<i>α</i>-MnO<sub>2</sub> 作为先进的双功能ORR/IOR电催化剂构建可充电锌空电池

王振; 赵慧; 周菊红; 盛可发; 王涛; 江彬彬

doi:10.19906/j.cnki.JFCT.2023066

α-MnO₂ 作为先进的双功能ORR/IOR电催化剂构建可充电锌空电池

doi: 10.19906/j.cnki.JFCT.2023066

安庆师范大学化学化工学院光电磁材料安徽省重点实验室, 安徽安庆 246011

基金项目: 安徽省自然科学基金（2008085QB53），安徽省教育厅高校科学研究重点项目（KJ2021A0642, KJ2021A0655），光电磁材料安徽省重点实验室开放基金（ZD2022004）资助

详细信息

通讯作者:
E-mail: wangtao@aqnu.edu.cn

bbjiang0726@126.com

中图分类号: O643.36
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出版历程
- 收稿日期: 2023-07-13
- 修回日期: 2023-08-13
- 录用日期: 2023-08-14
- 网络出版日期: 2023-09-18
- 刊出日期: 2024-02-02

α-MnO₂ as an advanced bifunctional ORR/IOR electrocatalyst for Zn-air battery

Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials, School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246011, China

Funds: The project was supported by Anhui Province Natural Science Foundation (2008085QB53), Natural Science Research Project of Anhui Province Education Department (KJ2021A0642, KJ2021A0655), Open Project of Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials (ZD2022004).

摘要

摘要: 析氧反应（oxygen evolution reaction, OER）和氧还原反应（oxygen reduction reaction, ORR）是可充电锌空电池（rechargeable Zn-air batteries, RZABs）重要的两个反应。其中，析氧反应具有较高的热力学平衡电位和复杂的反应路径，实际应用中需要高的充电电压驱动其发生，这将带来一系列问题并且限制了RZABs的商业化应用。基于此，本研究构造α-MnO₂并作为ORR/IOR双功能催化剂。在碱性体系中引入反应改性剂KI，α-MnO₂对碘离子氧化反应（iodide oxidation reaction, IOR）具有更低的阳极氧化电位和更快的催化动力学。当1.0 mol/L KOH电解液中添加0.5 mol/L KI时，相比于OER（1.709 V @10 mA/cm²），α-MnO₂在IOR过程中电流密度达到10 mA/cm²时阳极电位减小了398 mV（1.311 V vs. RHE），且表现出低至57.5 mV/dec塔菲尔斜率。相对于与Pt/C，在含有KI的KOH电解液中，α-MnO₂表现出与Pt/C相媲美的ORR活性。此外，以α-MnO₂为空气电极组装成RZAB后，该电池也表现出了优异的充电活性和良好的循环寿命，在5 mA/cm²电流密度下，充放电电压间隙由0.97 V缩减为0.61 V，能量转换效率由54.9%提升至66.2%。
- 可充电锌空电池 /
- 析氧反应 /
- 碘离子氧化反应 /
- α-MnO₂
Abstract: Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are important reactions for rechargeable Zinc-air batteries (RZABs). Unfortunatly, OER holds a high thermodynamic equilibrium potential and complex reaction path, which require an large votage to derive this reaction and greatly hinder its commercial application. Herein, α-MnO₂ was successfully achieved and as the bifunctional ORR/iodide oxidation reaction (IOR) electrocatalyst. In alkline media, α-MnO₂ exhibits fast kinetics and low oxidation potential for IOR. Expectedly, α-MnO₂ exhibits remarkable IOR activity in 1.0 mol/L KOH with 0.5 mol/L KI. Compared with potential at 10 mA/cm² for OER (1.709 V vs. RHE), the potential at 10 mA/cm² reduce 398 mV (1.311 V vs. RHE) for α-MnO₂ during IOR process. α-MnO₂ also provides small Tafel slope of 57.5 mV/dec. Additionly, α-MnO₂ represents outsanding ORR performances with respect to Pt/C. As an air electrode for RZAB, the fabricated RZAB delivers excellent performances. To be specific, at 5 mA/cm², the voltage gap between charging and discharging reduces from 0.97 V to 0.61 V, energy efficiency increses from 54.9% to 66.2%. This work provide an unique strategy to construct bifunction ORR/IOR electrocatalysts and promote the commercialization of RZABs.
- rechargeable zinc-air battery /
- oxygen evolution reaction /
- iodide oxidation reaction /
- α-MnO₂

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FIG. 2933. FIG. 2933.

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图 1 α-MnO₂的（a）XRD谱图，（b）SEM，（c）TEM和（d）高分辨TEM图片

Figure 1 (a) XRD pattern, (b) SEM, (c) TEM and (d) high resolution TEM image of α-MnO₂

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图 2 α-MnO₂的（a）全扫描XPS光谱谱图和（b）Mn 2p的高分辨XPS光谱谱图

Figure 2 (a) The full XPS scan spectrum of α-MnO₂ and (b) high-resolution XPS spectrum of Mn 2p of α-MnO₂

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图 3 （a）α-MnO₂、RuO₂和Pt/C在1.0 mol/L KOH中的OER曲线，（b）α-MnO₂在不同浓度KI的电解液中的LSV曲线，（c）α-MnO₂、RuO₂和Pt/C在1.0 mol/L KOH+0.5 mol/L KI中的LSV曲线和（d）相应的塔菲尔斜率

Figure 3 (a) The LSV curves of α-MnO₂, RuO₂ and Pt/C in 1.0 mol/L KOH, (b) the LSV curves of α-MnO₂ in KOH containing different concentration of KI, (c) the LSV curves of α-MnO₂, RuO₂ and Pt/C in 1.0 mol/L KOH containing 0.5 mol/L KI and (d) corresponding Tafel slopes

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图 4 （a）Pt/C在含有不同浓度的KI的1.0 mol/L KOH电解液中的LSV曲线，（b）α-MnO₂和Pt/C在含有不同浓度的KI的1.0 mol/L KOH电解液中达到10 mA/cm²电流密度时的电位柱状图和（c）α-MnO₂的V-t曲线

Figure 4 (a) LSV curves of Pt/C in KOH with different concentrations of KI, (b) potentials of α-MnO₂ and Pt/C at 10 mA/cm² in KOH with different concentrations of KI and (c) V-t curve of α-MnO₂

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图 5 α-MnO₂在不同含量KI的0.1 mol/L KOH中（a）CV曲线（实线为O₂饱和溶液，虚线为N₂饱和溶液）和（b）LSV曲线（1600 r/min），Pt/C催化剂在不同含量KI的0.1 mol/L KOH中（c）CV曲线（实线为O₂饱和溶液，虚线为N₂饱和溶液）和（d）LSV曲线（1600 r/min）

Figure 5 (a) CV curves (solid line is O₂ saturated solution, dotted line is N₂ saturated solution) and (b) LSV curves of α-MnO₂ (1600 r/min) in 0.1 mol/L KOH solution containing different concentration of KI, and (c) CV curves (solid line is O₂ saturated solution, dotted line is N₂ saturated solution) and (d) LSV curves of Pt/C (1600 r/min) in 0.1 mol/L KOH solution containing different concentration of KI

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图 6 α-MnO₂在0.1 mol/L KOH+0.05 mol/L KI中（a）不同扫速下的LSV曲线和（b）相应的K-L图；α-MnO₂与商业Pt/C在不同电解液中（c）α-MnO₂和Pt/C的LSV曲线（实线为KOH+1/2 KI，虚线为纯KOH）和（d）相应的ΔE（ΔE=E_j=10 – E_1/2）对比

Figure 6 (a) LSV curves of α-MnO₂ in 0.1 mol/L KOH with 0.05 mol/L KI under different scan rate and (b) corresponding K-L plots; (c) LSV curves of α-MnO₂ and Pt/C (the solid line is KOH+1/2 KI, dasded line is KOH); (d) the ΔE (ΔE=E_j=10 – E_1/2) value of α-MnO₂ and Pt/C

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图 7 α-MnO₂在1.0 mol/L KOH+0.5 mol/L KI溶液中IOR测试后的（a）XRD谱图；（b）TEM；（c）高分辨TEM图片和（d）Mn 2p的高分辨XPS光谱谱图；α-MnO₂在0.1 mol/L KOH+0.05 mol/L KI溶液中ORR测试后的（e）XRD谱图；（f）TEM；（g）高分辨TEM图片和（h）Mn 2p的高分辨XPS光谱谱图

Figure 7 (a) XRD pattern; (b) TEM; (c) high resolution TEM image and (d) high-resolution XPS spectrum of Mn 2p of α-MnO₂ after IOR testing in 1.0 mol/L KOH+0.5 mol/L KI solution; (e) XRD pattern; (f) TEM; (g) high resolution TEM image and (h) high-resolution XPS spectrum of Mn 2p of α-MnO₂ after ORR testing in 0.1 mol/L KOH+0.05 mol/L KI solution

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图 8 （a）自组装的RZAB在不同电解液中的开路电压；（b）充放电极化曲线以及（c）恒流放电-充电循环曲线

Figure 8 (a) The open-circuit voltage of fabircated rechargeable Zn-air battery in electrolyte with/without KI; (b) The charge/discharge curves and (c) galvanostatic charge/discharge plots at 10 mA/cm² in electrolyte with/without KI

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表 1 不同催化剂的IOR比较

Table 1 Comparison of IOR of different catalysts

Catalyst	Electrolyte	IOR potential	E_OER− E_IOR (@10 mA/cm²)	Ref.
20% Pt/C	1.0 mol/L KOH+0.5 mol/L KI	1.24 V @10 mA/cm²	450 mV	[5]
RuTiO-550	0.1 mol/L KOH+0.1 mol/L NaI	1.29 V @10 mA/cm²	−	[30]
Ni-Co(OH)₂ NSAs	1.0 mol/L KOH+0.33 mol/L KI	1.32 V @50 mA/cm², 1.33 V @100 mA/cm²	320 mV	[31]
Pt/RuO₂/CC	0.1 mol/L KOH+0.033 mol/L KI	1.42 V @10 mA/cm²	310 mV	[45]
α-MnO₂	1.0 mol/L KOH+0.5 mol/L KI	1.311 V @10 mA/cm²	398 mV	this work

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表 2 不同催化剂的ORR和ΔE比较

Table 2 Comparison of ORR and ΔE of different catalysts

Catalyst	E_1/2/V	E_j=10/V	ΔE (E_j=10–E_1/2)/V	Reference
MnO₂-IL_0.5	0.83	1.624	0.794	[8]
24Co-MnO₂	0.787	1.66	0.872	[44]
MnO₂/NRGO-Urea	0.80	1.69	0.89	[47]
MnO₂/C	0.67	1.75	1.08	[47]
CoO:MnO₂@C-CC	0.78	1.45	0.67	[48]
MnO-FeCo	0.88	1.501	0.621	[49]
α-MnO₂/Co₃O₄	0.76	1.784	1.024	[50]
MC@NC-0.3	0.82	1.59	0.77	[51]
CoFe@CNT/MnO	0.85	1.423	0.573	[52]
α-MnO₂	0.746	1.311 V （IOR）	0.565	this work

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