铂钴合金纳米电催化剂的制备及性能研究

doi:10.15541/jim20200253

无机材料学报 ›› 2021, Vol. 36 ›› Issue (3): 299-305.DOI: 10.15541/jim20200253 CSTR: 32189.14.10.15541/jim20200253

所属专题：能源材料论文精选(2021)

铂钴合金纳米电催化剂的制备及性能研究

朱勇¹(), 顾军¹^,²(), 于涛¹^,³, 何海佟¹, 姚睿¹

1. 南京大学物理学院, 南京 210093
2. 南京东焱氢能源科技有限公司, 南京 211100
3. 南京大学固体微结构物理国家重点实验室, 南京 210093

收稿日期:2020-05-12 修回日期:2020-07-06 出版日期:2021-03-20 网络出版日期:2020-08-01
通讯作者: 顾军, 副教授. E-mail: junguca@nju.edu.cn
作者简介:朱勇(1994-), 男, 硕士研究生. E-mail: Zyong_mail@yeah.net
基金资助:
中央高校基本科研业务费专项资金(14380168)

Synthesis and Property of Platinum-cobalt Alloy Nano Catalyst

ZHU Yong¹(), GU Jun¹^,²(), YU Tao¹^,³, HE Haitong¹, YAO Rui¹

1. College of Physics, Nanjing University, Nanjing 210093, China
2. Nanjing Doinpower Technology Co., Ltd., Nanjing 211135, China
3. National Laboratory of Solid-State Microstructures, Nanjing University, Nanjing 210093, China

Received:2020-05-12 Revised:2020-07-06 Published:2021-03-20 Online:2020-08-01
Contact: GU Jun, associate professor. E-mail: junguca@nju.edu.cn
About author:ZHU Yong(1994-), male, Master candidate. E-mail: Zyong_mail@yeah.net
Supported by:
Fundamental Research Funds for the Central Universities(14380168)

摘要/Abstract

摘要：

研制高活性的电催化剂是实现质子交换膜燃料电池的商业化应用必须解决的关键技术之一。本研究以三乙胺为碱性络合剂、硼氢化钠为还原剂, 采用液相合成法制备PtCo纳米合金电催化剂, 再通过高温热处理实现最佳电化学性能。采用各种表征方法对催化剂的微观结构及电化学性能进行测定, 探究硼氢化钠、三乙胺的添加量及高温热处理对催化剂电化学性能的影响。结果显示, 适量的硼氢化钠可提升催化剂的电化学活性面积, 三乙胺可以改变催化剂的质量活性, 高温热处理能有效提升催化剂的质量活性, 极大提升催化剂的氧还原反应(ORR)能力; 在同一测试体系下, 添加100 mg硼氢化钠及100 μL三乙胺在500 ℃高温热处理条件下制备的PtCo纳米合金电催化剂的质量活性达到133 mA/mg_Pt, 是田中贵金属工业株式会社(TKK)商用PtCo合金催化剂的3倍。

关键词: 电催化剂, PtCo合金, 高温热处理, 氧还原反应, 电化学活性面积

Abstract:

In order to achieve the commercialization of proton exchange membrane fuel cells (PEMFCs), it is necessary to synthesize electrocatalyst with higher electrochemical activity. In this study, PtCo nano-alloy electrocatalyst was prepared by liquid phase synthesis method with sodium borohydride as reducing agent, triethylamine as complexing agent, and by sequential heat-treatment. The physical properties of the catalyst were characterized by different analytical methods. We studied the effects of heat-treatment temperature, different amounts of sodium borohydride and triethylamine on electrochemical performance. The results show that heat-treatment can greatly improve the mass activity of the catalyst, and 500 ℃ is the optimal temperature for preparing the catalyst with the highest catalytic performance towards oxygen reduction reaction(ORR). Compared with commercial TKK-PtCo alloy catalyst under the same test system, the as-prepared catalysts exhibits advantages of more uniform particle size distribution, smaller particle size and higher electrochemical performance. In particular, the mass activity (MA) of the prepared catalyst is 133 mA/mg_Pt, which is 3 times of TKK-PtCo alloy catalyst.

Key words: electrocatalyst, platinum-cobalt alloy, heat-treatment, oxygen reduction reaction, active specific surface area

中图分类号:

O646

朱勇, 顾军, 于涛, 何海佟, 姚睿. 铂钴合金纳米电催化剂的制备及性能研究[J]. 无机材料学报, 2021, 36(3): 299-305.

ZHU Yong, GU Jun, YU Tao, HE Haitong, YAO Rui. Synthesis and Property of Platinum-cobalt Alloy Nano Catalyst[J]. Journal of Inorganic Materials, 2021, 36(3): 299-305.

图/表 11

图1 Pt2.8Co/C、Pt2.8Co/C-500和TKK-PtCo/C的XRD图谱

Fig. 1 XRD patterns of Pt2.8Co/C, Pt2.8Co/C-500 and TKK-PtCo/C

图2 Pt2.8Co/C(a)、Pt2.8Co/C-500(b)和TKK-PtCo/C(c)的TEM照片及粒径分布图

Fig. 2 TEM images and particle size distributions of Pt2.8Co/C(a), Pt2.8Co/C-500(b) and TKK-PtCo/C(c)

图3 Pt2.8Co/C-500的EDS图谱

Fig. 3 EDS mappings of Pt2.8Co/C-500 (a) TEM image; (b) PtCo alloy; (c) Co; (d) Pt

图4 不同NaBH4添加量所制备的DN-Pt2.8Co/C的ECSA直方图(a); 不同三乙胺添加量所制备DTL-Pt2.8Co/C的MA直方图(b)

Fig. 4 ECSA histogram for DN-Pt2.8Co/C with different amounts of NaBH4 (a); MA histogram for DTL-Pt2.8Co/C with different amounts of triethylamine (b)

图5 Pt2.8Co/C、Pt2.8Co/C-500、TKK-PtCo/C的CV (a)和LSV曲线(b); 加速稳定性测试(ADT)前后Pt2.8Co/C-500(c, d), TKK-PtCo/C(e, f)的CV(c, e)和LSV(d, f)曲线

Fig. 5 CV(a) and LSV (b) curves for Pt2.8Co/C, Pt2.8Co/C-500 and TKK-PtCo/C; CV(c, e) and LSV(d, f) curves of Pt2.8Co/C-500 (c, d) and TKK-PtCo/C (e, f) before and after durability tests

表1 PtCo合金电催化剂的ECSA和MA数据

Table 1 ECSA and MA parameters of platinum-cobalt alloy nano catalysts

Sample	ECSA/(m²∙g_Pt^-1)	MA/(mA∙mg_Pt^-1)
Pt_2.8Co/C	51.6	54.2
Pt_2.8Co/C-500	43.5	133.0
TKK-PtCo/C	28.1	44.3
ADT-Pt_2.8Co/C-500	24.6	71.0
ADT-TKK-PtCo/C	15.7	27.2

图S1 Pt2.8Co/C-500的能谱图

Fig. S1 Energy spectrum of Pt2.8Co/C-500

图S2 不同NaBH4添加量所制备的DN-Pt2.8Co/C和TKK-PtCo/C合金催化剂的CV(a)和LSV(b)曲线

Fig. S2 CV(a) and LSV(b) curves of TKK-PtCo/C and DN-Pt2.8Co/C

图S3 不同三乙胺添加量所制备的DTL-Pt2.8Co/C的LSV曲线

Fig. S3 LSV curves of DTL-Pt2.8Co/C with different triethylamine

图S4 高温热处理前后的Pt2.8Co/C电化学活性面积(a)和质量活性(b)直方图

Fig. S4 ECSA (a) and MA (b) histograms of Pt2.8Co/C with different heat-treatment temperatures

图S5 ADT-Pt2.8Co/C-500的TEM照片及粒径分布图=S

Fig. S5 TEM images and particle size distribution of ADT-Pt2.8Co/C-500= S

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铂钴合金纳米电催化剂的制备及性能研究

Synthesis and Property of Platinum-cobalt Alloy Nano Catalyst

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