【原】北京大学深圳研究院—富含氧缺陷的β- MnO2@Graphene包裹体用于高速率和长寿命水性锌离子电池

   近年来，人们对网格化电化学储能的兴趣日益浓厚，其中锌离子电池(AZIBs)尤其受到关注。在AZIBs的各种正极材料中，锰氧化物因其高能量密度和低成本而日益突出。但反应动力学迟缓，循环稳定性差，影响了其实际应用。在此，我们证明了缺陷工程和界面优化的联合使用可以同时提高MnO₂阴极的速率能力和循环稳定性。合成了具有丰富氧空位(V_O)的β-MnO₂和石墨烯氧化物(GO)包裹体，其中本体中的VO加速充放电动力学，而表面的GO抑制Mn的溶解。该电极在电流速率为4C的情况下，即使在2000次循环后，仍具有~ 129.6 mAh g^-1的持续可逆容量，优于目前最先进的MnO₂基阴极。氧化石墨烯涂层与表面VO直接相互作用以及β-MnO₂在循环过程中结构演化的规律可以解释β-MnO₂优异的性能。本研究的组合设计方案为AZIBs制备高速率、长寿命阴极提供了一条实用的途径。

图1 β- MnO₂和β-MnO₂@GO的XRD谱图。β-MnO₂@ GO的透射电镜、HRTEM形貌和相关EDS图(b和c中的插入物分别显示了GO层的存在和衍射图)。e β- MnO₂和β- MnO₂@GO的红外光谱比较。f C 1s和g O 1s的XPS峰。h β- MnO₂和β- MnO₂@GO在含氧气氛下的TGA曲线

图2 β-MnO₂和β-MnO₂@GO电极在第二循环(0.1C电流)的速率性能和恒流充放电(GCD)曲线对比。c β-MnO2@GO电极在不同速率电流下的GCD曲线。β-MnO₂和β-MnO₂@GO电极在e1c和f4c速率电流下的循环性能

图3 a在0.1C下的恒电流充放电曲线 b, c β-MnO₂@GO电极在原始点#H和#J处的XRD谱图和SEM形貌。d-g TEM和HRTEM图像的β-MnO₂@GO完全放电状态在第一个周期。h, i对选定点的O 1s和Zn 2p谱进行XPS分析。以c为单位的比例尺为~ 2 μm

图4.含和不含V_O时β-MnO₂的态电子密度。能量参照费米能级。b以β-MnO₂和β-MnO₂@GO为活性材料电极的电阻抗谱。c, d GITT曲线和计算的扩散系数

图5 a DFT计算了氧化石墨烯在β-MnO₂(110)、(101)、(100)和(001)表面V_O上的结合构型和吸附能(Ea)。b β-MnO₂电极在1C电流下循环50、100、150和200次后的原始状态和带电状态的XRD图。c, d β-MnO2电极中活性材料在1C电流下循环200次后的TEM形貌，显示结构完整性的下降，以及相应的HRTEM图像(插入ZnMn₂O₄尖晶石的衍射图)。e在1C电流下循环50、100、150和200次后，β-MnO₂@GO电极的原始状态和带电状态的XRD图。f, g β- MnO₂@ GO电极中活性材料在1C电流下循环200次后的TEM形貌，显示维持良好的纳米棒形貌，以及相应的HRTEM图像(镶嵌，衍射环显示ZnxMn₂O₄纳米晶尖晶石的(211)和(101)面)

   北京大学深圳研究院Feng Pan,Qinghe Zhao和Shunning Li等人于2021年发表在Nano-Micro Letters（https://link./article/10.1007%2Fs40820-021-00691-7）上。原文：Oxygen‑Deficient β‑MnO₂@Graphene Oxide Cathode for High‑Rate and Long‑Life Aqueous Zinc Ion Batteries。

潘锋，

      男，教授，博士生导师，北京大学深圳研究生院副院长、新材料学院创院院长，美国劳伦斯伯克利国家实验室高级访问科学家。

1985年获北大化学系学士；

1988年获中科院福建物构所硕士；

1994年获英国Strathclyde大学博士(获最佳博士论文奖)；

1994-1996年瑞士ETH博士后。

  研究领域

1. 新能源材料基因组研究（设计、计算、合成、表征）；

2. 纳米与晶体的结构与性能；

3. 新型装备研究与开发（3D打印、高功率等离子）；

4. 动力与储能电池及关键材料；

5. 新型太阳能电池与关键材料（柔性薄膜、银浆）；

6. 新型室温热电材料；

代表性论文

2019年度

18.Gui-Liang Xu, Qiang Liu, Kenneth K.S. Lau, Yuzi Liu, Xiang Liu, Han Gao, Xinwei Zhou, Minghao Zhuang, Yang Ren, Jiadong Li, Minhua Shao, Minggao Ouyang,Feng Pan, Zonghai Chen, Khalil Amine*, Guohua Chen*. Building ultra-conformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes,Nature Energy, (2019)(Accept).

17.Wei Zhang, Yan Li, Lijun Wu, Yandong Duan, Kim Kisslinger, Chunlin Chen, David C. Bock,Feng Pan, Yimei Zhu, Amy C. Marschilok, Esther S. Takeuchi, Kenneth J. Takeuchi, and Feng Wang*. Multi-electron transfer enabled by topotactic reaction in magnetite,Nat. Commun., (2019) (on-line) DOI: 10.1038/s41467-019-08851-5.

16.Dong Chen, Shunning Li, Jianshu Jie, Sibai Li, Shisheng Zheng, Mouyi Weng, Changcheng Yu, Shucheng Li, Dajun Chen,Feng Pan*. A descriptor of 'Material Genes’: Effective atomic size in structural unit of ionic crystals,SCI. CHINA Technol. Sc., (2019)(on-line). DOI: 10.1007/s11431-018-9461-x.

15.JianShu Jie, MouYi Weng, Dong Chen, ShuCheng Li, WeiJi Xiao, Jiaxin Zheng, LinWang Wang*,Feng Pan*. A new MaterialGo database and its comparison with other high-throughput electronic structure databases for their predicted energy band gap,Sci. China Technol. Sc., (2019).（Accept）

14.Jiaxin Zheng, Yaokun Ye, Tongchao Liu, Xinguo Xiao, Chongmin Wang, Feng Wang,Feng Pan*. Ni/Li disordering in layered Li(NixMnyCoz)O2: Electrochemical impact, origin and control, Acc. Chem. Res., (2019)(Accept).

13.Mouyi Weng, Zhi Wang, Guoyu Qian, Yaokun Ye, Zhefeng Chen, Xin Chen, Shisheng Zheng,Feng Pan*, Identify crystal structures by a new paradigm based on graph theory for building materials big data,Sci. China Chem., (2019).（特邀）

12.Jianshu Jie, Zongxiang Hu, Guoyu Qian, Mouyi Weng, Shunning Li, Shucheng Li, Mingyu Hu, Dong Chen, Weiji Xiao, Jiaxin Zheng, Lin-Wang Wang*,Feng Pan*. Discovering unusual structures from exception using big data and machine learning techniques,Sci. Bull., (2019)(Accept).

11.Guoyu Qian, Xiangbiao Liao, Yuxiang Zhu,Feng Pan*, Xi Chen*, Yuan Yang*. Designing flexible lithium-ion batteries by structural engineering,ACS Energy Lett., 4(2019), 690-701.

10.Defei Kong, Mingjian Zhang*, Yinguo Xiao, Jiangtao Hu, Wenguang Zhao, Lei Han,Feng Pan*. Insights into the structural evolution and Li/O loss in high-Ni layered oxide cathodes,Nano Energy, 59(2019), 327-335.

9.Jinlong Yang, Yinguo Xiao, Qinghe Zhao, Guangxing Zhang, Rui Wang, Gaofeng Teng, Xin Chen, Mouyi Weng, Daping He, Shichun Mu, Yuan Lin,Feng Pan*. Synergistic effect of charge transfer and short H-bonding on nanocatalyst surface for efficient oxygen evolution reaction,Nano Energy, 59(2019), 443-452.

8.Dawei Wang, Chao Xin, Mingjian Zhang, Jianming Bai, Jiaxin Zheng, Ronghui Kou, Jun Young Peter Ko, Ashfia Huq, Guiming Zhong, Cheng-Jun Sun, Yong Yang, Zonghai Chen, Yinguo Xiao, Khalil Amine,Feng Pan*, Feng Wang*. Intrinsic role of cationic substitution in tuning Li/Ni mixing in high-Ni layered oxides,Chem. Mater., (2019)(on-line). DOI: 10.1021/acs.chemmater.8b04673.

7.Yue Gu, Mouyi Weng, GaofenGaofeng Teng, Hua Zeng, Jianshu Jie, Weiji Xiao, Jiaxin Zheng*,Feng Pan*. Tuning polaronic redox behavior in Olivine phosphate,Phys. Chem. Chem. Phys., 21(2019), 4578-4583.

6.Xin Li, Zijian Wang, Hai Lin, Yidong Liu*, Yong Min,Feng Pan*. Composite electrolytes of pyrrolidone-derivatives-PEO enable to enhance performance of all solid state lithium-ion batteries.Electrochim. Acta, 293(2019), 25-29.

5.Jianhang Cen, Shunning Li*, Jiaxin Zheng,Feng Pan*. Electron polarons in the subsurface layer of Mo/W-doped BiVO4 surfaces,RSC Adv., 9(2)(2019), 819-823.

4.Bocong Zheng, Zhongzhen Wu*, Suihan Cui, Shu Xiao, Liangliang Liu, Hai Lin, Ricky K.Y. Fu, Xiubo Tian,Feng Pan*. Discharge and Deposition Characteristics of High-Power impulse Magnetron Sputtering Using Various Target Materials,IEEE T. Plasma Sci., 47(1)(2019), 193-198.

3. Jun Tang, Xiongwei Zhong, Haiqiao Li, Yan Li,Feng Pan*, Baomin Xu*, In-situ and selectively laser reduced graphene oxide sheets as excellent conductive additive for high rate capability LiFePO4 lithium ion batteries,Journal of Power Sources, 412 (2019) 677–682.PDF

2.Jianhang Cen, Shunning Li*, Jiaxin Zheng,Feng Pan*. Electron polarons in the subsurface layer of Mo/W-doped BiVO4surfaces,RSC Adv., 9(2)(2019), 819-823.

1.Yehuan Li, Xin Chen, Mingjian Zhang, Yuanmin Zhu, Wenju Ren, Zongwei Mei*, Meng Gu*,Feng Pan*. Oxygen vacancy-rich MoO3-x nanobelts for photocatalytic N2 reduction to NH3 in pure water,Catal. Sci. Technol., (2019). DOI: 10.1039/c8cy02357c.