钴基电极材料的改性策略及其应用研究

孙兴伟; 白杰; 李春萍; 梁海欧; 许瞳; 孙炜岩

doi:10.13801/j.cnki.fhclxb.20220929.002

钴基电极材料的改性策略及其应用研究

doi: 10.13801/j.cnki.fhclxb.20220929.002

内蒙古工业大学　化工学院，内蒙古工业催化重点实验室，呼和浩特 010051

基金项目: 国家自然科学基金(21965025)

详细信息

通讯作者:
孙兴伟，博士，讲师，研究方向为电化学能源存储与转化　E-mail: sxw@imut.edu.cn

中图分类号: O61
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- 文章访问数: 1155
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出版历程
- 收稿日期: 2022-07-25
- 修回日期: 2022-09-09
- 录用日期: 2022-09-17
- 网络出版日期: 2022-10-06
- 刊出日期: 2023-05-15

Modification strategy and application of cobalt-based electrode materials

College of Chemical Engineering, Inner Mongolia University of Technology, Inner Mongolia Key Laboratory of Industrial Catalysis, Hohhot 010051, China

Funds: National Natural Science Foundation of China (21965025)

摘要

摘要: 钴基材料作为非贵金属材料中重要的一员，因其具有较高理论容量、良好的催化活性及出色的热/化学稳定性，被广泛应用在超级电容器(SCs)和电催化等电化学能源储存与转化领域中。然而目前在钴基材料的应用中还存在诸多缺陷，如导电性偏低，活性位点暴露的不充分，测试过程中活性组分易团聚、分解，结构稳定性较差等。近年来，许多研究报道了改性钴基材料来提升其电化学性能，基于此，本综述详细介绍了近几年对钴基材料的改性研究，主要包括形貌调控、元素掺杂、构筑异质结、缺陷工程及与载体材料复合。然后，对其在SCs、电催化氧还原反应(ORR)、析氧反应(OER)及析氢反应(HER)中的应用进行系统性的总结。最后，提出钴基材料当前存在的问题和未来的发展方向。
- 钴基材料 /
- 改性策略 /
- 超级电容器 /
- 氧还原反应 /
- 析氧反应 /
- 析氢反应
Abstract: As an important member of non-precious metal materials, cobalt-based materials have been widely used in electrochemical energy storage and conversion fields such as supercapacitors and electrocatalysis due to their high theoretical capacity, good catalytic activity, and excellent thermal/chemical stability. However, cobalt-based materials have also many shortcomings, such as low conductivity, insufficient exposure of active sites, easy agglomeration and decomposition of active components during testing, poor structural stability, etc. In recent years, many studies have reported the modification of cobalt-based materials to improve their electrochemical performance. Based on this, this review introduces the modification research of cobalt-based materials in recent years in detail, mainly including morphology control, elemental doping, heterostructure construction, defect engineering and composite with specific supports materials, etc. Then, their electrochemistry applications including supercapacitors (SCs), electrocatalytic oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is systematically summarized. Finally, the current problems and future development directions of cobalt-based materials are proposed.
- cobalt-based materials /
- modification strategy /
- supercapacitors /
- oxygen reduction reaction /
- oxygen evolution reaction /
- hydrogen evolution reaction

HTML全文

图 1 钴基材料的改性策略示意图

Figure 1. Schematic illustration of modification strategy of cobalt-based materials

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图 2 CoP纳米框架(CoP NFs)的SEM图像((a), (b))、TEM图像((c), (d))、HRTEM图像(e)、SAED图像(f)和TEM-EDX能谱面扫图像(g)^[22]

Figure 2. SEM images ((a), (b)), TEM images ((c), (d)), HRTEM image (e), SAED pattern (f) and TEM-EDX elemental mapping images (g) for CoP nanoframes (CoP NFs)^[22]

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图 3 (a) 未掺杂和N掺Co₃O₄(110)表面的计算结构和OH^–吸附能(E_ad)；(b) 析氧反应(OER)循环的示意图；(c) 未掺杂Co₃O₄和N掺杂Co₃O₄的总态密度和预计态密度^[31]

Figure 3. (a) Calculated structures and OH⁻ adsorption energies (E_ad) of the undoped and N-doped Co₃O₄ (110) surfaces; (b) Schematic illustration of the oxygen evolution reaction (OER) cycle; (c) Total density of states and projected densities of states of undoped Co₃O₄ and N-doped Co₃O₄^[31]

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图 4 (a) B掺杂具有氧空位的CoO纳米线(CoO-Ov)、CoO和标准Co(OH)₂在Co K边缘的傅里叶变换光谱；(b) X射线吸收近边缘结构(XANES)光谱；通过氧缔合机制在CoO(111)表面(c)和B掺杂的CoO-Ov(111)(d)表面上不同电极电位下OER的自由能图^[45]

U—Electrode potential; R—Radial distance

Figure 4. (a) Fourier transform spectra at the Co K-edge for vacancies in CoO nanowires by B doping (B doped CoO-Ov) , CoO and standard Co(OH)₂; (b) Overlaid X-ray absorption near edge structure (XANES) spectra; Free energy diagrams for OER at different electrode potential on CoO(111) surface (c) and B doped CoO-Ov (111) surface (d) through oxygen associative mechanism^[45]

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图 5 (a) 拉伸应变对后期过渡金属d带位置影响的能量图；(b) 沿xx方向计算的应变图；(c) HRTEM图像；(d) 沿图5(c)中白线的应变线剖面^[47]

E_F—Fermi level

Figure 5. (a) Energy diagrams explaining the effect of tensile strain on the d-band position of late transition metals; (b) Strain map taken along the xx direction calculated; (c) HRTEM image; (d) Line profiles of strain along the white line in Fig.5(c)^[47]

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图 6 (a) CoO-CoSe₂@N-CNTs/rGO的制备过程示意图；(b) OER的自由能图；(c)态密度(DOS)图^[49]

DCDA—Dicyandiamide; GO—Graphene oxide; rGO—Reduced graphene oxide; N-CNT—N doping carbon nanotube; DOS—Density of states; U_NHE—Potential vs normal hydrogen electrode

Figure 6. (a) Schematic illustration of the preparation process of CoO-CoSe₂@N-CNTs/rGO; (b) Free energy diagram of OER; (c) Density of state (DOS) patterns^[49]

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图 7 (a) 纳米片MoS₂修饰的空心纳米片CoP异质结复合材料(MCPS)的SEM图像；(b) 元素面扫图像；(c) HRTEM图像；(d) 在不同活性位点的氢吸附能的DFT计算^[51]

ΔG_ads—Gibbs free energy of reactive adsorption intermediates

Figure 7. (a) SEM image of MoS₂ nanosheets arrays on CoP hollow structure (MCPS); (b) Element mapping images; (c) HRTEM image; (d) DFT calculation of hydrogen adsorption energy on different sites^[51]

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图 8 纯Co (a)和Co₄N (b)的几何结构；(c) OER的自由能图；(d) Co和Co₄N的d轨道的DOS^[67]

ε_d—d-band center; NC—Nitrogen doped carbon

Figure 8. Geometric structures of pure Co (a) and Co₄N (b); (c) Free energy diagrams for OER; (d) DOS for d orbitals of Co and Co₄N^[67]

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表 1 不同元素掺杂钴基电极材料的电化学性能

Table 1. Electrochemical performance of cobalt-based electrode materials with doped different elements

Electrode material	Electrolyte/Reaction	Specific capacitance	ORR E_1/2/V	OER/HER E₁₀/mV	Tafel slop value/ (mV·dec⁻¹)	Ref.
Ni-CoP₃	1.0 mol·L⁻¹ KOH/SCs	0.7 mA·h·cm⁻² at 2.5 mA·cm⁻²	−	−	−	[28]
Zn-Co₃O₄	1.0 mol·L⁻¹ KOH/OER	−	−	151	−	[29]
Fe-CoP UNSs/NF	1.0 mol·L⁻¹ KOH/HER	−	−	67	66.22	[30]
N-Co₃O₄	1.0 mol·L⁻¹ KOH/OER	−	−	190	29.8	[31]
S-CoSe₂	0.5 mol·L⁻¹ H₂SO₄/HER	−	−	88	50	[32]
Co-I-N/G	1.0 mol·L⁻¹ KOH/HER	−	−	52	56.1	[33]
Mo-CoP	1.0 mol·L⁻¹ KOH/OER/HER	−	−	305/40	56/65	[34]
Fe-CoP	1.0 mol·L⁻¹ KOH/OER/HER	−	−	310/78	67/75	[35]
Bi-CoP	0.1/1.0 KOH/ORR/OER	−	0.81	370	−	[36]
Mn-ZnO	2.0 mol·L⁻¹ KOH/SCs	515 F·g⁻¹ at 2 mA·g⁻¹	−	−	−	[37]
NCO	0.1/1.0 KOH/ORR/OER	−	0.65	275	74/54	[38]
NCoHPOF-450	1.0/3.0 KOH/OER/SCs	206.3 F·g⁻¹ at 1 A·g⁻¹	−	276	57.11	[39]
N-doped NiCo₂O₄	0.1/0.1 KOH/ORR/OER	−	0.63	419	113/74	[40]
Fe, Mn-Co₃S₄	6.0 mol·L⁻¹ KOH/SCs	390 mA·h·g⁻¹at 5 A·g⁻¹	−	−	−	[41]
N-CoP	0.5 mol·L⁻¹ H₂SO₄/HER	−	−	42	41.2	[42]
Notes: SCs—Supercapacitors; OER—Oxygen evolution reaction; HER—Hydrogen evolution reaction; ORR—Oxygen reduction reaction; E_1/2—Limiting current density; E₁₀—Overpotential at current density of 10 mA·cm⁻²; Fe-CoP UNSs/NF—Iron doped cobalt phosphide ultrathin nanosheets (Fe-CoP UNSs) with a 2.3 nm thickness on a nickel foam (NF) substrate; NCO—Atomically-thin nickel-doped spinel cobalt oxide; Co−I−N/G—Doping the carbon substrate with iodine atoms can effectively modulate the electronic structure of the atomically dispersed Co sites in a Co−N−C catalyst; NCoHPOF—Monoclinic-phase cobalt-phosphates, NH₄Co₃(HPO₄)₂(H₂PO₄)F₂; NCoHPOF-450—Monoclinic-phase cobalt-phosphates was calcined at 450℃.

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