, aggregation and charge transport in conjugated polymers Noriega, Rodrigo; Rivnay, Jonathan; Vandewal, Koen Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3722	journal	August 2013
Polythiophene nanoparticles that display reversible multichromism in aqueous media Salikolimi, Krishnachary; Kawamoto, Masuki; He, Pan Polymer Journal, Vol. 49, Issue 5 https://doi.org/10.1038/pj.2017.5	journal	February 2017
A salt-philic, solvent-phobic interfacial coating design for lithium metal electrodes Huang, Zhuojun; Lai, Jian-Cheng; Liao, Sheng-Lun Nature Energy, Vol. 8, Issue 6, p. 577-585 https://doi.org/10.1038/s41560-023-01252-5	journal	April 2023
Salt-philic and solvent-phobic Park, Min-Sik; Kim, Jung Ho Nature Energy, Vol. 8, Issue 6 https://doi.org/10.1038/s41560-023-01257-0	journal	April 2023
Oscillatory solvation chemistry for a 500 Wh kg−1 Li-metal pouch cell Zhang, Shuoqing; Li, Ruhong; Deng, Tao Nature Energy, Vol. 9, Issue 10 https://doi.org/10.1038/s41560-024-01621-8	journal	August 2024
Organic mixed ionic–electronic conductors Paulsen, Bryan D.; Tybrandt, Klas; Stavrinidou, Eleni Nature Materials, Vol. 19, Issue 1 https://doi.org/10.1038/s41563-019-0435-z	journal	August 2019
Lithium doped poly(3-hexylthiophene) for efficient hole transporter and sensitizer in metal free quaterthiophene dye treated hybrid solar cells Pirashanthan, Arumugam; Velauthapillai, Dhayalan; Robertson, Neil Scientific Reports, Vol. 11, Issue 1 https://doi.org/10.1038/s41598-021-99762-3	journal	October 2021
Electrode activation via vesiculation: improved reversible capacity of γ-Fe₂O₃@C/MWNT composite anodes for lithium-ion batteries Liu, Yongfei; Xu, Junmin; Qin, Xiaoying Journal of Materials Chemistry A, Vol. 3, Issue 18 https://doi.org/10.1039/C5TA00701A	journal	January 2015
An insight into the role of side chains in the microstructure and carrier mobility of high-performance conjugated polymers Pan, Yuchai; Huang, Jianyao; Gao, Dong Polymer Chemistry, Vol. 12, Issue 16 https://doi.org/10.1039/D1PY00105A	journal	January 2021
Mixed ionic and electronic conducting binders containing PEDOT:PSS and organic ionic plastic crystals toward carbon-free solid-state battery cathodes del Olmo, Rafael; Mendes, Tiago C.; Forsyth, Maria Journal of Materials Chemistry A, Vol. 10, Issue 37 https://doi.org/10.1039/D1TA09628A	journal	January 2022
Enhancing composite electrode performance: insights into interfacial interactions Ren, Haoze; Takeuchi, Esther S.; Marschilok, Amy C. Chemical Communications, Vol. 60, Issue 15 https://doi.org/10.1039/D3CC05608B	journal	January 2024
Polythiophene side chain chemistry and its impact on advanced composite anodes for lithium-ion batteries Li, Han; Ren, Haoze; Sun, Zeyuan Chemical Communications, Vol. 61, Issue 1 https://doi.org/10.1039/D4CC06117A	journal	January 2025
Construction of solid-liquid fluorine transport channel to enable highly reversible conversion cathodes Chen, Keyi; Lei, Meng; Yao, Zhenguo Science Advances, Vol. 7, Issue 45 https://doi.org/10.1126/sciadv.abj1491	journal	November 2021
Role of hydrophobicity on interfacial fluid flow: Theory and some applications Lorenz, B.; Rodriguez, N.; Mangiagalli, P. The European Physical Journal E, Vol. 37, Issue 6 https://doi.org/10.1140/epje/i2014-14057-6	journal	June 2014
Review—Conducting Polymer-Based Binders for Lithium-Ion Batteries and Beyond Nguyen, Van At; Kuss, Christian Journal of The Electrochemical Society, Vol. 167, Issue 6 https://doi.org/10.1149/1945-7111/ab856b	journal	January 2020
A Review on Application of LiFePO4 based composites as electrode materials for Lithium Ion Batteries Xin, Yue-Ming; Xu, Hai-Yan; Ruan, Jun-Hai International Journal of Electrochemical Science, Vol. 16, Issue 6 https://doi.org/10.20964/2021.06.33	journal	June 2021

Similar Records

Polyethylene Glycol Surface Modification and Polythiophene Side-Chain Chemistry: A Combined Strategy toward High-Capacity Lithium-Ion Battery Anodes

Journal Article · Wed Jul 30 00:00:00 EDT 2025 · ACS Applied Energy Materials · OSTI ID:2583412

Insights into the Chemistry of the Cathodic Electrolyte Interphase for PTFE-Based Dry-Processed Cathodes

Journal Article · Fri Aug 18 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces · OSTI ID:1996673

Solvent‐Phobic and Ionophilic Carboxylated Polythiophene Layer for Fluoride‐Rich Cathode Electrolyte Interphase

Citation Formats

References (66)

Similar Records

Related Subjects