“2合1”策略构建双功能氧电极反应电催化剂用于可充电锌-空气电池

doi:10.1016/S1872-2067(21)63979-7

催化学报 ›› 2022, Vol. 43 ›› Issue (11): 2906-2912.DOI: 10.1016/S1872-2067(21)63979-7

“2合1”策略构建双功能氧电极反应电催化剂用于可充电锌-空气电池

刘会兵^†, 谢日鑫^†, 牛自强, 贾巧焕, 杨柳^*(), 王世涛, 曹达鹏^#()

北京化工大学有机无机复合材料国家重点实验室, 北京 100029

收稿日期:2022-03-26 接受日期:2022-05-16 出版日期:2022-11-18 发布日期:2022-10-20
通讯作者: 杨柳,曹达鹏
作者简介:^† 共同第一作者
基金资助:
国家重点研发计划项目(2019YFA0210300);北京化工大学优秀人才和国家博士后创新人才计划(BX20200041)

Two-in-one strategy to construct bifunctional oxygen electrocatalysts for rechargeable Zn-air battery

Huibing Liu^†, Rixin Xie^†, Ziqiang Niu, Qiaohuan Jia, Liu Yang^*(), Shitao Wang, Dapeng Cao^#()

State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China

Received:2022-03-26 Accepted:2022-05-16 Online:2022-11-18 Published:2022-10-20
Contact: Liu Yang, Dapeng Cao
About author:^† Contributed equally to this work.
Supported by:
National Key Research and Development Project(2019YFA0210300);Outstanding Talent Fund from Beijing University of Chemical Technology and China National Postdoctoral Program of Innovative Talents(BX20200041)

摘要/Abstract

摘要：

可循环充放电的锌空气电池具有理论能量密度高、环境友好和相对安全性等特性, 因而广受关注. 但锌空气电池的性能受到氧电极上缓慢的氧还原反应(ORR)/析氧反应(OER)动力学的限制. 目前, 贵金属催化剂Pt/C, IrO₂和RuO₂被认为是ORR/OER性能较好的电催化剂, 然而高成本阻碍了其商业化应用. 因此, 开发非贵金属ORR/OER催化剂具有十分重要的意义. 目前, 氮掺杂多孔碳(NPC)是有效的非贵金属基ORR催化剂之一, 因为高电负性的氮可以调控碳原子的电子结构, 使催化剂表面电荷再分配, 有效调节催化剂对反应中间体的化学吸附能, 进而促进ORR电催化反应, 碱性条件下其ORR电催化性能甚至能超过商业Pt/C催化剂. 但NPC缺乏OER活性位点, 不是一种良好的双功能氧电极反应电催化剂. 文献研究表明, 金属氧化物或氢氧化物(MOOH)被认为是真正的OER活性中心, 但它们几乎没有ORR活性. 因此, 将高ORR和OER活性中心(如MOOH和NPC)整合到一种复合材料中的“2合1”策略对设计高效双功能氧电极催化剂具有重要意义.

本文采用“2合1”策略合成了金属羟基氧化物负载于NPC的双功能氧电极反应催化剂(PA-CoFe@NPC), 其中NPC作为ORR催化活性位点, 金属羟基氧化物作为OER催化活性位点. 该双功能催化剂PA-CoFe@NPC表现出较好的ORR和OER催化活性, ORR起始电位为0.95 V, 半波电位为0.85 V vs. RHE; 对于OER反应, 仅需要384 mV过电势即可得到10 mA cm^‒2的电流密度. 该催化剂OER和ORR的电势差为0.76 V, 优于对比样20%Pt/C+IrO₂ (0.85 V). 将该双功能氧电极催化剂用于锌-空气电池的氧电极, 所制备的锌-空气电池表现出较好的充放电性能和较高的功率密度(156.3 mW cm^‒2), 并且170 h连续充放电循环稳定, 其稳定性以及活性明显优于20%Pt/C+IrO₂作为氧电极所制备的锌-空气电池的性能. 综上, 本文所报道的“2合1”策略为设计多功能电催化剂提供了一种新思路.

关键词: 2合1策略, 双功能催化剂, 氧还原, 氧析出, 锌-空气电池

Abstract:

Integrating two different catalytic active sites into one composite is a useful 2-in-1 strategy for designing high-efficient bifunctional catalysts, which can easily tailor the activity of each reaction. Hence, we adopt the 2-in-1 strategy to design the metal oxyhydroxide supported on N-doped porous carbons (PA-CoFe@NPC) as the oxygen bifunctional catalyst, where NPC provides the activity for oxygen reduction reaction (ORR) while the metal oxyhydroxide is responsible for oxygen evolution reaction (OER). Results demonstrate that the PA-CoFe@NPC indeed exhibits both super ORR and OER activities. Impressively, using bifunctional PA-CoFe@NPC as the oxygen electrode, the resulting Zn-air battery exhibits outstanding charge and discharge performance with the peak power density of 156.3 mW cm^‒2, and also exhibits a long-term cycle stability with continuous cyclic charge and discharge of 170 hours that is obviously better than the 20% Pt/C+IrO₂based one. The 2-in-1 strategy in this work can be efficiently extended to design other bi- or multi-functional electrocatalysts.

Key words: Two-in-one strategy, Bifunctional catalyst, Oxygen reduction, Oxygen evolution, Zn-air battery

刘会兵, 谢日鑫, 牛自强, 贾巧焕, 杨柳, 王世涛, 曹达鹏. “2合1”策略构建双功能氧电极反应电催化剂用于可充电锌-空气电池[J]. 催化学报, 2022, 43(11): 2906-2912.

Huibing Liu, Rixin Xie, Ziqiang Niu, Qiaohuan Jia, Liu Yang, Shitao Wang, Dapeng Cao. Two-in-one strategy to construct bifunctional oxygen electrocatalysts for rechargeable Zn-air battery[J]. Chinese Journal of Catalysis, 2022, 43(11): 2906-2912.

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图/表 5

Fig. 1. (a) Synthesis diagram of PA-CoFe@NPC. (b) SEM image of P-PA-CoFe@NPC. (c) TEM image of P-PA-CoFe@NPC. (d-h) EDS mappings for P-PA-CoFe@NPC.

Fig. 2. All ORR measurements were implemented in O2-saturated 0.1 mol L?1 KOH electrolyte. (a) ORR polarization curves. (b) Tafel plots of PA-CoFe@NPC, PA-Co@NPC, PA-Fe@NPC, NPC and 20% Pt/C. (c) The n (upper) and the H2O2 yield (lower) of PA-CoFe@NPC and 20% Pt/C at 0.2-0.8 V from RRDE. (d) I-t chronoamperometric response of PA-CoFe@NPC and 20% Pt/C.

Fig. 3. OER performance of PA-CoFe@NPC, PA-Co@NPC, PA-Fe@NPC, NPC and 20% Pt/C+IrO2 samples in 0.1 mol L-1 KOH. (a) OER LSV plots. (b) Tafel plots. (c) Nyquist plots. (d) OER and ORR LSV curves.

Fig. 4. (a) TEM image of PA-CoFe@NPC. (b) HRTEM image of PA-CoFe@NPC (scale bar, 5 nm). (c-i) EDS mappings of PA-CoFe@NPC after the OER. (j) Co 2p XPS spectra of PA-CoFe@NPC before and after the OER. (k) Fe 2p XPS spectra of PA-CoFe@NPC before and after the OER.

Fig. 5. (a) The sketch mapping of Zn-air battery. (b) Open circuit voltage of PA-CoFe@NPC based battery. (c) The discharging curves and power density of PA-CoFe@NPC and 20% Pt/C+IrO2 based Zn-air batteries. (d) Charging and discharging curves of PA-CoFe@NPC and 20% Pt/C+IrO2-based batteries. (e) The stability of PA-CoFe@NPC and 20% Pt/C+IrO2 based battery at 5 mA cm-2 of 170 h cyclic charge and discharge test.

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“2合1”策略构建双功能氧电极反应电催化剂用于可充电锌-空气电池

Two-in-one strategy to construct bifunctional oxygen electrocatalysts for rechargeable Zn-air battery

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