Nanocellulose‐Carboxymethylcellulose Electrolyte for Stable, High‐Rate Zinc‐Ion Batteries

Xu, Lin; Meng, Taotao; Zheng, Xueying; Li, Tangyuan; Brozena, Alexandra H.; Mao, Yimin; Zhang, Qian; Clifford, Bryson Callie; Rao, Jiancun; Hu, Liangbing

doi:10.1002/adfm.202302098

Nanocellulose‐Carboxymethylcellulose Electrolyte for Stable, High‐Rate Zinc‐Ion Batteries

Journal Article · Sun Apr 02 00:00:00 EDT 2023 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202302098· OSTI ID:1968087

^[1]; Meng, Taotao ^[1]; Zheng, Xueying ^[1]; Li, Tangyuan ^[1]; Brozena, Alexandra H. ^[1]; Mao, Yimin ^[1]; Zhang, Qian ^[1]; Clifford, Bryson Callie ^[1]; Rao, Jiancun ^[2]; ^[1]

Department of Materials Science and Engineering University of Maryland College Park MD 20742 USA
Advanced Imaging and Microscopy Laboratory University of Maryland College Park MD 20742 USA

Abstract

Aqueous Zn ion batteries (ZIBs) are one of the most promising battery chemistries for grid‐scale renewable energy storage. However, their application is limited by issues such as Zn dendrite formation and undesirable side reactions that can occur in the presence of excess free water molecules and ions. In this study, a nanocellulose‐carboxymethylcellulose (CMC) hydrogel electrolyte is demonstrated that features stable cycling performance and high Zn ²⁺ conductivity (26 mS cm ⁻¹ ), which is attributed to the material's strong mechanical strength (≈70 MPa) and water‐bonding ability. With this electrolyte, the Zn‐metal anode shows exceptional cycling stability at an ultra‐high rate, with the ability to sustain a current density as high as 80 mA cm ⁻² for more than 3500 cycles and a cumulative capacity of 17.6 Ah cm ⁻² (40 mA cm ⁻² ). Additionally, side reactions, such as hydrogen evolution and surface passivation, are substantially reduced due to the strong water‐bonding capacity of the CMC. Full Zn||MnO ₂ batteries fabricated with this electrolyte demonstrate excellent high‐rate performance and long‐term cycling stability (>500 cycles at 8C). These results suggest the cellulose‐CMC electrolyte as a promising low‐cost, easy‐to‐fabricate, and sustainable aqueous‐based electrolyte for ZIBs with excellent electrochemical performance that can help pave the way toward grid‐scale energy storage for renewable energy sources.

View Journal Article

Research Organization:: Univ. of Maryland, College Park, MD (United States)

Sponsoring Organization:: USDOE; USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AR0001588

OSTI ID:: 1968087

Alternate ID(s):: OSTI ID: 2422394
OSTI ID: 1968089

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 27 Vol. 33; ISSN 1616-301X

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

Country of Publication:: Germany

Language:: English

References (69)

Antifreezing Hydrogel with High Zinc Reversibility for Flexible and Durable Aqueous Batteries by Cooperative Hydrated Cations Zhu, Minshen; Wang, Xiaojie; Tang, Hongmei Advanced Functional Materials, Vol. 30, Issue 6 https://doi.org/10.1002/adfm.201907218	journal	November 2019
Highly Reversible Zn Anode Enabled by Controllable Formation of Nucleation Sites for Zn‐Based Batteries Liang, Pengcheng; Yi, Jin; Liu, Xiaoyu Advanced Functional Materials, Vol. 30, Issue 13 https://doi.org/10.1002/adfm.201908528	journal	March 2020
Fast‐Charging and Ultrahigh‐Capacity Zinc Metal Anode for High‐Performance Aqueous Zinc‐Ion Batteries Cao, Penghui; Zhou, Xiangyang; Wei, Anran Advanced Functional Materials, Vol. 31, Issue 20 https://doi.org/10.1002/adfm.202100398	journal	March 2021
Cations Coordination‐Regulated Reversibility Enhancement for Aqueous Zn‐Ion Battery Qian, Long; Yao, Wentao; Yao, Rui Advanced Functional Materials, Vol. 31, Issue 40 https://doi.org/10.1002/adfm.202105736	journal	July 2021
Sn Alloying to Inhibit Hydrogen Evolution of Zn Metal Anode in Rechargeable Aqueous Batteries Wang, Luyao; Huang, Weiwei; Guo, Wenbin Advanced Functional Materials, Vol. 32, Issue 1 https://doi.org/10.1002/adfm.202108533	journal	October 2021
Super‐Assembled Hierarchical Cellulose Aerogel‐Gelatin Solid Electrolyte for Implantable and Biodegradable Zinc Ion Battery Zhou, Junjie; Zhang, Runhao; Xu, Ran Advanced Functional Materials, Vol. 32, Issue 21 https://doi.org/10.1002/adfm.202111406	journal	February 2022
Single‐Ion‐Functionalized Nanocellulose Membranes Enable Lean‐Electrolyte and Deeply Cycled Aqueous Zinc‐Metal Batteries Ge, Xuesong; Zhang, Weihua; Song, Fuchen Advanced Functional Materials, Vol. 32, Issue 26 https://doi.org/10.1002/adfm.202200429	journal	March 2022
Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode Xia, Chuan; Guo, Jing; Lei, Yongjiu Advanced Materials, Vol. 30, Issue 5 https://doi.org/10.1002/adma.201705580	journal	December 2017
Dendrite‐Free Zinc Deposition Induced by Tin‐Modified Multifunctional 3D Host for Stable Zinc‐Based Flow Battery Yin, Yanbin; Wang, Shengnan; Zhang, Qi Advanced Materials, Vol. 32, Issue 6 https://doi.org/10.1002/adma.201906803	journal	December 2019
Hydrogen‐Free and Dendrite‐Free All‐Solid‐State Zn‐Ion Batteries Ma, Longtao; Chen, Shengmei; Li, Na Advanced Materials, Vol. 32, Issue 14 https://doi.org/10.1002/adma.201908121	journal	April 2020
Surface‐Preferred Crystal Plane for a Stable and Reversible Zinc Anode Zhou, Miao; Guo, Shan; Li, Jialin Advanced Materials, Vol. 33, Issue 21 https://doi.org/10.1002/adma.202100187	journal	April 2021
Printed Zinc Paper Batteries Yang, Peihua; Li, Jia; Lee, Seok Woo Advanced Science, Vol. 9, Issue 2 https://doi.org/10.1002/advs.202103894	journal	November 2021
Nanoporous CaCO ₃ Coatings Enabled Uniform Zn Stripping/Plating for Long-Life Zinc Rechargeable Aqueous Batteries Kang, Litao; Cui, Mangwei; Jiang, Fuyi Advanced Energy Materials, Vol. 8, Issue 25 https://doi.org/10.1002/aenm.201801090	journal	July 2018
Super‐Stretchable Zinc–Air Batteries Based on an Alkaline‐Tolerant Dual‐Network Hydrogel Electrolyte Ma, Longtao; Chen, Shengmei; Wang, Donghong Advanced Energy Materials, Vol. 9, Issue 12 https://doi.org/10.1002/aenm.201803046	journal	January 2019
A Room‐Temperature Molten Hydrate Electrolyte for Rechargeable Zinc–Air Batteries Chen, Chih‐Yao; Matsumoto, Kazuhiko; Kubota, Keigo Advanced Energy Materials, Vol. 9, Issue 22 https://doi.org/10.1002/aenm.201900196	journal	April 2019
Understanding the Design Principles of Advanced Aqueous Zinc‐Ion Battery Cathodes: From Transport Kinetics to Structural Engineering, and Future Perspectives Yong, Bo; Ma, Dingtao; Wang, Yanyi Advanced Energy Materials, Vol. 10, Issue 45 https://doi.org/10.1002/aenm.202002354	journal	October 2020
3D‐Printed Multi‐Channel Metal Lattices Enabling Localized Electric‐Field Redistribution for Dendrite‐Free Aqueous Zn Ion Batteries Zhang, Guanhua; Zhang, Xianan; Liu, Huaizhi Advanced Energy Materials, Vol. 11, Issue 19 https://doi.org/10.1002/aenm.202003927	journal	March 2021
Ultrafast Zinc–Ion–Conductor Interface toward High‐Rate and Stable Zinc Metal Batteries Yan, Huibo; Li, Songmei; Nan, Yang Advanced Energy Materials, Vol. 11, Issue 18 https://doi.org/10.1002/aenm.202100186	journal	April 2021
Manipulating Crystallographic Orientation of Zinc Deposition for Dendrite‐free Zinc Ion Batteries Cao, Jin; Zhang, Dongdong; Gu, Chao Advanced Energy Materials, Vol. 11, Issue 29 https://doi.org/10.1002/aenm.202101299	journal	June 2021
High Depth‐of‐Discharge Zinc Rechargeability Enabled by a Self‐Assembled Polymeric Coating Arnot, David J.; Lim, Matthew B.; Bell, Nelson S. Advanced Energy Materials, Vol. 11, Issue 38 https://doi.org/10.1002/aenm.202101594	journal	August 2021
Sustainable Battery Materials for Next‐Generation Electrical Energy Storage Yu, Xingwen; Manthiram, Arumugam Advanced Energy and Sustainability Research, Vol. 2, Issue 5 https://doi.org/10.1002/aesr.202000102	journal	March 2021
Highly Reversible and Rechargeable Safe Zn Batteries Based on a Triethyl Phosphate Electrolyte Naveed, Ahmad; Yang, Huijun; Yang, Jun Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201813223	journal	February 2019
Constructing a Super‐Saturated Electrolyte Front Surface for Stable Rechargeable Aqueous Zinc Batteries Yang, Huijun; Chang, Zhi; Qiao, Yu Angewandte Chemie International Edition, Vol. 59, Issue 24 https://doi.org/10.1002/anie.202001844	journal	April 2020
Stabilizing Interface pH by N‐Modified Graphdiyne for Dendrite‐Free and High‐Rate Aqueous Zn‐Ion Batteries Yang, Qi; Li, Liang; Hussain, Tanveer Angewandte Chemie International Edition, Vol. 61, Issue 6 https://doi.org/10.1002/anie.202112304	journal	December 2021
Hierarchically Nanostructured Solid‐State Electrolyte for Flexible Rechargeable Zinc–Air Batteries Xu, Mi; Dou, Haozhen; Zhang, Zhen Angewandte Chemie International Edition, Vol. 61, Issue 23 https://doi.org/10.1002/anie.202117703	journal	April 2022
Stabilized Rechargeable Aqueous Zinc Batteries Using Ethylene Glycol as Water Blocker Wang, Nan; Yang, Yang; Qiu, Xuan ChemSusChem, Vol. 13, Issue 20 https://doi.org/10.1002/cssc.202001750	journal	August 2020
A Nanofibrillated Cellulose/Polyacrylamide Electrolyte-Based Flexible and Sewable High-Performance Zn-MnO ₂ Battery with Superior Shear Resistance Wang, Donghong; Li, Hongfei; Liu, Zhuoxin Small, Vol. 14, Issue 51 https://doi.org/10.1002/smll.201803978	journal	November 2018
Cellulose nanofiber-based hydrogels with high mechanical strength Abe, Kentaro; Yano, Hiroyuki Cellulose, Vol. 19, Issue 6 https://doi.org/10.1007/s10570-012-9784-3	journal	September 2012
Novel cotton cellulose by cationisation during the mercerisation process—part 1: chemical and morphological changes Tarbuk, Anita; Grancaric, Ana Marija; Leskovac, Mirela Cellulose, Vol. 21, Issue 3 https://doi.org/10.1007/s10570-014-0245-z	journal	March 2014
Highly reversible and dendrite-free Zn electrodeposition enabled by a thin metallic interfacial layer in aqueous batteries Zhang, Yuanjun; Wang, Guanyao; Yu, Fangfang Chemical Engineering Journal, Vol. 416 https://doi.org/10.1016/j.cej.2020.128062	journal	July 2021
Cotton-derived cellulose film as a dendrite-inhibiting separator to stabilize the zinc metal anode of aqueous zinc ion batteries Zhou, Weijun; Chen, Minfeng; Tian, Qinghua Energy Storage Materials, Vol. 44 https://doi.org/10.1016/j.ensm.2021.10.002	journal	January 2022
Highly enhanced reversibility of a Zn anode by in-situ texturing Liu, Yi; Hu, Junping; Lu, Qiongqiong Energy Storage Materials, Vol. 47 https://doi.org/10.1016/j.ensm.2022.01.059	journal	May 2022
A high strength, anti-corrosion and sustainable separator for aqueous zinc-based battery by natural bamboo cellulose Fu, Jinzhou; Wang, Hanwei; Xiao, Ping Energy Storage Materials, Vol. 48 https://doi.org/10.1016/j.ensm.2022.02.052	journal	June 2022
An ion redistributor enabled by cost-effective weighing paper interlayer for dendrite free aqueous zinc-ion battery Guo, Yi; Cai, Wenlong; Lin, Yi Energy Storage Materials, Vol. 50 https://doi.org/10.1016/j.ensm.2022.06.001	journal	September 2022
Facile fabrication of self-healing carboxymethyl cellulose hydrogels Zheng, Wen Jiang; Gao, Jie; Wei, Zhao European Polymer Journal, Vol. 72 https://doi.org/10.1016/j.eurpolymj.2015.06.013	journal	November 2015
Scientific Challenges for the Implementation of Zn-Ion Batteries Blanc, Lauren E.; Kundu, Dipan; Nazar, Linda F. Joule, Vol. 4, Issue 4 https://doi.org/10.1016/j.joule.2020.03.002	journal	April 2020
Natural macromolecule based carboxymethyl cellulose as a gel polymer electrolyte with adjustable porosity for lithium ion batteries Zhu, Y. S.; Xiao, S. Y.; Li, M. X. Journal of Power Sources, Vol. 288 https://doi.org/10.1016/j.jpowsour.2015.04.117	journal	August 2015
Bacterial cellulose hydrogel: A promising electrolyte for flexible zinc-air batteries Zhang, Yanan; Chen, Yajun; Li, Xin Journal of Power Sources, Vol. 482 https://doi.org/10.1016/j.jpowsour.2020.228963	journal	January 2021
A sustainable chitosan-zinc electrolyte for high-rate zinc-metal batteries Wu, Meiling; Zhang, Ye; Xu, Lin Matter, Vol. 5, Issue 10 https://doi.org/10.1016/j.matt.2022.07.015	journal	October 2022
Multifunctional tin layer enabled long-life and stable anode for aqueous zinc-ion batteries Guo, W.; Zhang, Y.; Tong, X. Materials Today Energy, Vol. 20 https://doi.org/10.1016/j.mtener.2021.100675	journal	June 2021
A piece of common cellulose paper but with outstanding functions for advanced aqueous zinc-ion batteries Yang, Zefang; Li, Wenbin; Zhang, Qi Materials Today Energy, Vol. 28 https://doi.org/10.1016/j.mtener.2022.101076	journal	August 2022
“Water-in-deep eutectic solvent” electrolytes enable zinc metal anodes for rechargeable aqueous batteries Zhao, Jingwen; Zhang, Jian; Yang, Wuhai Nano Energy, Vol. 57 https://doi.org/10.1016/j.nanoen.2018.12.086	journal	March 2019
Modulating Zn deposition via ceramic-cellulose separator with interfacial polarization effect for durable zinc anode Cao, Jin; Zhang, Dongdong; Gu, Chao Nano Energy, Vol. 89 https://doi.org/10.1016/j.nanoen.2021.106322	journal	November 2021
Tuning Zn2+ coordination tunnel by hierarchical gel electrolyte for dendrite-free zinc anode Zhang, Bingyao; Qin, Liping; Fang, Yun Science Bulletin, Vol. 67, Issue 9 https://doi.org/10.1016/j.scib.2022.01.027	journal	May 2022
Emerging trends in sustainable battery chemistries Xu, Panpan; Tan, Darren H. S.; Chen, Zheng Trends in Chemistry, Vol. 3, Issue 8 https://doi.org/10.1016/j.trechm.2021.04.007	journal	August 2021
Emerging Engineered Wood for Building Applications Ding, Yu; Pang, Zhenqian; Lan, Kai Chemical Reviews, Vol. 123, Issue 5 https://doi.org/10.1021/acs.chemrev.2c00450	journal	October 2022
An Organic Cathode Based Dual-Ion Aqueous Zinc Battery Enabled by a Cellulose Membrane Glatz, Hadrien; Lizundia, Erlantz; Pacifico, Fiona ACS Applied Energy Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsaem.8b01851	journal	January 2019
Flexible Hydrogel Electrolyte with Superior Mechanical Properties Based on Poly(vinyl alcohol) and Bacterial Cellulose for the Solid-State Zinc–Air Batteries Zhao, Nana; Wu, Feng; Xing, Yi ACS Applied Materials & Interfaces, Vol. 11, Issue 17 https://doi.org/10.1021/acsami.9b00758	journal	March 2019
Undesired Reactions in Aqueous Rechargeable Zinc Ion Batteries Verma, Vivek; Kumar, Sonal; Manalastas, William ACS Energy Letters, Vol. 6, Issue 5 https://doi.org/10.1021/acsenergylett.1c00393	journal	April 2021
Recyclable and Ultrafast Fabrication of Zinc Oxide Interface Layer Enabling Highly Reversible Dendrite-Free Zn Anode Ma, Chenhui; Yang, Konghua; Zhao, Shibo ACS Energy Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acsenergylett.2c02735	journal	January 2023
Waterproof and Tailorable Elastic Rechargeable Yarn Zinc Ion Batteries by a Cross-Linked Polyacrylamide Electrolyte Li, Hongfei; Liu, Zhuoxin; Liang, Guojin ACS Nano, Vol. 12, Issue 4 https://doi.org/10.1021/acsnano.7b09003	journal	March 2018
Selected-Control Hydrothermal Synthesis of α- and β-MnO ₂ Single Crystal Nanowires Wang, Xun; Li, Yadong Journal of the American Chemical Society, Vol. 124, Issue 12 https://doi.org/10.1021/ja0177105	journal	March 2002
Zn/MnO ₂ Battery Chemistry With H ⁺ and Zn ²⁺ Coinsertion Sun, Wei; Wang, Fei; Hou, Singyuk Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b04471	journal	July 2017
Pursuit of reversible Zn electrochemistry: a time-honored challenge towards low-cost and green energy storage Zhang, Yaojian; Chen, Zheng; Qiu, Huayu NPG Asia Materials, Vol. 12, Issue 1 https://doi.org/10.1038/s41427-019-0167-1	journal	January 2020
Ampere-hour-scale zinc–air pouch cells Shinde, Sambhaji S.; Jung, Jin Young; Wagh, Nayantara K. Nature Energy, Vol. 6, Issue 6 https://doi.org/10.1038/s41560-021-00807-8	journal	April 2021
Highly reversible zinc metal anode for aqueous batteries Wang, Fei; Borodin, Oleg; Gao, Tao Nature Materials, Vol. 17, Issue 6 https://doi.org/10.1038/s41563-018-0063-z	journal	April 2018
Material science as a cornerstone driving battery research Tarascon, Jean-Marie Nature Materials, Vol. 21, Issue 9 https://doi.org/10.1038/s41563-022-01342-x	journal	August 2022
Research on cellulose nanocrystals produced from cellulose sources with various polymorphs Gong, Jie; Li, Jun; Xu, Jun RSC Advances, Vol. 7, Issue 53 https://doi.org/10.1039/C7RA06222B	journal	January 2017
High-performance flexible and self-healable quasi-solid-state zinc-ion hybrid supercapacitor based on borax-crosslinked polyvinyl alcohol/nanocellulose hydrogel electrolyte Chen, Minfeng; Chen, Jizhang; Zhou, Weijun Journal of Materials Chemistry A, Vol. 7, Issue 46 https://doi.org/10.1039/C9TA10944G	journal	January 2019
Fundamentals and perspectives in developing zinc-ion battery electrolytes: a comprehensive review Zhang, Tengsheng; Tang, Yan; Guo, Shan Energy & Environmental Science, Vol. 13, Issue 12 https://doi.org/10.1039/D0EE02620D	journal	January 2020
Ultra-long-life and highly reversible Zn metal anodes enabled by a desolvation and deanionization interface layer Zhang, Xiaotan; Li, Jiangxu; Liu, Dongyan Energy & Environmental Science, Vol. 14, Issue 5 https://doi.org/10.1039/D0EE03898A	journal	January 2021
Zinc ion trapping in a cellulose hydrogel as a solid electrolyte for a safe and flexible supercapacitor Yang, Lvye; Song, Lian; Feng, Yi Journal of Materials Chemistry A, Vol. 8, Issue 25 https://doi.org/10.1039/D0TA04360E	journal	January 2020
A stretchable solid-state zinc ion battery based on a cellulose nanofiber–polyacrylamide hydrogel electrolyte and a Mg_0.23V₂O₅·1.0H₂O cathode Xu, Wangwang; Liu, Chaozheng; Wu, Qinglin Journal of Materials Chemistry A, Vol. 8, Issue 35 https://doi.org/10.1039/D0TA06467J	journal	January 2020
Roadmap for advanced aqueous batteries: From design of materials to applications Chao, Dongliang; Zhou, Wanhai; Xie, Fangxi Science Advances, Vol. 6, Issue 21 https://doi.org/10.1126/sciadv.aba4098	journal	May 2020
A cellulose-derived supramolecule for fast ion transport Dong, Qi; Zhang, Xin; Qian, Ji Science Advances, Vol. 8, Issue 49 https://doi.org/10.1126/sciadv.add2031	journal	December 2022
Transport: A roadblock to climate change mitigation? Creutzig, F.; Jochem, P.; Edelenbosch, O. Y. Science, Vol. 350, Issue 6263 https://doi.org/10.1126/science.aac8033	journal	November 2015
Water Absorption in Carboxymethyl Cellulose Boruvkova, Karolina; Wiener, Jakub AUTEX Research Journal, Vol. 11, Issue 4 https://doi.org/10.1515/aut-2011-110404	journal	December 2011
Nanocellulose sheets from oil palm empty fruit bunches treated with NaOH solution Fahma, Farah; Lestari, Faiza Ayu; Kartika, Ika Amalia Karbala International Journal of Modern Science, Vol. 7, Issue 1 https://doi.org/10.33640/2405-609X.1892	journal	March 2021
An Integrated Approach to Optimizing Cellulose Mercerization Ferro, Monica; Mannu, Alberto; Panzeri, Walter Polymers, Vol. 12, Issue 7 https://doi.org/10.3390/polym12071559	journal	July 2020

Similar Records

Related Subjects

25 ENERGY STORAGE
Zn ion batteries
biopolymeric electrolytes
carboxymethyl cellulose
high-rate performance
nano-cellulose

Nanocellulose‐Carboxymethylcellulose Electrolyte for Stable, High‐Rate Zinc‐Ion Batteries

Citation Formats

References (69)

Similar Records

Related Subjects