应用超微电极和粉末微电极技术研究有机溶剂和正极材料对氧气还原反应和氧气生成反应的影响

doi:10.7503/cjcu20160727

摘要/Abstract

摘要：

采用碳纤维超微电极分别研究了O₂在二甲基亚砜、乙腈和四甘醇二甲醚3种有机溶剂中的电化学反应, 结果表明, 当阳离子只含四丁胺离子时, 反应呈可逆的一电子转移; 而阳离子只含锂离子时, O₂的还原和氧化均经历了多电子转移过程. 利用超导炭黑和乙炔黑制作粉末微电极进行电化学测试, 结果表明, 在这2种正极材料上, 氧气还原反应(ORR)过程相似, 氧气生成反应(OER)过程区别明显. 此外, Tafel分析结果表明, 对于不同有机溶剂和正极材料, O₂还原均经历了初始的一电子转移步骤.

关键词: 超微电极, 粉末微电极, 氧气还原反应, 氧气生成反应, Tafel分析

Abstract:

Carbon fiber ultra-microelectrode was used to study the electrochemical reactions of O₂ in dimethyl sulfoxide, acetonitrile and tetraethylene glycol dimethyl ether. The results suggested that in tetrabutyl-ammonium-ion(TBA⁺)-containing electrolytes, the electrochemical reactions were reversible reactions of one-electron transfer; while in lithium-ion(Li⁺)-containing electrolyte, multiple-electrons transfer occurred during the oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). Powder microelectrodes of super P and conductive acetylene black were used as working electrodes to conduct electrochemical experiments. The results showed the ORRs were similar, but the OER had differences on these two materials. Besides, Tafel analyses indicated that during the ORR, one-electron transfer always took place at first whether in different non-aqueous solvents or on different cathodes.

Key words: Ultra-microelectrode, Powder microelectrode, Oxygen reduction reaction(ORR), Oxygen evolution reaction(OER), Tafel analysis

中图分类号:

O646

TrendMD:

Feng WU, 李伟伦, 姚莹, 吴锋, 张存中. 应用超微电极和粉末微电极技术研究有机溶剂和正极材料对氧气还原反应和氧气生成反应的影响. 高等学校化学学报, 2017, 38(4): 642.

LI Weilun, YAO Ying, ZHANG Cunzhong. Applications of Carbon Fiber Ultra-microelectrode and Powder Microelectrode in Exploring Influences of Non-aqueous Solvents and Cathode Materials on ORR and OER^†. Chem. J. Chinese Universities, 2017, 38(4): 642.

图/表 12

Fig.1 Current-voltage behavior observed on CFUME in O2-saturated 0.1 mol/L TBACF3SO3/DMSO(A), 0.1 mol/L TBACF3SO3/MeCN(B), 0.1 mol/L TBACF3SO3/TEGDME(C) and Cottrell plots obtained for the current time transients recorded in O2 saturated 0.1 mol/L TBACF3SO3/DMSO(D)

Table 1 Oxygen diffusion coefficient and solubility in electrolytes

Solvent	10⁵Diffusion coefficient /(cm²·s^-1)	Solubility of oxygen/(mmol·L^-1)
DMSO	2.65	2.38
MECN	6.51	8.54
TEGDME	3.27	4.15

Fig.2 Scan rate dependent cyclic voltammograms obtained on CFUME in O2-saturated 0.1 mol/L LiCF3SO3/DMSO(A), 0.1 mol/L LiCF3SO3/MeCN(B) and 0.1 mol/L LiCF3SO3/TEGDME(C)

Fig.3 Cyclic voltammograms for the ORR and OER on CFUME at various potential windows in O2-saturated 0.1 mol/L LiCF3SO3/DMSO(A), 0.1 mol/L LiCF3SO3/MeCN(B), 0.1 mol/L LiCF3SO3/TEGDME(C) and cathodic Tafel plot obtained in O2-saturated 0.1 mol/L LiCF3SO3/DMSO during ORR(D)(A)—(C) Scan rate: 500 mV/s; (D) scan rate: 10 mV/s.

Table 2 Kinetics parameters of ORR obtained from OCP for different electrolytes and electrodes(scan rate: 10 mV/s)

Electrode	Electrolyte	Tafel slope/(mV·dec^-1)	10⁵ Exchange current density(A·cm^-2)	10⁵ Standard rate constant/(cm·s^-1)
CFUME	0.1 mol/L Li⁺/DMSO	115	17.4	75.8
CFUME	0.1 mol/L Li⁺/MeCN	111	15.2	19.4
CFUME	0.1 mol/L Li⁺/TEGDME	121	1.75	4.37
Super P PME	1 mol/L Li⁺/TEGDME	117	1.45	3.62
CAB PME	1 mol/L Li⁺/TEGDME	119	1.25	3.12

Table 3 Properties of peak potentials during ORR and OER for different electrolytes and electrodes(scan rate: 500 mV/s)

Electrode	Electrolyte	E_pc1 /V	E_pa1/V	E_pa2/V	\|E_pc1-E_pa1\|/V
CFUME	0.1 mol/L Li⁺/DMSO	2.53	3.43	4.62	0.90
CFUME	0.1 mol/L Li⁺/MeCN	2.45	3.79	4.67	1.34
CFUME	0.1 mol/L Li⁺/TEGDME	2.23	3.83	4.55	1.60
Super P PME	1 mol/L Li⁺/TEGDME	2.50	3.63	4.63	1.13
CAB PME	1 mol/L Li⁺/TEGDME	2.45	3.82	4.43	1.37

Table 4 Properties of peak currents during ORR and OER for different electrolytes and electrodes(scan rate: 500 mV/s)

Electrode	Electrolyte	J_pc1 /(mA·cm^-2)	J_pa1/(mA·cm^-2)	J_pa1/J_pc1(%)
CFUME	0.1 mol/L Li⁺/DMSO	13.56	5.14	37.91
CFUME	0.1 mol/L Li⁺/MeCN	7.21	2.77	38.42
CFUME	0.1 mol/L Li⁺/TEGDME	6.43	5.45	84.50
Super P PME	1 mol/L Li⁺/TEGDME	5.20	1.22	23.45
CAB PME	1 mol/L Li⁺/TEGDME	4.24	1.02	24.05

Fig.4 Cyclability of the ORR/OER on CFUME at the scan rate of 500 mV/s in O2-saturated 0.1 mol/L LiCF3SO3/DMSO(A), 0.1 mol/L LiCF3SO3/MeCN(B) and 0.1 mol/L LiCF3SO3/TEGDME(C)

Fig.5 Scan rate dependent cyclic voltammograms obtained in O2-saturated 1 mol/L LiCF3SO3/TEGDME on Super P PME(A) and CAB PME(B)Insets of (A) and (B): peak current vs. square root of the scan rate.

Fig.6 Cyclic voltammograms for the ORR and OER in O2-saturated 1 mol/L LiCF3SO3/TEGDME at various potential windows on Super P PME(A) and CAB PME(B)Scan rate: 50 mV/s. Inset: cathodic Tafel plot; scan rate: 10 mV/s.

Fig.7 Cyclability of the ORR/OER in O2-saturated 1 mol/L LiCF3SO3/TEGDME on Super P PME(A) and CAB PME(B)Scan rate: 100 mV/s.

Fig.8 Galvanostatic discharge curves in O2-saturated 1 mol/L LiCF3SO3/TEGDME on different powder microelectrodesCurrent density: 0.2 mA/cm2. a. Super P PME; b. CAB PME.

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