一种新型的甲酸/铁离子燃料电池

doi:10.7503/cjcu20160457

摘要/Abstract

摘要：

以甲酸为燃料、 Fe³⁺为氧化剂组成了一种新型的甲酸/铁离子燃料电池, 阳极催化剂为多壁碳纳米管(MWCNT)或β-环糊精修饰的MWCNT(β-CD-MWCNT)负载的金属钯或钯锡纳米颗粒: PdSn/MWCNT, Pd/β-CD-MWCNT和PdSn/β-CD-MWCNT. 运用循环伏安(CV)和计时电流(CA)等技术研究了各催化剂在碱性条件下对甲酸氧化反应的电催化活性. 结果表明, 加入适量的金属锡能促进钯对甲酸的电催化氧化, 甲酸氧化电位提前, 电流密度增加; 环糊精的改性对催化剂电催化活性有一定提升. 将上述催化剂制成电池阳极片, 碳粉制成电极阴极片, 组成甲酸/铁离子燃料电池并测试其放电性能. 结果表明, 电池的开路电压在0.981.20 V之间; 以PdSn/β-CD-MWCNT为阳极时, 其最大放电电流密度达50 mA/cm², 最大功率密度达12.6 mW/cm², 远优于以Pd/C为阳极的电池性能.

关键词: 甲酸氧化, 钯催化剂, 铁离子电池, 燃料电池

Abstract:

A new formic acid/iron ion(Ⅲ) fuel cell was constructed with formic acid as the fuel and Fe³⁺ as oxidant. Multi-walled carbon nanotubes(MWCNTs) and β-cyclodextrin(β-CD) modified MWCNT(β-CD-MWCNT)-supported palladium-based catalysts, PdSn/MWCNT, Pd/β-CD-MWCNT and PdSn/β-CD-MWCNT, were synthesized and used to electro-catalyze formic acid oxidation. Cyclic voltammograms(CVs) and chronoamperograms(CAs) were applied to investigate the electroactivity of the catalysts for formic acid oxidation in alkaline media. The results showed that addition of suitable amount of tin to palladium and modification of MWCNT with β-CD can promote electrocatalytic activity of Pd/MWCNT catalyst for formic acid oxidation. The formic acid/iron ion(Ⅲ) fuel cell with the prepared Pd-based catalysts as anode and carbon powder as cathode presents the open circuit voltage of 0.98—1.20 V. The fuel cell with PdSn/β-CD-MWCNT as anode exhibits the maximum current density of 50 mA/cm² and the maximum power density of 12.6 mW/cm², showing a much better cell performance than the fuel cell with Pd/C as the anode.

Key words: Formic acid oxidation, Palladium catalyst, Iron ion cell, Fuel cell

中图分类号:

TrendMD:

邹涛, 易清风, 张媛媛, 邓中梁, 雷鸣, 周秀林. 一种新型的甲酸/铁离子燃料电池. 高等学校化学学报, 2017, 38(1): 101.

ZOU Tao, YI Qingfeng, ZHANG Yuanyuan, DENG Zhongliang, LEI Ming, ZHOU Xiulin. A New Formic Acid/Iron Ion Fuel Cell^†. Chem. J. Chinese Universities, 2017, 38(1): 101.

图/表 8

Fig.1 CVs of the prepared catalysts in 1.0 mol/L NaOH solution at 50 mV/sa. PdSn/β-CD-MWCNT; b. PdSn/MWCNT;c. Pd/β-CD-MWCNT; d. Pd/C.

Fig.2 CVs of the prepared catalysts in 1.0 mol/L NaOH+0.5 mol/L HCOOH solution at 50 mV/sa. PdSn/β-CD-MWCNT; b. PdSn/MWCNT;c. Pd/β-CD-MWCNT; d. Pd/C.

Fig.3 Chronoamperometric responses of the prepared catalysts in 1.0 mol/L NaOH+0.5 mol/L HCOOH solution at -0.2 Va. PdSn/β-CD-MWCNT; b. PdSn/MWCNT;c. Pd/β-CD-MWCNT; d. Pd/C.

Fig.4 LSVs of carbon electrode in 0.5 mol/L NaCl+0.5 mol/L Fe3+ solution at sweep rates of 0.1 mV/s(a) and 1.0 mV/s(b)

Fig.5 Formic acid/ Fe3+ cell polarization curves(A) and plots of power density vs. cell current density(B) with different anode catalystsAnolyte: 1.0 mol/L NaOH+0.5 mol/L HCOOH; catholyte 0.5 mol/L NaCl+0.5 mol/L FeCl3, cathode: carbon powder. Anode catalyst: a. PdSn/β-CD-MWCNT; b. PdSn/MWCNT; c. Pd/β-CD-MWCNT; d. Pd/C.

Fig.6 Stability test of formic acid/iron fuel cell with PdSn/β-CD-MWCNT anode at 12 mA/cm2Cathode, anolyte and catholyte are the same as Fig.5.

Fig.7 Dependence of anolyte pH value upon discharging time at 12 mA/cm2The other conditions are the same as Fig.5.

Fig.8 Dependence of the concentration of Fe3+ and Fe2+ upon the bubbling time of oxygen gas at a flow rate of 20 mL/min

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