自支撑非晶Ce-FeHPi/NF电极的电解海水性能研究

doi:10.15541/jim20240172

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1348-1356.DOI: 10.15541/jim20240172 CSTR: 32189.14.10.15541/jim20240172

所属专题：【能源环境】氢能材料(202412)

自支撑非晶Ce-FeHPi/NF电极的电解海水性能研究

肖文艳¹^,²(), 付艳¹^,², 杨书镔¹^,², 朱洁¹^,², 程照阳², 温小煦¹^,², 唐嘉繁¹^,², 于亮¹^,², 张骞²()

1.西南石油大学油气藏地质及开发工程国家重点实验室, 成都 610500
2.西南石油大学新能源与材料学院新能源材料及技术研究中心, 成都 610500

收稿日期:2024-04-08 修回日期:2024-07-25 出版日期:2024-09-02 网络出版日期:2024-09-02
通讯作者: 张骞, 副教授. E-mail: zhangqian@swpu.edu.cn
作者简介:肖文艳(1999-), 女, 硕士研究生. E-mail: xiao18780293769@163.com
基金资助:
四川省重大科技专项揭榜挂帅项目(2022ZDZX0042)

Seawater Electrolysis Performance of Self-supported Amorphous Ce-FeHPi/NF Electrode

XIAO Wenyan¹^,²(), FU Yan¹^,², YANG Shubin¹^,², ZHU Jie¹^,², CHENG Zhaoyang², WEN Xiaoxu¹^,², TANG Jiafan¹^,², YU Liang¹^,², ZHANG Qian²()

1. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
2. The Center of New Energy Materials and Technology, School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China

Received:2024-04-08 Revised:2024-07-25 Published:2024-09-02 Online:2024-09-02
Contact: ZHANG Qian, associate professor. E-mail: zhangqian@swpu.edu.cn
About author:Xiao Wenyan (1999-), female, Master candidate. E-mail: xiao18780293769@163.com
Supported by:
Major Science and Technology Projects of Sichuan Province(2022ZDZX0042)

摘要/Abstract

摘要：

为了解决现有的能源危机, 实现持续的海水电解, 需要设计高效的电催化剂来应对阳极析氧反应缓慢与氯离子(Cl^-)腐蚀的问题。本研究在泡沫镍(NF)骨架上采用一步式水热法制备了一种具有独特纳米结构的改性Ce-FeHPi/NF电极。实验结果表明, Ce掺杂调节了FeHPi/NF的表面形貌, 形成了非晶型纳米球, 这不仅使催化层生长为致密紧实的纳米结构, 而且大幅提高了电极的活性表面积, 从而明显提高了电催化活性。此外, 磷酸基可有效排斥电极表面的Cl^-, 增强其耐腐蚀性, 使其在海水中长期稳定运行。10%Ce-FeHPi/NF电极在碱性模拟海水(1 mol·L^-1 KOH + 0.5 mol·L^-1 NaCl)电解液中, 仅需要较低的过电位(296 mV)即可达到100 mA·cm^-2的电流密度。在1 mol·L^-1 KOH + 1 mol·L^-1 NaCl电解液中, 10%Ce-FeHPi/NF电极在恒电位1.774 V(vs. RHE)下实现了超过130 h的稳定运行。本研究所制备的改性纳米结构材料有效提高了电极的析氧活性, 为海水电解阳极催化材料的发展提供了一条新的途径。

关键词: 海水电解, 阳极材料, 磷酸化合物, 一步式水热

Abstract:

To solve the existing energy crisis and achieve continuous seawater electrolysis, it is necessary to design efficient electrocatalysts to deal with the problems of slow anodic oxygen evolution and chloride ion (Cl^-) corrosion. In this study, a unique nanostructural modified Ce-FeHPi/NF electrode was prepared by a one-step hydrothermal method on a nickel foam (NF) skeleton. The experimental results show that Ce doping regulates the surface morphology of FeHPi/NF, forming amorphous nanospheres, which not only enables the catalytic layer to grow into a compact nanostructure, but also greatly increases the active surface area of the electrode, significantly improving the electrocatalytic activity. In addition, the presence of phosphoric acid group can effectively repel Cl^- on surface of the electrode, which enhances its corrosion resistance, and stabilizes it in seawater for a long time. The 10%Ce-FeHPi/NF electrode in alkaline simulated seawater (1 mol·L^-1 KOH + 0.5 mol·L^-1 NaCl) electrolyte requires only a low overpotential of 296 mV to reach a current density of 100 mA·cm^-2. In 1 mol·L^-1 KOH + 1 mol·L^-1 NaCl, the 10%Ce-FeHPi/NF electrode runs stably for more than 130 h at a constant potential of 1.774 V (vs. RHE). Therefore, the modified nanostructured material prepared in this study can effectively improve the oxygen evolution activity of electrodes, and provide a new way for the development of seawater electrolytic anode catalytic materials.

Key words: seawater electrolysis, anode material, phosphorylation compound, one-step hydrothermal

中图分类号:

TQ151

肖文艳, 付艳, 杨书镔, 朱洁, 程照阳, 温小煦, 唐嘉繁, 于亮, 张骞. 自支撑非晶Ce-FeHPi/NF电极的电解海水性能研究[J]. 无机材料学报, 2024, 39(12): 1348-1356.

XIAO Wenyan, FU Yan, YANG Shubin, ZHU Jie, CHENG Zhaoyang, WEN Xiaoxu, TANG Jiafan, YU Liang, ZHANG Qian. Seawater Electrolysis Performance of Self-supported Amorphous Ce-FeHPi/NF Electrode[J]. Journal of Inorganic Materials, 2024, 39(12): 1348-1356.

图/表 19

图1 Ce-FeHPi/NF制备流程

Fig. 1 Preparation flow of the Ce-FeHPi/NF

图2 (a)FeHPi/NF、(b)5%Ce-FeHPi/NF、(c)15%Ce-FeHPi/NF和(d~f)10%Ce-FeHPi/NF的SEM照片

Fig. 2 SEM images of (a) FeHPi/NF, (b) 5%Ce-FeHPi/NF, (c) 15%Ce-FeHPi/NF, and (d-f) 10%Ce-FeHPi/NF

图3 (a)FeHPi/NF和(b)10%Ce-FeHPi/NF的氮气吸脱附曲线和孔径分布曲线

Fig. 3 Nitrogen adsorption/desorption curves and pore size distributions for (a) FeHPi/NF and (b) 10%Ce-FeHPi/NF

图4 FeHPi/NF和Ce-FeHPi/NF的XRD谱图

Fig. 4 XRD patterns of FeHPi/NF and Ce-FeHPi/NF (a) Large angle analysis; (b) Magnified patterns

图5 不同样品的水接触角(WCA)

Fig. 5 Water contact angles (WCA) of different samples (a) NF; (b) FeHPi/NF; (c) 10%Ce-FeHPi/NF

图6 FeHPi/NF和Ce-FeHPi/NF的XPS谱图

Fig. 6 XPS spectra of FeHPi/NF and Ce-FeHPi/NF (a) Full spectra; (b) Fe2p; (c) P2p; (d) O1s; (e) Ce3d; (f) C1s

图7 Ce-FeHPi/NF在不同电解液中的(a, b)OER极化曲线、(c, d)过电位和(e, f)Tafel图谱

Fig. 7 (a, b) OER polarization curves, (c, d) overpotentials, and (e, f) Tafel plots of Ce-FeHPi/NF samples in different electrolytes (a, c, e) 1 mol·L-1 KOH; (b, d, f) 1 mol·L-1 KOH + 0.5 mol·L-1 NaCl; Colorful figures are available on website

图8 FeHPi/NF和Ce-FeHPi/NF的双层电容

Fig. 8 Double layer capacitances of FeHPi/NF and Ce-FeHPi/NF Electrolyte: 1 mol·L-1 KOH

图9 NF、FeHPi/NF和Ce-FeHPi/NF的奈奎斯特谱图

Fig. 9 Nyquist plots of NF, FeHPi/NF and Ce-FeHPi/NF Colorful figures are available on website

图10 10%Ce-FeHPi/NF在不同电解液中的I-t曲线

Fig. 10 I-t curves of 10%Ce-FeHPi/NF samples in different electrolytes

表S1 ICP-OES分析10%Ce-FeHPi/NF中Fe、P和Ce的含量

Table S1 Amounts of Fe, P and Ce in 10%Ce-FeHPi/NF determined by ICP-OES

Element	Weight/%
Fe	1.0341
Ce	0.2593
P	2.8334

图S1 10%Ce-FeHPi/NF的EDS图谱

Fig. S1 EDS spectra of 10%Ce-FeHPi/NF

图S2 电极在不同电解液中的(a, b)OER极化曲线、(c, d)过电位和(e, f)Tafel图谱

Fig. S2 (a, b) OER polarization curves, (c, d) overpotentials, and (e, f) Tafel plots of electrodes in different electrolytes (a, c, e) 1 mol·L-1 KOH; (b, d, f) 1 mol·L-1 KOH + 0.5 mol·L-1 NaCl

图S3 在非法拉第反应区间不同扫描速率下的循环伏安曲线

Fig. S3 Cyclic voltammetric curves at different scanning rates in non-Faraday reaction intervals (a) FeHPi/NF; (b) 5%Ce-FeHPi/NF; (c) 10%Ce-FeHPi/NF; (d) 15%Ce-FeHPi/NF; 1 mol·L-1 KOH

图S4 Cdl归一化后的LSV极化曲线

Fig. S4 LSV polarization curves normalized by Cdl

图S5 10%Ce-FeHPi/NF(a)在不同电解液中的OER极化曲线、(b)在1 mol·L-1 KOH + 0.5 mol·L-1 NaCl中的恒电流阶跃图

Fig. S5 (a) OER polarization curves in different electrolytes, and (b) constant current step plot of 10%Ce-FeHPi/NF in 1 mol·L-1 KOH + 0.5 mol·L-1 NaCl

图S6 长期稳定性测试后电解液的余氯检测结果(1 mol·L-1 KOH + 1 mol·L-1 NaCl, E=1.774 V(vs. RHE), 130 h)

Fig. S6 Residual chlorine testing for the electrolyte after the long-term stability test (1 mol·L-1 KOH + 1 mol·L-1 NaCl, E=1.774 V(vs. RHE), 130 h)

图S7 10%Ce-FeHPi/NF的法拉第效率测试

Fig. S7 Faraday efficiency test of 10%Ce-FeHPi/NF (a) Schematic diagram of testing equipment; (b) Faraday efficiency results

图S8 10%Ce-FeHPi/NF长时间反应后的(a~e)XPS谱图和(f)SEM照片

Fig. S8 (a-e) XPS spectra and (f) SEM image of 10%Ce-FeHPi/NF after long reaction (a) Full spectra; (b) Fe2p; (c) Ce3d; (d) P2p; (e) O1s

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自支撑非晶Ce-FeHPi/NF电极的电解海水性能研究

Seawater Electrolysis Performance of Self-supported Amorphous Ce-FeHPi/NF Electrode

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