The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commerci...The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications.To address these issues,a novel anode-free Zniodine battery(AFZIB)was designed via a simple,low-cost and scalable approach.Iodine plays bifunctional roles in improving the AFZIB overall performance:enabling high-performance Zn-rich cathode and modulating Zn deposition behavior.On the cathode side,the ZnI_(2) serves as Zn-rich cathode material.The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI_(2) to enhance electron conductivity and suppress the shuttle effect of iodine species.On the anode side,trace I_(3)^(−) additive in the electrolyte creates surface reconstruction on the commercial Cu foil.The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility(average coulombic efficiency>99.91% over 7,000 cycles).Based on such a configuration,AFZIB exhibits significantly increased energy density(162 Wh kg^(−1)) and durable cycle stability(63.8% capacity retention after 200 cycles)under practical application conditions.Considering the low cost and simple preparation methods of the electrode materials,this work paves the way for the practical application of AZMBs.展开更多
使用低成本、高安全性的水系电解液使二次锌金属电池(AZMBs)成为大规模储能系统是最有前途的选择.然而,锌金属负极在水系电解液中热力学稳定性较差,严重阻碍了AZMBs的实际应用.在此,我们通过在锌表面涂覆氟化石墨并利用氟化石墨和锌之...使用低成本、高安全性的水系电解液使二次锌金属电池(AZMBs)成为大规模储能系统是最有前途的选择.然而,锌金属负极在水系电解液中热力学稳定性较差,严重阻碍了AZMBs的实际应用.在此,我们通过在锌表面涂覆氟化石墨并利用氟化石墨和锌之间原位的界面反应开发了一种富氟的杂化人工固体电解质界面来解决上述问题.疏水的氟化石墨可以有效地限制电解液和电极之间的接触,从而显著提高锌负极的抗腐蚀能力.同时,由氟化石墨和锌原位反应生成的ZnF_(2)共同组成的富氟杂化界面可以促进Zn2+的脱溶剂化作用,并均匀化锌离子通量,从而有效地抑制了副反应发生和枝晶生长.因此,在苛刻的测试条件下(10 mA cm^(−2),1 mA h cm^(−2)和30 mA cm^(−2),10 mA h cm^(−2)),对称电池可以分别稳定地循环1400和200小时以上,远远超过了裸锌的性能.此外,使用载量为6 mg cm^(−2)的MnO_(2)正极组装的Zn/MnO_(2)全电池在1 A g^(−1)的条件下经过2000次循环,仍能保持80%以上的容量.本文提出的这种构建富氟杂化ASEI的方法可以为设计高性能AZMBs提供一种有效的潜在策略.展开更多
基金This work was financially supported by Shaanxi Yanchang Petroleum CO.,Ltd(18529)Yiwu Research Institute of Fudan University(21557),the National Science Foundation of China(22075048)the Shanghai International Collaboration Research Project(19520713900).
文摘The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications.To address these issues,a novel anode-free Zniodine battery(AFZIB)was designed via a simple,low-cost and scalable approach.Iodine plays bifunctional roles in improving the AFZIB overall performance:enabling high-performance Zn-rich cathode and modulating Zn deposition behavior.On the cathode side,the ZnI_(2) serves as Zn-rich cathode material.The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI_(2) to enhance electron conductivity and suppress the shuttle effect of iodine species.On the anode side,trace I_(3)^(−) additive in the electrolyte creates surface reconstruction on the commercial Cu foil.The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility(average coulombic efficiency>99.91% over 7,000 cycles).Based on such a configuration,AFZIB exhibits significantly increased energy density(162 Wh kg^(−1)) and durable cycle stability(63.8% capacity retention after 200 cycles)under practical application conditions.Considering the low cost and simple preparation methods of the electrode materials,this work paves the way for the practical application of AZMBs.
基金financially supported by the National Natural Science Foundation of China(22075048 and 52201201)Shaanxi Yanchang Petroleum Co.,Ltd.(18529)+2 种基金Yiwu Research Institute of Fudan University(20-1-06)Shanghai International Collaboration Research Project(19520713900)the State Key Lab of Advanced Metals and Materials(2022Z-11).
文摘使用低成本、高安全性的水系电解液使二次锌金属电池(AZMBs)成为大规模储能系统是最有前途的选择.然而,锌金属负极在水系电解液中热力学稳定性较差,严重阻碍了AZMBs的实际应用.在此,我们通过在锌表面涂覆氟化石墨并利用氟化石墨和锌之间原位的界面反应开发了一种富氟的杂化人工固体电解质界面来解决上述问题.疏水的氟化石墨可以有效地限制电解液和电极之间的接触,从而显著提高锌负极的抗腐蚀能力.同时,由氟化石墨和锌原位反应生成的ZnF_(2)共同组成的富氟杂化界面可以促进Zn2+的脱溶剂化作用,并均匀化锌离子通量,从而有效地抑制了副反应发生和枝晶生长.因此,在苛刻的测试条件下(10 mA cm^(−2),1 mA h cm^(−2)和30 mA cm^(−2),10 mA h cm^(−2)),对称电池可以分别稳定地循环1400和200小时以上,远远超过了裸锌的性能.此外,使用载量为6 mg cm^(−2)的MnO_(2)正极组装的Zn/MnO_(2)全电池在1 A g^(−1)的条件下经过2000次循环,仍能保持80%以上的容量.本文提出的这种构建富氟杂化ASEI的方法可以为设计高性能AZMBs提供一种有效的潜在策略.
