Controlling Ion Uptake in Carboxylated Mixed Conductors

Sun, Zeyuan; Sun, Mengting; Qin, Siyu; Wang, Meng; Zheng, Yulong; Khau, Brian; Li, Han; Gartner, Thomas E.; Takacs, Christopher J; Reichmanis, Elsa

doi:10.1002/adma.202414963

Title: Controlling Ion Uptake in Carboxylated Mixed Conductors

Journal Article · 03 December 2024 · Advanced Materials

DOI: https://doi.org/10.1002/adma.202414963 · OSTI ID:2479806

^[1];

^[2];

^[1];

^[3];

^[1]

Lehigh Univ., Bethlehem, PA (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Organic mixed ionic‐electronic conductors (OMIECs) have garnered significant attention due to their capacity to transport both ions and electrons, making them ideal for applications in energy storage, neuromorphics, and bioelectronics. However, charge compensation mechanisms during the polymer redox process remain poorly understood, and are often oversimplified as single‐ion injection with little attention to counterion effects. To advance understanding and design strategies toward next‐generation OMIEC systems, a series of p‐channel carboxylated mixed conductors is investigated. Varying side‐chain functionality, distinctive swelling character is uncovered during electrochemical doping/dedoping with model chao‐/kosmotropic electrolytes. Carboxylic acid functionalized polymers demonstrate strong deswelling and mass reduction during doping, indicating cation expulsion, while ethoxycarbonyl counterparts exhibit prominent mass increase, pointing to an anion‐driven doping mechanism. By employing operando grazing incidence X‐ray fluorescence (GIXRF), it is revealed that the carboxyl functionalized polymer engages in robust cation interaction, whereas ester functionalization shifts the mechanism towards no cation involvement. It is demonstrated that cations are pivotal in mitigating swelling by counterbalancing anions, enabling efficient anion uptake without compromising performance. These findings underscore the transformative influence of functionality‐driven factors and side‐chain chemistry in governing ion dynamics and conduction, providing new frameworks for designing OMIECs with enhanced performance and reduced swelling.

View Journal Article

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 2479806

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 8 Vol. 37; ISSN 1521-4095; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors Savva, Achilleas; Hallani, Rawad; Cendra, Camila Advanced Functional Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adfm.201907657	journal	January 2020
Controlling Electrochemically Induced Volume Changes in Conjugated Polymers by Chemical Design: from Theory to Devices Moser, Maximilian; Gladisch, Johannes; Ghosh, Sarbani Advanced Functional Materials, Vol. 31, Issue 26 https://doi.org/10.1002/adfm.202100723	journal	April 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
Polarons in Conjugated Polyelectrolytes: A First‐Principles Perspective Wan, Yangyang; Zhang, Xu; Bazan, Guillermo C. Advanced Functional Materials, Vol. 32, Issue 52 https://doi.org/10.1002/adfm.202209394	journal	October 2022
Synthesis and properties of carboxy‐functionalized poly(3‐alkylthienylenes) Bäuerle, Peter; Gaudl, Kai‐Uwe; Würthner, Frank Advanced Materials, Vol. 2, Issue 10 https://doi.org/10.1002/adma.19900021011	journal	October 1990
Complementary Logic Circuits Based on High-Performance n-Type Organic Electrochemical Transistors Sun, Hengda; Vagin, Mikhail; Wang, Suhao Advanced Materials, Vol. 30, Issue 9 https://doi.org/10.1002/adma.201704916	journal	January 2018
Balancing Charge Storage and Mobility in an Oligo(Ether) Functionalized Dioxythiophene Copolymer for Organic‐ and Aqueous‐ Based Electrochemical Devices and Transistors Savagian, Lisa R.; Österholm, Anna M.; Ponder, James F. Advanced Materials, Vol. 30, Issue 50 https://doi.org/10.1002/adma.201804647	journal	August 2018
A Low‐Swelling Polymeric Mixed Conductor Operating in Aqueous Electrolytes Nicolini, Tommaso; Surgailis, Jokubas; Savva, Achilleas Advanced Materials, Vol. 33, Issue 2 https://doi.org/10.1002/adma.202005723	journal	November 2020
Charge Carrier Induced Structural Ordering And Disordering in Organic Mixed Ionic Electronic Conductors Quill, Tyler J.; LeCroy, Garrett; Marks, Adam Advanced Materials, Vol. 36, Issue 15 https://doi.org/10.1002/adma.202310157	journal	January 2024
The Role of Side Chains and Hydration on Mixed Charge Transport in n‐Type Polymer Films Surgailis, Jokūbas; Flagg, Lucas Q.; Richter, Lee J. Advanced Materials https://doi.org/10.1002/adma.202313121	journal	April 2024
Recent Technological Advances in Fabrication and Application of Organic Electrochemical Transistors Chen, Shuai; Surendran, Abhijith; Wu, Xihu Advanced Materials Technologies, Vol. 5, Issue 12 https://doi.org/10.1002/admt.202000523	journal	September 2020
Ionic Solvent Shell Drives Electroactuation in Organic Mixed Ionic‐Electronic Conductors Bonafè, Filippo; Decataldo, Francesco; Cramer, Tobias Advanced Science, Vol. 11, Issue 18 https://doi.org/10.1002/advs.202308746	journal	March 2024
Recent advances in conjugated polymer energy storage Mike, Jared F.; Lutkenhaus, Jodie L. Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 7 https://doi.org/10.1002/polb.23256	journal	February 2013
Electrochemistry of Thin Films with In Situ/Operando Grazing Incidence X‐Ray Scattering: Bypassing Electrolyte Scattering for High Fidelity Time Resolved Studies Paulsen, Bryan D.; Giovannitti, Alexander; Wu, Ruiheng Small, Vol. 17, Issue 42 https://doi.org/10.1002/smll.202103213	journal	September 2021
Nanostructured Polypyrrole as a flexible electrode material of supercapacitor Huang, Yang; Li, Hongfei; Wang, Zifeng Nano Energy, Vol. 22 https://doi.org/10.1016/j.nanoen.2016.02.047	journal	April 2016
In situ observation of dynamic elastic modulus in polypyrrole actuators Pytel, Rachel Z.; Thomas, Edwin L.; Hunter, Ian W. Polymer, Vol. 49, Issue 8 https://doi.org/10.1016/j.polymer.2008.01.053	journal	April 2008
Conjugated Polymers in Bioelectronics Inal, Sahika; Rivnay, Jonathan; Suiu, Andreea-Otilia Accounts of Chemical Research, Vol. 51, Issue 6 https://doi.org/10.1021/acs.accounts.7b00624	journal	May 2018
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
Enhancement of Conjugated Polymer Microstructure and Mixed-Conducting Properties via Chalcogenophene Heteroatom Substitution Paulsen, Bryan D.; Meli, Dilara; Moser, Maximilian Chemistry of Materials, Vol. 36, Issue 4 https://doi.org/10.1021/acs.chemmater.3c02309	journal	February 2024
Anion-Dependent Doping and Charge Transport in Organic Electrochemical Transistors Flagg, Lucas Q.; Giridharagopal, Rajiv; Guo, Jiajie Chemistry of Materials, Vol. 30, Issue 15 https://doi.org/10.1021/acs.chemmater.8b02220	journal	July 2018
Influence of Water on the Performance of Organic Electrochemical Transistors Savva, Achilleas; Cendra, Camila; Giugni, Andrea Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b04335	journal	January 2019
Organic Bioelectronics: Bridging the Signaling Gap between Biology and Technology Simon, Daniel T.; Gabrielsson, Erik O.; Tybrandt, Klas Chemical Reviews, Vol. 116, Issue 21 https://doi.org/10.1021/acs.chemrev.6b00146	journal	July 2016
Influence of Side Chains on the n-Type Organic Electrochemical Transistor Performance Ohayon, David; Savva, Achilleas; Du, Weiyuan ACS Applied Materials & Interfaces, Vol. 13, Issue 3 https://doi.org/10.1021/acsami.0c18599	journal	January 2021
Quantitative Composition and Mesoscale Ion Distribution in p-Type Organic Mixed Ionic-Electronic Conductors Wu, Ruiheng; Paulsen, Bryan D.; Ma, Qing ACS Applied Materials & Interfaces, Vol. 15, Issue 25 https://doi.org/10.1021/acsami.3c04449	journal	June 2023
Subsurface Profiling of Ion Migration and Swelling in Conducting Polymer Actuators with Modulated Electrochemical Atomic Force Microscopy Bonafè, Filippo; Dong, Chaoqun; Malliaras, George G. ACS Applied Materials & Interfaces, Vol. 16, Issue 28 https://doi.org/10.1021/acsami.4c08459	journal	July 2024
The Key Role of Side Chain Linkage in Structure Formation and Mixed Conduction of Ethylene Glycol Substituted Polythiophenes Schmode, Philip; Savva, Achilleas; Kahl, Robert ACS Applied Materials & Interfaces, Vol. 12, Issue 11 https://doi.org/10.1021/acsami.9b21604	journal	February 2020
Influences of Cations’ Solvation on Charge Storage Performance in Polyimide Anodes for Aqueous Multivalent Ion Batteries Nimkar, Amey; Malchick, Fyodor; Gavriel, Bar ACS Energy Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acsenergylett.1c01007	journal	June 2021
Revealing the Impact of Molecular Weight on Mixed Conduction in Glycolated Polythiophenes through Electrolyte Choice Tropp, Joshua; Meli, Dilara; Wu, Ruiheng ACS Materials Letters, Vol. 5, Issue 5 https://doi.org/10.1021/acsmaterialslett.2c01114	journal	April 2023
Carboxylic Acid Functionalization Yields Solvent-Resistant Organic Electrochemical Transistors Khau, Brian V.; Savagian, Lisa R.; De Keersmaecker, Michel ACS Materials Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsmaterialslett.9b00373	journal	October 2019
P-Type Electrochemical Doping Can Occur by Cation Expulsion in a High-Performing Polymer for Organic Electrochemical Transistors Flagg, Lucas Q.; Bischak, Connor G.; Quezada, Ramsess J. ACS Materials Letters, Vol. 2, Issue 3 https://doi.org/10.1021/acsmaterialslett.9b00501	journal	February 2020
Significant Enhancement of the Electrical Conductivity of Conjugated Polymers by Post-Processing Side Chain Removal Ponder, James F.; Gregory, Shawn A.; Atassi, Amalie Journal of the American Chemical Society, Vol. 144, Issue 3 https://doi.org/10.1021/jacs.1c11558	journal	January 2022
Effects of Side-Chain Length and Functionality on Polar Poly(dioxythiophene)s for Saline-Based Organic Electrochemical Transistors DiTullio, Brandon T.; Savagian, Lisa R.; Bardagot, Olivier Journal of the American Chemical Society, Vol. 145, Issue 1 https://doi.org/10.1021/jacs.2c08850	journal	December 2022
Hydration of a Side-Chain-Free n-Type Semiconducting Ladder Polymer Driven by Electrochemical Doping Guo, Jiajie; Flagg, Lucas Q.; Tran, Duyen K. Journal of the American Chemical Society, Vol. 145, Issue 3 https://doi.org/10.1021/jacs.2c11468	journal	January 2023
Polymer Crystallinity Controls Water Uptake in Glycol Side-Chain Polymer Organic Electrochemical Transistors Flagg, Lucas Q.; Bischak, Connor G.; Onorato, Jonathan W. Journal of the American Chemical Society, Vol. 141, Issue 10 https://doi.org/10.1021/jacs.8b12640	journal	February 2019
Hydration of Sodium, Potassium, and Chloride Ions in Solution and the Concept of Structure Maker/Breaker Mancinelli, R.; Botti, A.; Bruni, F. The Journal of Physical Chemistry B, Vol. 111, Issue 48 https://doi.org/10.1021/jp075913v	journal	December 2007
N-type organic electrochemical transistors with stability in water Giovannitti, Alexander; Nielsen, Christian B.; Sbircea, Dan-Tiberiu Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13066	journal	October 2016
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
Influence of PEDOT:PSS crystallinity and composition on electrochemical transistor performance and long-term stability Kim, Seong-Min; Kim, Chang-Hyun; Kim, Youngseok Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06084-6	journal	September 2018
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
A biohybrid synapse with neurotransmitter-mediated plasticity Keene, Scott T.; Lubrano, Claudia; Kazemzadeh, Setareh Nature Materials, Vol. 19, Issue 9 https://doi.org/10.1038/s41563-020-0703-y	journal	June 2020
An ordered, self-assembled nanocomposite with efficient electronic and ionic transport Quill, Tyler J.; LeCroy, Garrett; Halat, David M. Nature Materials, Vol. 22, Issue 3 https://doi.org/10.1038/s41563-023-01476-6	journal	February 2023
The role of the electrolyte in non-conjugated radical polymers for metal-free aqueous energy storage electrodes Ma, Ting; Li, Cheng-Han; Thakur, Ratul Mitra Nature Materials, Vol. 22, Issue 4 https://doi.org/10.1038/s41563-023-01518-z	journal	March 2023
Low energy ion scattering (LEIS). A practical introduction to its theory, instrumentation, and applications Cushman, Cody V.; Brüner, Philipp; Zakel, Julia Anal. Methods, Vol. 8, Issue 17 https://doi.org/10.1039/C6AY00765A	journal	January 2016
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
Understanding specific ion effects and the Hofmeister series Gregory, Kasimir P.; Elliott, Gareth R.; Robertson, Hayden Physical Chemistry Chemical Physics, Vol. 24, Issue 21 https://doi.org/10.1039/D2CP00847E	journal	January 2022
Impact of doping on the mechanical properties of conjugated polymers Paleti, Sri Harish Kumar; Kim, Youngseok; Kimpel, Joost Chemical Society Reviews, Vol. 53, Issue 4 https://doi.org/10.1039/D3CS00833A	journal	January 2024
Controlling the mode of operation of organic transistors through side-chain engineering Giovannitti, Alexander; Sbircea, Dan-Tiberiu; Inal, Sahika Proceedings of the National Academy of Sciences, Vol. 113, Issue 43 https://doi.org/10.1073/pnas.1608780113	journal	October 2016
Breath figure–derived porous semiconducting films for organic electronics Zhang, Xinan; Wang, Binghao; Huang, Lizhen Science Advances, Vol. 6, Issue 13 https://doi.org/10.1126/sciadv.aaz1042	journal	March 2020
Ambipolar inverters based on cofacial vertical organic electrochemical transistor pairs for biosignal amplification Rashid, Reem B.; Du, Weiyuan; Griggs, Sophie Science Advances, Vol. 7, Issue 37 https://doi.org/10.1126/sciadv.abh1055	journal	September 2021
Direct quantification of ion composition and mobility in organic mixed ionic-electronic conductors Wu, Ruiheng; Ji, Xudong; Ma, Qing Science Advances, Vol. 10, Issue 17 https://doi.org/10.1126/sciadv.adn8628	journal	April 2024

Similar Records

P-Type Electrochemical Doping Can Occur by Cation Expulsion in a High Performing Polymer for Organic Electrochemical Transistors

Journal Article · 2020 · ACS Materials Letters · OSTI ID:1756065

Flagg, Lucas Q.; Bischak, Connor G.; Quezada, Ramsess J.; +3 more

A Low‐Swelling Polymeric Mixed Conductor Operating in Aqueous Electrolytes

Journal Article · 2020 · Advanced Materials · OSTI ID:1804222

Nicolini, Tommaso; Surgailis, Jokubas; Savva, Achilleas; +8 more

Resonant X-ray Diffraction Reveals the Location of Counterions in Doped Organic Mixed Ionic Conductors

Journal Article · 2023 · Chemistry of Materials · OSTI ID:2350943

Flagg, Lucas Q.; Onorato, Jonathan W.; Luscombe, Christine K.; +9 more

Related Subjects

carboxylated polythiophenes
grazing incidence x-ray fluorescence
ion dynamics
mixed ionic-electronic conductors

Title: Controlling Ion Uptake in Carboxylated Mixed Conductors

Citation Formats

References (50)

Similar Records

Related Subjects