Highly reversible Zn anode with a practical areal capacity enabled by a sustainable electrolyte and superacid interfacial chemistry

Li, Chang; Shyamsunder, Abhinandan; Hoane, Alexis Grace; Long, Daniel M.; Kwok, Chun Yuen; Kotula, Paul G.; Zavadil, Kevin R.; Gewirth, Andrew A.; Nazar, Linda F.

doi:10.1016/j.joule.2022.04.017

Title: Highly reversible Zn anode with a practical areal capacity enabled by a sustainable electrolyte and superacid interfacial chemistry

Journal Article · 17 May 2022 · Joule

DOI: https://doi.org/10.1016/j.joule.2022.04.017 · OSTI ID:1872004

Li, Chang ^[1]; Shyamsunder, Abhinandan ^[1]; Hoane, Alexis Grace ^[2]; Long, Daniel M. ^[3]; Kwok, Chun Yuen ^[4]; Kotula, Paul G. ^[5]; Zavadil, Kevin R. ^[1]; Gewirth, Andrew A. ^[2]; Nazar, Linda F. ^[1]

Univ. of Waterloo, ON (Canada); Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of Waterloo, ON (Canada)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Aqueous zinc-metal batteries are plagued by poor Zn reversibility owing to zinc dendrite and layered double hydroxide (LDH) formation. Here, we introduce a novel additive—N,N-dimethylformamidium trifluoromethanesulfonate (DOTf)—in a low-cost aqueous electrolyte that can very effectively address these issues. The initial water-assisted dissociation of DOTf into triflic superacid creates a robust nanostructured solid-electrolyte interface (SEI)—revealed by operando spectroscopy and cryomicroscopy—which excludes water and enables dense Zn deposition. We demonstrate excellent Zn plating/stripping in a Zn||Cu asymmetric cell for more than 3,500 cycles. Furthermore, near 100% CE is realized at a combined high current density of 4 mA cm^-2 and an areal capacity of 4 mAh cm^-2 over long-term cycling. Zn||Zn_0.25V₂O₅·nH₂O full cells retain ~83% of their capacity after 1,000 cycles with mass-limited Zn anodes. By restricting the depth of discharge, the cathodes exhibit less proton intercalation and LDH formation with an extended lifetime of 2,000 cycles.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

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

Grant/Contract Number:: NA0003525

OSTI ID:: 1872004

Report Number(s):: SAND2022-6489J; 706092

Journal Information:: Joule, Journal Name: Joule Journal Issue: 5 Vol. 6; ISSN 2542-4351

Publisher:: Elsevier - Cell PressCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

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
Designing Dendrite‐Free Zinc Anodes for Advanced Aqueous Zinc Batteries Hao, Junnan; Li, Xiaolong; Zhang, Shilin Advanced Functional Materials, Vol. 30, Issue 30 https://doi.org/10.1002/adfm.202001263	journal	June 2020
Stabilizing Zinc Anode Reactions by Polyethylene Oxide Polymer in Mild Aqueous Electrolytes Jin, Yan; Han, Kee Sung; Shao, Yuyan Advanced Functional Materials, Vol. 30, Issue 43 https://doi.org/10.1002/adfm.202003932	journal	September 2020
Engineering Polymer Glue towards 90% Zinc Utilization for 1000 Hours to Make High‐Performance Zn‐Ion Batteries Jiao, Yiding; Li, Fangyan; Jin, Xin Advanced Functional Materials, Vol. 31, Issue 49 https://doi.org/10.1002/adfm.202107652	journal	September 2021
Electrolyte Design for In Situ Construction of Highly Zn ²⁺ ‐Conductive Solid Electrolyte Interphase to Enable High‐Performance Aqueous Zn‐Ion Batteries under Practical Conditions Zeng, Xiaohui; Mao, Jianfeng; Hao, Junnan Advanced Materials, Vol. 33, Issue 11 https://doi.org/10.1002/adma.202007416	journal	February 2021
Stabilizing Zinc Anodes by Regulating the Electrical Double Layer with Saccharin Anions Huang, Cong; Zhao, Xin; Liu, Shuang Advanced Materials, Vol. 33, Issue 38 https://doi.org/10.1002/adma.202100445	journal	August 2021
Reducing Water Activity by Zeolite Molecular Sieve Membrane for Long‐Life Rechargeable Zinc Battery Yang, Huijun; Qiao, Yu; Chang, Zhi Advanced Materials, Vol. 33, Issue 38 https://doi.org/10.1002/adma.202102415	journal	August 2021
The Three‐Dimensional Dendrite‐Free Zinc Anode on a Copper Mesh with a Zinc‐Oriented Polyacrylamide Electrolyte Additive Zhang, Qi; Luan, Jingyi; Fu, Liang Angewandte Chemie International Edition, Vol. 58, Issue 44 https://doi.org/10.1002/anie.201907830	journal	September 2019
Zinc–Organic Battery with a Wide Operation‐Temperature Window from −70 to 150 °C Wang, Nan; Dong, Xiaoli; Wang, Bingliang Angewandte Chemie International Edition, Vol. 59, Issue 34 https://doi.org/10.1002/anie.202005603	journal	July 2020
Hydrophobic Organic‐Electrolyte‐Protected Zinc Anodes for Aqueous Zinc Batteries Cao, Longsheng; Li, Dan; Deng, Tao Angewandte Chemie International Edition, Vol. 59, Issue 43 https://doi.org/10.1002/anie.202008634	journal	August 2020
Boosting Zinc Electrode Reversibility in Aqueous Electrolytes by Using Low‐Cost Antisolvents Hao, Junnan; Yuan, Libei; Ye, Chao Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202016531	journal	February 2021
Functionalized Phosphonium Cations Enable Zinc Metal Reversibility in Aqueous Electrolytes Ma, Lin; Pollard, Travis P.; Zhang, Yong Angewandte Chemie International Edition, Vol. 60, Issue 22 https://doi.org/10.1002/anie.202017020	journal	April 2021
Electrochemical synthesis of trimethylamine by cathodic reduction of dimethylformamide using Cu and Pd cathodes Jia, Ruilong; Song, Xiuli; Yang, Tailai Journal of Electroanalytical Chemistry, Vol. 741 https://doi.org/10.1016/j.jelechem.2015.01.012	journal	March 2015
A Metal-Organic Framework Host for Highly Reversible Dendrite-free Zinc Metal Anodes Wang, Zhuo; Huang, Jianhang; Guo, Zhaowei Joule, Vol. 3, Issue 5 https://doi.org/10.1016/j.joule.2019.02.012	journal	May 2019
Practical Evaluation of Li-Ion Batteries Li, Hong Joule, Vol. 3, Issue 4 https://doi.org/10.1016/j.joule.2019.03.028	journal	April 2019
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
Hydrated Eutectic Electrolytes with Ligand-Oriented Solvation Shells for Long-Cycling Zinc-Organic Batteries Yang, Wuhai; Du, Xiaofan; Zhao, Jingwen Joule, Vol. 4, Issue 7 https://doi.org/10.1016/j.joule.2020.05.018	journal	July 2020
Rechargeable aqueous Zn-based energy storage devices Liu, Yiyang; Lu, Xu; Lai, Feili Joule, Vol. 5, Issue 11 https://doi.org/10.1016/j.joule.2021.10.011	journal	November 2021
“Soft Shorts” Hidden in Zinc Metal Anode Research Li, Qing; Chen, Ao; Wang, Donghong Joule, Vol. 6, Issue 2 https://doi.org/10.1016/j.joule.2021.12.009	journal	February 2022
Effects of Zn ²⁺ and H ⁺ Association with Naphthalene Diimide Electrodes for Aqueous Zn-Ion Batteries Na, Moony; Oh, Yusik; Byon, Hye Ryung Chemistry of Materials, Vol. 32, Issue 16 https://doi.org/10.1021/acs.chemmater.0c02357	journal	July 2020
Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal Pei, Allen; Zheng, Guangyuan; Shi, Feifei Nano Letters, Vol. 17, Issue 2 https://doi.org/10.1021/acs.nanolett.6b04755	journal	January 2017
Potential-Dependent Layering in the Electrochemical Double Layer of Water-in-Salt Electrolytes Zhang, Ruixian; Han, Mengwei; Ta, Kim ACS Applied Energy Materials, Vol. 3, Issue 8 https://doi.org/10.1021/acsaem.0c01534	journal	July 2020
Oxide versus Nonoxide Cathode Materials for Aqueous Zn Batteries: An Insight into the Charge Storage Mechanism and Consequences Thereof Oberholzer, Pascal; Tervoort, Elena; Bouzid, Assil ACS Applied Materials & Interfaces, Vol. 11, Issue 1 https://doi.org/10.1021/acsami.8b16284	journal	December 2018
Unveiling Critical Insight into the Zn Metal Anode Cyclability in Mildly Acidic Aqueous Electrolytes: Implications for Aqueous Zinc Batteries Glatz, Hadrien; Tervoort, Elena; Kundu, Dipan ACS Applied Materials & Interfaces, Vol. 12, Issue 3 https://doi.org/10.1021/acsami.9b16125	journal	December 2019
Multivalent-Ion versus Proton Insertion into Battery Electrodes Park, Min Je; Yaghoobnejad Asl, Hooman; Manthiram, Arumugam ACS Energy Letters, Vol. 5, Issue 7 https://doi.org/10.1021/acsenergylett.0c01021	journal	June 2020
Operando pH Measurements Decipher H ⁺ /Zn ²⁺ Intercalation Chemistry in High-Performance Aqueous Zn/δ-V ₂ O ₅ Batteries Liu, Xu; Euchner, Holger; Zarrabeitia, Maider ACS Energy Letters, Vol. 5, Issue 9 https://doi.org/10.1021/acsenergylett.0c01767	journal	September 2020
Energy Storage Chemistry in Aqueous Zinc Metal Batteries Wan, Fang; Zhou, Xunzhu; Lu, Yong ACS Energy Letters, Vol. 5, Issue 11 https://doi.org/10.1021/acsenergylett.0c02028	journal	October 2020
Alleviation of Dendrite Formation on Zinc Anodes via Electrolyte Additives Guo, Xiaoxia; Zhang, Zhenyu; Li, Jianwei ACS Energy Letters, Vol. 6, Issue 2 https://doi.org/10.1021/acsenergylett.0c02371	journal	January 2021
A Thin and Uniform Fluoride-Based Artificial Interphase for the Zinc Metal Anode Enabling Reversible Zn/MnO ₂ Batteries Han, Jin; Euchner, Holger; Kuenzel, Matthias ACS Energy Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsenergylett.1c01249	journal	August 2021
Tuning the Solvation Structure in Aqueous Zinc Batteries to Maximize Zn-Ion Intercalation and Optimize Dendrite-Free Zinc Plating Li, Chang; Kingsbury, Ryan; Zhou, Laidong ACS Energy Letters, Vol. 7, Issue 1 https://doi.org/10.1021/acsenergylett.1c02514	journal	January 2022
Solvation Structure Design for Aqueous Zn Metal Batteries Cao, Longsheng; Li, Dan; Hu, Enyuan Journal of the American Chemical Society, Vol. 142, Issue 51 https://doi.org/10.1021/jacs.0c09794	journal	December 2020
Characterizing the Structural Properties of N,N-Dimethylformamide-Based Ionic Liquid: Density-Functional Study Zhang, Lei; Li, Haoran; Wang, Yong The Journal of Physical Chemistry B, Vol. 111, Issue 37 https://doi.org/10.1021/jp0749064	journal	August 2007
Hydrolysis and Complexation of N , N -Dimethylformamide in New Nanostructurated Titanium Oxide Hybrid Organic–Inorganic Sols and Gel Cottineau, Thomas; Richard-Plouet, Mireille; Mevellec, Jean-Yves The Journal of Physical Chemistry C, Vol. 115, Issue 25 https://doi.org/10.1021/jp201864g	journal	June 2011
Solvation of Copper(II) Sulfate in Binary Water/N,N-Dimethylformamide Mixtures: From the Solution to the Gas Phase Tsierkezos, Nikos G.; Roithová, Jana; Schröder, Detlef The Journal of Physical Chemistry B, Vol. 112, Issue 14 https://doi.org/10.1021/jp710875x	journal	March 2008
Hyper-dendritic nanoporous zinc foam anodes Chamoun, Mylad; Hertzberg, Benjamin J.; Gupta, Tanya NPG Asia Materials, Vol. 7, Issue 4 https://doi.org/10.1038/am.2015.32	journal	April 2015
A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode Kundu, Dipan; Adams, Brian D.; Duffort, Victor Nature Energy, Vol. 1, Issue 10 https://doi.org/10.1038/nenergy.2016.119	journal	August 2016
Reversible aqueous zinc/manganese oxide energy storage from conversion reactions Pan, Huilin; Shao, Yuyan; Yan, Pengfei Nature Energy, Vol. 1, Issue 5 https://doi.org/10.1038/nenergy.2016.39	journal	April 2016
Polyaniline-intercalated manganese dioxide nanolayers as a high-performance cathode material for an aqueous zinc-ion battery Huang, Jianhang; Wang, Zhuo; Hou, Mengyan Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04949-4	journal	July 2018
Realizing high zinc reversibility in rechargeable batteries Ma, Lin; Schroeder, Marshall A.; Borodin, Oleg Nature Energy, Vol. 5, Issue 10 https://doi.org/10.1038/s41560-020-0674-x	journal	August 2020
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
Fluorinated interphase enables reversible aqueous zinc battery chemistries Cao, Longsheng; Li, Dan; Pollard, Travis Nature Nanotechnology, Vol. 16, Issue 8 https://doi.org/10.1038/s41565-021-00905-4	journal	May 2021
A non-flammable hydrous organic electrolyte for sustainable zinc batteries Han, Daliang; Cui, Changjun; Zhang, Kangyu Nature Sustainability, Vol. 5, Issue 3 https://doi.org/10.1038/s41893-021-00800-9	journal	December 2021
Brønsted acidic room temperature ionic liquids derived from N,N-dimethylformamide and similar protophilic amides Huang, Jing-Fang; Baker, Gary A.; Luo, Huimin Green Chem., Vol. 8, Issue 7 https://doi.org/10.1039/B604777G	journal	January 2006
Dynamic interphase–mediated assembly for deep cycling metal batteries Zhang, Weidong; Zhao, Qing; Hou, Yunpeng Science Advances, Vol. 7, Issue 49 https://doi.org/10.1126/sciadv.abl3752	journal	December 2021
Rechargeable nickel–3D zinc batteries: An energy-dense, safer alternative to lithium-ion Parker, Joseph F.; Chervin, Christopher N.; Pala, Irina R. Science, Vol. 356, Issue 6336 https://doi.org/10.1126/science.aak9991	journal	April 2017
Reversible epitaxial electrodeposition of metals in battery anodes Zheng, Jingxu; Zhao, Qing; Tang, Tian Science, Vol. 366, Issue 6465 https://doi.org/10.1126/science.aax6873	journal	October 2019
Highly Reversible Plating/Stripping of Porous Zinc Anodes for Multivalent Zinc Batteries Ko, Jesse S.; Bishop, Kelly; Seitzman, Natalie Journal of The Electrochemical Society, Vol. 167, Issue 14 https://doi.org/10.1149/1945-7111/abc206	journal	October 2020

Similar Records

Fluorinated interphase enables reversible aqueous zinc battery chemistries

Journal Article · 2021 · Nature Nanotechnology · OSTI ID:1787833

Cao, Longsheng; Li, Dan; Pollard, Travis; +17 more

Production of fast-charge Zn-based aqueous batteries via interfacial adsorption of ion-oligomer complexes

Journal Article · 2022 · Nature Communications · OSTI ID:1899727

Jin, Shuo; Yin, Jiefu; Gao, Xiaosi; +8 more

Fluoride-Rich, Organic–Inorganic Gradient Interphase Enabled by Sacrificial Solvation Shells for Reversible Zinc Metal Batteries

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:2480830

Xu, Wangwang; Li, Jiantao; Liao, Xiaobin; +6 more

Related Subjects

25 ENERGY STORAGE
SEIRAS
Superacid
XPS
Zn anode
Zn metal batteries
Zn-ion batteries
cryo-TEM

Title: Highly reversible Zn anode with a practical areal capacity enabled by a sustainable electrolyte and superacid interfacial chemistry

Citation Formats

References (47)

Similar Records

Related Subjects