磷化钴材料在电化学能源领域的研究进展

doi:10.16085/j.issn.1000-6613.2020-1045

摘要/Abstract

摘要：

当今时代，人类社会的发展日益依赖巨量的能源，这与不可再生资源有限的储量相矛盾，发展绿色清洁、高效可持续的可再生能源和能源利用技术迫在眉睫。磷化钴材料作为过渡金属磷化物的重要一员，由于其对氢的优异吸/脱附性能和特殊的晶体结构，广泛应用于电解水、超级电容器和二次电池等电化学能量储存与转化领域。然而目前磷化钴材料的应用还存在很多缺陷，在电解水反应中活性组分易分解，结构稳定性差；在超级电容器使用中活性位点暴露不足、电导率偏低；作为锂/钠离子电池电极材料在充放电过程中存在巨大的体积变化而导致循环稳定性降低等。本文对磷化钴的晶体结构、制备方法及改良方法作了总结，对其应用于电解水、超级电容器和锂/钠离子电池的生效机理和发展近况进行概述。最后提出了存在的问题和未来的发展方向。

关键词: 可再生能源, 磷化钴, 电化学, 电解水, 超级电容器, 锂/钠离子电池

Abstract:

In the current era, the development of human society increasingly depends on huge amounts of energy, which contradicts the limited reserves of non-renewable resources. The development of green, clean, efficient and sustainable new energy and energy utilization technologies is extremely urgent. As an important member of transition metal phosphides, cobalt phosphides have been widely used in electrochemical energy storage and conversion fields such as electrolysis of water, supercapacitors and secondary batteries due to its excellent performance of absorption/desorption of H and its special crystal structure. However, cobalt phosphides have also many shortcomings. In the process of electrolysis of water, the active components are easily decomposed and the structural stability is poor. When used in the supercapacitor, cobalt phosphides electrode materials suffer from the insufficient exposure of the active site and the lower conductivity. As anode materials for lithium / sodium ion batteries, the huge volume change results in poor cycle stability. In this review, the crystal structure, preparation methods and improved methods of cobalt phosphides were summarized, and the effective mechanism and development status of cobalt phosphides used in electrolysis of water, supercapacitor and lithium/sodium ion battery were summarized. In addition, the existing problems and future development directions for cobalt phosphide materials were also discussed.

Key words: renewable energy, cobalt phosphides, electrochemistry, water splitting, supercapacitor, lithium/sodium ion battery

中图分类号:

赵鹬, 周飞, 张伟伟, 李宁, 李世友, 李贵贤. 磷化钴材料在电化学能源领域的研究进展[J]. 化工进展, 2021, 40(4): 2188-2205.

ZHAO Yu, ZHOU Fei, ZHANG Weiwei, LI Ning, LI Shiyou, LI Guixian. Research progress of cobalt phosphide materials in the field of electrochemical energy[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2188-2205.

图/表 13

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产物	钴源	磷源	溶液	温度/℃	时间	形貌	文献
CoP	八羰基钴	TOP	1-十八烯、油胺	330	60min	纳米颗粒	[13]
Co₂P	八羰基钴	TOP	1-十八烯	290	40min	纳米颗粒	[13]
Co₂P	乙酰丙酮钴	TPP	油胺、甲苯	280	2h	中空纳米花	[36]
Co₂P	八羰基钴	TOP	1-十八烯，油胺	300	1h	纳米颗粒	[38]
CoP	八羰基钴	TOP	油胺	350	2.5h	纳米颗粒	[38]
CoP	乙酰丙酮钴	TOP	1-十八烯，油胺	320	2h	单分散纳米晶	[14]
Co₂P	乙酰丙酮钴	TOP	1-十八烯，油胺	280	2h	单分散纳米晶	[14]
CoP	乙酰丙酮钴	TPP	油胺、甲苯	300	3h	升温20min纳米棒，25min纳米花	[35]
Co₂P	乙酸钴	TPP	石墨烯分散于油胺	280	3h	Co₂P-Co/石墨烯中空纳米复合材料	[34]
Co₂P	硬脂酸钴	TOP	油胺、油酸、三辛胺	310	1h	纳米球	[87]
CoP	乙酰丙酮钴	TOP	1-十八烯，油胺	330	1h	纳米棒	[33]
Co₂P	乙酰丙酮钴	TPP	油胺	320	2h	纳米微球	[33]

产物	钴源	磷源	溶液	温度/℃	时间	形貌	文献
CoP	八羰基钴	TOP	1-十八烯、油胺	330	60min	纳米颗粒	[13]
Co₂P	八羰基钴	TOP	1-十八烯	290	40min	纳米颗粒	[13]
Co₂P	乙酰丙酮钴	TPP	油胺、甲苯	280	2h	中空纳米花	[36]
Co₂P	八羰基钴	TOP	1-十八烯，油胺	300	1h	纳米颗粒	[38]
CoP	八羰基钴	TOP	油胺	350	2.5h	纳米颗粒	[38]
CoP	乙酰丙酮钴	TOP	1-十八烯，油胺	320	2h	单分散纳米晶	[14]
Co₂P	乙酰丙酮钴	TOP	1-十八烯，油胺	280	2h	单分散纳米晶	[14]
CoP	乙酰丙酮钴	TPP	油胺、甲苯	300	3h	升温20min纳米棒，25min纳米花	[35]
Co₂P	乙酸钴	TPP	石墨烯分散于油胺	280	3h	Co₂P-Co/石墨烯中空纳米复合材料	[34]
Co₂P	硬脂酸钴	TOP	油胺、油酸、三辛胺	310	1h	纳米球	[87]
CoP	乙酰丙酮钴	TOP	1-十八烯，油胺	330	1h	纳米棒	[33]
Co₂P	乙酰丙酮钴	TPP	油胺	320	2h	纳米微球	[33]

催化剂	钴源	磷源	特征尺寸	比表面积 /m²·g^-1	用途	电解液	过电势/电流密度	文献
中空的Co₂P纳米颗粒	八羰基钴	TOP	约11nm的纳米颗粒		HER	0.5mol·L^-1 H₂SO₄	95mV/10mA·cm^-2	[13]
中空的CoP纳米颗粒	八羰基钴	TOP	约12nm的纳米颗粒		HER	0.5mol·L^-1 H₂SO₄	75mV/10mA·cm^-2	[13]
Co₂P/WC异质结	多金属氧酸盐（Co₇P₆W₁₈）	多金属氧酸盐（Co₇P₆W₁₈）	4.7nm的异质结	226	HER	0.5mol·L^-1 H₂SO₄	91mV/10mA·cm^-2	[25]
Co₂P-CoN核壳纳米颗粒	硝酸钴	TPP		174.81	HER	0.5mol·L^-1 H₂SO₄	98mV/10mA·cm^-2	[54]
Co-Co₂P纳米颗粒	酵母菌	酵母菌	约104.8nm的纳米颗粒	110.2	HER	0.5mol·L^-1 H₂SO₄	61.5mV/10mA·cm^-2	[42]
Ag@Co_xP核壳结构	乙酸钴	TPP	约23.7nm的纳米球		OER	1mol·L^-1 KOH	310mV/10mA·cm^-2	[37]
针状窄六方相Co₂P	氯化钴	磷化氢	长约70nm、宽约5nm的纳米针		OER	1mol·L^-1 KOH	310mV/10mA·cm^-2	[55]
O、Fe共掺杂的Co₂P 纳米线	硝酸钴	TPP			HER	1mol·L^-1 KOH	87.5mV/10mA·cm^-2	[45]
O、Fe共掺杂的Co₂P 纳米线	硝酸钴	TPP			OER	1mol·L^-1 KOH	274.5mV/10mA·cm^-2	[45]
分层的花状CoP/CoP₂/ Al₂O₃复合物	硝酸钴	红磷	约12.9nm的颗粒	25.8	HER	1mol·L^-1 KOH	138mV/10mA·cm^-2	[56]
					OER		300mV/10mA·cm^-2
					全水解		1.65V/10mA·cm^-2
碳纳米片/纳米管封装的Co₂P颗粒	硝酸钴	磷酸	平均2.3nm的颗粒	199.94	HER	1mol·L^-1 KOH	154mV/10mA·cm^-2	[60]
					OER		280mV/10mA·cm^-2
					全水解		1.64V/10mA·cm^-2
碳骨架封装的Cu-Co 双金属磷化物	BCP-ZIF	次磷酸钠			HER	1mol·L^-1 KOH	190mV/10mA·cm^-2	[31]
					OER		220mV/10mA·cm^-2
					全水解		1.74V/70mA·cm^-2

催化剂	钴源	磷源	特征尺寸	比表面积 /m²·g^-1	用途	电解液	过电势/电流密度	文献
中空的Co₂P纳米颗粒	八羰基钴	TOP	约11nm的纳米颗粒		HER	0.5mol·L^-1 H₂SO₄	95mV/10mA·cm^-2	[13]
中空的CoP纳米颗粒	八羰基钴	TOP	约12nm的纳米颗粒		HER	0.5mol·L^-1 H₂SO₄	75mV/10mA·cm^-2	[13]
Co₂P/WC异质结	多金属氧酸盐（Co₇P₆W₁₈）	多金属氧酸盐（Co₇P₆W₁₈）	4.7nm的异质结	226	HER	0.5mol·L^-1 H₂SO₄	91mV/10mA·cm^-2	[25]
Co₂P-CoN核壳纳米颗粒	硝酸钴	TPP		174.81	HER	0.5mol·L^-1 H₂SO₄	98mV/10mA·cm^-2	[54]
Co-Co₂P纳米颗粒	酵母菌	酵母菌	约104.8nm的纳米颗粒	110.2	HER	0.5mol·L^-1 H₂SO₄	61.5mV/10mA·cm^-2	[42]
Ag@Co_xP核壳结构	乙酸钴	TPP	约23.7nm的纳米球		OER	1mol·L^-1 KOH	310mV/10mA·cm^-2	[37]
针状窄六方相Co₂P	氯化钴	磷化氢	长约70nm、宽约5nm的纳米针		OER	1mol·L^-1 KOH	310mV/10mA·cm^-2	[55]
O、Fe共掺杂的Co₂P 纳米线	硝酸钴	TPP			HER	1mol·L^-1 KOH	87.5mV/10mA·cm^-2	[45]
O、Fe共掺杂的Co₂P 纳米线	硝酸钴	TPP			OER	1mol·L^-1 KOH	274.5mV/10mA·cm^-2	[45]
分层的花状CoP/CoP₂/ Al₂O₃复合物	硝酸钴	红磷	约12.9nm的颗粒	25.8	HER	1mol·L^-1 KOH	138mV/10mA·cm^-2	[56]
					OER		300mV/10mA·cm^-2
					全水解		1.65V/10mA·cm^-2
碳纳米片/纳米管封装的Co₂P颗粒	硝酸钴	磷酸	平均2.3nm的颗粒	199.94	HER	1mol·L^-1 KOH	154mV/10mA·cm^-2	[60]
					OER		280mV/10mA·cm^-2
					全水解		1.64V/10mA·cm^-2
碳骨架封装的Cu-Co 双金属磷化物	BCP-ZIF	次磷酸钠			HER	1mol·L^-1 KOH	190mV/10mA·cm^-2	[31]
					OER		220mV/10mA·cm^-2
					全水解		1.74V/70mA·cm^-2

材料	钴源	磷源	比表面积 /m²·g^-1	微观形态	电流密度/比容量	用作ASC电极时功率密度 /能量密度	文献
Co₂P纳米花	乙酰丙酮钴	TPP	29	直径10～20nm的纳米晶	1A·g^-1/416F·g^-1	0.3kW·kg^-1/24W·h·kg^-1	[35]
Co₂P中空纳米花	乙酰丙酮钴	TPP	19.37	约110nm的纳米球	1A·g^-1/412.7F·g^-1	0.85kW·kg^-1/30.5W·h·kg^-1	[36]
绒球状CoP中空微球	硝酸钴	次磷酸钠	24.6	最宽500nm的纳米针	1A·g^-1/449.4F·g^-1	0.3749kW·kg^-1/22.2W·h·kg^-1	[71]
CoP纳米线阵列	硝酸钴	次磷酸钠		3～8μm长的CoP纳米线阵列	3mA·cm^-2/1.89F·cm^-2		[72]
CoP纳米线阵列	硝酸钴	次磷酸钠			1mA·cm^-2/571.3mF·cm^-2	10.15mW·cm^-3/0.69mW·h·cm^-3	[73]
CoP纳米线	硝酸钴	次磷酸钠		直径约60nm的纳米线	1mA·cm^-2/8.66F·cm^-2	0.193kW·kg^-1/35.21W·h·kg^-1	[74]
CoP纳米管阵列	硝酸钴	次磷酸钠	472.22	CoP微晶尺寸约18.5nm	1A·g^-1/610F·g^-1	0.8kW·kg^-1/39W·h·kg^-1	[75]