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In situ polymerization of poly(3,4-ethylenedioxythiophene)protective layer towards stable zinc anode

Nano Research 2025年第1期18卷 382-394页

作者： Debin Luo Peng Zhou Xiaowei Lv Panpan Sun Xiaohua Sun Hewei Zhao College of Materials and Chemical Engineering Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion MaterialsChina Three Gorges UniversityYichang 443002China Hubei Three Gorges Laboratory Yichang 443007China School of Chemistry Beihang UniversityBeijing 100191China

Aqueous zinc-ion devices are considered promising candidates for energy storage due to their high safety,low cost and relatively high energy ***,the dendrite growth,hydrogen evolution reaction(HER)and corrosion of the zinc anode significantly limit the development of Zn-ion ***,an inexpensive poly(3,4-ethylenedioxythiophene)(PEDOT)protective layer was constructed in situ on the Zn surface using electropolymerization to suppress dendrite growth and side reactions,thereby enhancing the reversibility of *** and theoretical calculations revealed that this hydrophilic protective layer promotes the desolvation process of hydrated Zn^(2+)and facilitates the transport of zinc ions,thus improving the thermodynamic and kinetic properties of Zn^(2+)deposition and inhibiting interfacial side ***,the optimized PEDOT@Zn symmetric battery exhibited a cycling stability exceeding 1250 h at 0.5 mA·cm^(-2)and 0.25 mAh·cm^(-2),with a significantly reduced overpotential(from 91.8 to 35 mV).With the assistance of the PEDOT protective layer,the PEDOT@Zn//Cu battery maintained approximately 99.5%Coulombic efficiency after 450 ***-situ scanning electron microscopy(SEM)and in situ optical microscopy characterizations further confirmed that the PEDOT protective layer can effectively suppress the growth of zinc ***,the Zn-ion capacitors assembled by the PEDOT@Zn and activated carbon also demonstrated outstanding cycling stability.

关键词： zinc-ion devices zinc anode poly(3 4-ethylenedioxythiophene)(PEDOT) dendrite desolvation process

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Growth and inhibition of zinc anode dendrites in Zn-air batteries:Model and experiment

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Chinese Journal of Chemical Engineering 2024年第3期67卷 268-281页

作者： Cuiping He Qingyi Gou Yanqing Hou Jianguo Wang Xiang You Ni Yang Lin Tian Gang Xie Yuanliang Chen Kunming University of Science and Technology State Key Laboratory of Complex Nonferrous Metal Resources Clean UtilizationKunming 650093China Kunming University of Science and Technology Faculty of Metallurgical and Energy EngineeringKunming 650093China China Copper Co.Ltd KunmingYunnan 650051China State Key Laboratory of Advanced Metallurgy for Non-ferrous Metals Kunming 650051China Sichuan Shunying Power Battery Materials Co.Ltd Sichuan 620076China

zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material ***,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation *** this context,Zn dendrite growth has a greater impact on the cycle *** this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed *** simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main *** experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.

关键词： Zn-air battery zinc anode zinc dendrite Simulated dendrite growth Inhibit dendrite growth Phase-field model

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Recent advances in interfacial modification of zinc anode for aqueous rechargeable zinc ion batteries

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Journal of Energy Chemistry 2023年第8期83卷 287-303,I0009页

作者： Qing Wen Hao Fu Ru-de Cui He-Zhang Chen Rui-Han Ji Lin-Bo Tang Cheng Yan Jing Mao Ke-Hua Dai Xia-Hui Zhang Jun-Chao Zheng School of Metallurgy and Environment Central South UniversityChangsha 410083HunanChina Engineering Research Center of the Ministry of Education for Advanced Battery Materials Central South UniversityChangsha 410083HunanChina School of Chemistry and Chemical Engineering Hunan University of Science and TechnologyXiangtan 411201HunanChina School of Mechanical Medical and Process EngineeringQueensland University of TechnologyBrisbaneQueensland 4001Australia School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001HenanChina College of Chemistry Tianjin Normal UniversityTianjin 300387China School of Mechanical and Materials Engineering Washington State UniversityPullman 99164WashingtonUnited States

To tackle energy crisis and achieve sustainable development, aqueous rechargeable zinc ion batteries have gained widespread attention in large-scale energy storage for their low cost, high safety, high theoretical capacity, and environmental compatibility in recent years. However, zinc anode in aqueous zinc ion batteries is still facing several challenges such as dendrite growth and side reactions(e.g., hydrogen evolution), which cause poor reversibility and the failure of batteries. To address these issues, interfacial modification of Zn anodes has received great attention by tuning the interaction between the anode and the electrolyte. Herein, we present recent advances in the interfacial modification of zinc anode in this review. Besides, the challenges of reported approaches of interfacial modification are also ***, we provide an outlook for the exploration of novel zinc anode for aqueous zinc ion *** hope that this review will be helpful in designing and fabricating dendrite-free and hydrogenevolution-free Zn anodes and promoting the practical application of aqueous rechargeable zinc ion batteries.

关键词： zinc ion batteries zinc anode Interfacial modification Functional coating

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MXene ink hosting zinc anode for high performance aqueous zinc metal batteries

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Journal of Energy Chemistry 2023年第1期76卷 187-194,I0005页

作者： Jae Min Park Milan Jana Sang Ha Baek Taehun Kang Peixun Xiong Jeong Hee Park Jun Soo Kim Ali Shayesteh Zeraati Mikhail Shekhirev Paul V.Braun Yury Gogotsi Ho Seok Park School of Chemical Engineering Sungkyunkwan University2066SeoburoJangan-guSuwon 440-746Republic of Korea Department of Chemical and Petroleum Engineering University of Calgary2500 University Dr NWCalgary T2N 1N4Canada Department of Materials Science and Engineering Materials Research LaboratoryBeckman Institute for Advanced Science and TechnologyUniversity of Ilinois at Urbana-ChampaignUrbanaIL61801USA A.J.Drexel Nanomaterials Institute and Department of Materials Science and Engineering Drexel UniversityPhiladelphiaPA 19104USA SKKU Institute of Energy Science and Technology(SIEST) Sungkyunkwan University2066SeoburoJangan-guSuwon 440-746Republic of Korea SKKU Advanced Institute of Nano Technology(SAINT) Sungkyunkwan University 2066SeoburoJangan-guSuwon 440-746Republic of Korea

Despite the safety,low cost,and high theoretical capacity(820 mA h g^(-1))of Zn metal anodes,the practical application of aqueous Zn metal batteries remains a critical challenge due to the Zn dendrite growth,corrosion,and hydrogen evolution ***,we demonstrate the MXene ink hosting Zn metal anodes(MX@Zn)for high-performance and patternable Zn metal full *** as-designed MX@Zn electrode is more facile and reversible than bare Zn and CC@Zn,as verified by better cyclic stability and lower overpotentials of symmetric cells with the plating capacity of 0.05 mA h cm^(-2)at 0.1 m A cm^(-2)and of 1 m A h cm^(-2)at 1 m A cm^(-2).The MX@Zn|MnO_(2)full cells deliver a high specific capacity of 281.9 m A h g^(-1),91.5%of the theoretical capacity,achieving 50%capacity retention from 60 mA g^(-1)to 300 mA g^(-1)and 79.7%of initial capacity after 200 ***,the patterned devices based on the MX@Zn electrode achieve high energy and power densities of 348.57 Wh kg^(-1)and 1556 W kg^(-1),respectively,along with a capacity retention of 64%and Coulombic efficiency of 99%over 500 *** high performance of MX@Zn is attributed to the high electrical conductivity and hydrophilicity of MXene and rapid ion diffusion through the 3D interconnected porous channels.

关键词： MXene ink zinc anode Metal batteries Patterning Electrodeposition

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Highly reversible and long-lived zinc anode assisted by polymer-based hydrophilic coating

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Frontiers of Materials Science 2023年第4期17卷 93-102页

作者： Hang Chen Xinghan Yuan Hongmei Qin Chuanxi Xiong School of Materials Science and Engineering Wuhan University of TechnologyWuhan 430070China

Rechargeable aqueous zinc-ion batteries(AZIBs)are the most promising candidates for the energy storage due to their high safety,rich resources,and large specific ***,AZIBs using neutral or slightly acidic electrolytes still face side effects and zinc dendrites on the anode *** stabilize the Zn anode,a chemically stable and multi-functional coating of polyvinylidene fluoride(PVDF)and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)was prepared on the Zn *** anhydride groups in 6FDA can improve the hydrophilicity,promoting the migration of zinc ***,PVDF is compatible with 6FDA because of the presence of organic F-containing groups,which can also effectively reduce the nucleation overpotential and exhibit the dendrite-free Zn deposition/*** PVDF/6FDA@Zn symmetric cell can cycle for 5000 h at a current density of 0.5 mA·cm^(−2),maintaining the extremely low polarization voltage and overpotential of 28 and 8 mV,*** PVDF/6FDA@Zn||MnO2 full cell can remain a specific capacity of~90 mAh·g^(−1)after 2000 cycles at 1.5 A·g^(−1).This simple method achieves a reversible Zn anode,providing an inspiring strategy for ultra-long-cycle AZIBs.

关键词： aqueous zinc ion battery zinc anode polyvinylidene fluoride composite film

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Stabilizing zinc anode via a chelation and desolvation electrolyte additive

Advanced Powder Materials

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Advanced Powder Materials 2022年第1期1卷 97-105页

作者： Jin Cao Dongdong Zhang Rungroj Chanajaree Yilei Yue Zhiyuan Zeng Xinyu Zhang Jiaqian Qin International Graduate Program of Nanoscience&Technology Chulalongkorn UniversityBangkok10330Thailand Metallurgy and Materials Science Research Institute Chulalongkorn UniversityBangkok10330Thailand State Key Laboratory of Metastable Materials Science and Technology Yanshan UniversityQinhuangdao066004China Department of Materials Science and Engineering City University of Hong Kong83 Tat Chee AvenueKowloonHong Kong999077China Research Unit of Advanced Materials for Energy Storage Chulalongkorn UniversityBangkok10330Thailand

The uncontrollable dendrites growth and intricately water-induced side reactions occurred on zinc anode leads to safety issues and poor electrochemical kinetics,which largely limit the widespread application of zinc-ion batteries(ZIBs).Herein,ethylenediaminetetraacetic acid disodium salt(EDTA-2Na)is utilized as an electrolyte additive to strengthen the reversibility and cycling stability of zinc *** results and theoretical calculation demonstrate that the EDTA-2Na presents a much stronger coordination with Zn^(2+)when comparing with H_(2)O molecular,implying the EDTA-2Na is capable to enter the solvation shell of[Zn(OH_(2))_(6)]^(2+)and coordinate with Zn^(2+)ions,thus achieving a flat and smooth zinc deposition with less by-products(Zn_(4)SO_(4)(OH)6·xH_(2)O and H_(2)).Consequently,the zinc symmetric battery with EDTA-2Na additive delivers an excellent cycling stability up to 1800 h under current density of 1 mA cm^(-2),and the hydrogen evolution reaction(HER),corrosion,by-product issues are significantly ***,the rate performance and stability of coin-type and pouch-type Zn||MnO2/graphite batteries are significantly boosted via EDTA-2Na additive(248 mAh g^(-1)at 0.1 A g^(-1),81.3%after 1000 cycles at a A g^(-1)).This kind of electrolyte additive with chelation and desolvation functions shed lights on strategies of improving zinc anode stability for further application of ZIBs.

关键词： zinc-ion battery zinc anode Dendrites EDTA-2Na Desolvation

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Functional group differentiation of isomeric solvents enables distinct zinc anode chemistry

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Nano Research Energy 2023年第2期2卷 218-228页

作者： Chao Liu Qing Li Yilun Lin Zhiquan Wei Yihan Yang Cuiping Han Minshen Zhu Haiyan Zhang Hongfei Li School of Materials and Energy Guangdong University of TechnologyGuangzhou 510006China Songshan Lake Materials Laboratory Dongguan 523808China Department of Materials Science and Engineering City University of Hong KongHong Kong 999077China School of System Design and Intelligent Manufacturing Southern University of Science and TechnologyShenzhen 518055China Faculty of Materials Science and Engineering/Institute of Technology for Carbon Neutrality Shenzhen Institutes of Advanced TechnologyChinese Academy of SciencesShenzhen 518055China Research Center for Materials Architecturesand Integration of Nanomembranes(MAIN)TU ChemnitzChemnitz 09126Germany

Electrolytes hold the key to realizing reliable zinc(Zn)*** organic molecules have been proven effective in stabilizing Zn anodes;however,irrational comparisons exist due to the uncontrolled molecular weights and functional group *** this work,two“isomeric molecules”:1,2-dimethoxyethane(DME)and 1-methoxy-2-propanol(PM),with identical molecular weights but different functional groups,have been studied as co-solvents in electrolytes,which have delivered distinct electrochemical *** and simulative study indicates the dipole moment induced by the hydroxyl groups in PM(higher molecular polarity than ether groups in DME)reconstructs the space charge region,enhances the concentration of Zn^(2+)in the vicinity of Zn anodes,and in-situ derives different solid electrolyte interphase(SEI)models and electrode-electrolyte interfaces,resulting in exceptional cycling ***,the Zn||Cu cell with PM worked over 2000 cycles with high Coulombic efficiency(CE)of 99.7%.The Zn||Zn symmetric cell cycled over 2000 h at 1 mA·cm^(−2),and showed excellent stability at an ultrahigh current density of 10 mA·cm^(−2)and capacity of 20 mAh·cm^(−2)over 200 h(depth of discharge,DOD of 70%).The Zn||sodium vanadate pouch cell with a high mass loading of 6.3 mg·cm^(−2)and a high capacity of 24 mAh demonstrates superior cyclability after 570 *** work can be a good starting point to provide reliable guidance on electrolyte design for practical aqueous Zn batteries.

关键词： functional group isomeric solvents zinc anode solid electrolyte interphase(SEI)model

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Hetero Nucleus Growth Stabilizing zinc anode for High‑Biosecurity zinc‑Ion Batteries

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Nano-Micro Letters 2023年第12期15卷 349-360页

作者： Jingjing Li Zhexuan Liu Shaohua Han Peng Zhou Bingan Lu Jianda Zhou Zhiyuan Zeng Zhizhao Chen Jiang Zhou Department of Plastic Surgery and National Clinical Research Center for Geriatric Disorders Xiangya HospitalCentral South UniversityChangsha 410008People’s Republic of China School of Materials Science and Engineering Hunan Provincial Key Laboratory of Electronic Packaging and Advanced Functional MaterialsCentral South UniversityChangsha 410083People’s Republic of China Hunan Provincial Key Defense Laboratory of High Temperature Wear‑Resisting Materials and Preparation Technology Hunan University of Science and TechnologyXiangtan 411201People’s Republic of China School of Physics and Electronics Hunan UniversityChangsha 410082People’s Republic of China Department of Plastic Surgery The Third Xiangya HospitalCentral South UniversityChangsha 410013People’s Republic of China Department of Materials Science and Engineering City University of Hong Kong83 Tat Chee AvenueKowloon 999077Hong KongPeople’s Republic of China

Biocompatible devices are widely employed in modernized lives and medical fields in the forms of wearable and implantable devices,raising higher requirements on the battery biocompatibility,high safety,low cost,and excellent electrochemical performance,which become the evaluation criteria toward developing feasible biocompatible ***,through conducting the battery implantation tests and leakage scene simulations on New Zealand rabbits,zinc sulfate electrolyte is proved to exhibit higher biosecurity and turns out to be one of the ideal zinc salts for biocompatible zinc-ion batteries(ZIBs).Furthermore,in order to mitigate the notorious dendrite growth and hydrogen evolution in mildly acidic electrolyte as well as improve their operating stability,Sn hetero nucleus is introduced to stabilize the zinc anode,which not only facilitates the planar zinc deposition,but also contributes to higher hydrogen evolution ***,a long lifetime of 1500 h for the symmetrical cell,the specific capacity of 150 mAh g^(-1)under 0.5 A g^(-1)for the Zn-MnO_(2)battery and 212 mAh g^(-1)under 5 A g^(-1)for the Zn—NH4V4O10 battery are *** work may provide unique perspectives on biocompatible ZIBs toward the biosecurity of their cell components.

关键词： Aqueous zinc-ion batteries Biocompatible devices Operating stability zinc anode zinc salts electrolyte

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High donor-number and low content electrolyte additive for stabilizing zinc metal anode

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Journal of Energy Chemistry 2024年第8期95卷 626-635,I0014页

作者： Yuxin Gong Ruifan Lin Bo Wang Huaizheng Ren Lei Wang Han Zhang Jianxin Wang Deyu Li Yueping Xiong Dianlong Wang Huakun Liu Shixue Dou MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage State Key Laboratory of Urban Water Resource and EnvironmentSchool of Chemistry and Chemical EngineeringHarbin Institute of TechnologyHarbin 150001HeilongjiangChina Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) College of ChemistryNankai UniversityTianjin 300071China Institute of Energy Material Science University of Shanghai for Science and TechnologyShanghai 200093China

The aqueous zinc ion batteries(AZIBs)are thought as promising competitors for electrochemical energy storage,though their wide application is curbed by the uncontrollable dendrite growth and gas evolution side ***,to stabilize both zinc anodes and water molecules,we developed a modified electrolyte by adding a trace amount of N,N-diethylformanmide(DEF)into the ZnSO_(4)electrolyte for the first time in zinc ion *** effectiveness of DEF is predicted by the comparison of donor number and its preferential adsorption behavior on the zinc anode is further demonstrated by several spectroscopy characterizations,electrochemical methods,and molecular dynamics *** modified electrolyte with 5%*** content can ensure a stable cycling life longer than 3400 h of Zn‖Zn symmetric cells and an ultra-reversible Zn stripping/plating process with a high coulombic efficiency of 99.7%.The Zn‖VO_(2)full cell maintains a capacity retention of 83.5%and a 104 mA h g^(-1)mass capacity after *** work provides insights into the role of interfacial adsorption behavior and the donor number of additive molecules in designing low-content and effective aqueous electrolytes.

关键词： Aqueous zinc ion batteries zinc anode Electrolyte additives Donor number zinc dendrites

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An Electrochemical Perspective of Aqueous zinc Metal anode

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Nano-Micro Letters 2024年第1期16卷 274-312页

作者： Huibo Yan Songmei Li Jinyan Zhong Bin Li School of Materials Science and Engineering Beihang UniversityBeijing 100191People’s Republic of China

Based on the attributes of nonflammability,environmental benignity,and cost-effectiveness of aqueous electrolytes,as well as the favorable compatibility of zinc metal with them,aqueous zinc ions batteries(AZIBs)become the leading energy storage candidate to meet the requirements of safety and low ***,aqueous electrolytes,acting as a double-edged sword,also play a negative role by directly or indirectly causing various parasitic reactions at the zinc anode *** reactions include hydrogen evolution reaction,passivation,and dendrites,resulting in poor Coulombic efficiency and short lifespan of AZIBs.A comprehensive review of aqueous electrolytes chemistry,zinc chemistry,mechanism and chemistry of parasitic reactions,and their relationship is ***,the understanding of strategies for suppressing parasitic reactions from an electrochemical perspective is not profound *** this review,firstly,the chemistry of electrolytes,zinc anodes,and parasitic reactions and their relationship in AZIBs are deeply ***,the strategies for suppressing parasitic reactions from the perspective of enhancing the inherent thermodynamic stability of electrolytes and anodes,and lowering the dynamics of parasitic reactions at Zn/electrolyte interfaces are ***,the perspectives on the future development direction of aqueous electrolytes,zinc anodes,and Zn/electrolyte interfaces are presented.

关键词： Aqueous zinc ions batteries Parasitic reactions Aqueous electrolyte zinc anode

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