Co2Ni1O4/不锈钢复合材料的制备及其电催化析氧性能

曾庆乐; 刘小超; 刘超; 漆小鹏

doi:10.13801/j.cnki.fhclxb.20210223.005

Co₂Ni₁O₄/不锈钢复合材料的制备及其电催化析氧性能

曾庆乐^1,,
刘小超^1,,
刘超^1,,
漆小鹏^1, ,

江西理工大学　材料冶金化学学部，赣州 341000

基金项目: 江西省重点研发计划(20202BBEL53023)；国家自然科学基金(22065015)

详细信息

通讯作者:
漆小鹏，博士，副教授，硕士生导师，研究方向为电解水催化材料　E-mail：qxpai@163.com

中图分类号: TB331；TQ426
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出版历程
- 收稿日期: 2020-11-15
- 录用日期: 2021-02-11
- 网络出版日期: 2021-02-22
- 刊出日期: 2021-10-31

Synthesis and electrocatalytic oxygen evolution performances of Co₂Ni₁O₄/stainless steel composites

Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China

摘要

摘要: 电解水包括析氢反应(HER)与析氧反应(OER)，由于OER是复杂的4电子转移过程，制作出具有优异耐久性的高活性的非贵金属OER电催化剂对于电解水至关重要。为了降低成本，选择304型不锈钢网(SS)作为基体，使用电沉积的方法制备钴-镍双氢氧化物，利用真空煅烧的方法制备钴-镍氧化物。使用XRD、SEM、TEM、XPS和电化学工作站对Co₂Ni₁O₄/SS复合材料的晶体结构、形貌和电催化OER性能进行了研究。结果表明：电沉积制备的钴-镍双氢氧化物煅烧之后转变成尖晶石结构的钴-镍氧化物；在不锈钢表面成功合成了大量密集的层状结构；在1.0 mol/L KOH电解液中，Co₂Ni₁O₄/SS电极表现出优异的OER电催化性能，达到10 mA·cm⁻²电流密度时所需要的过电位仅为240 mV，Tafel斜率为53.92 mV·dec⁻¹，并且表现出优异的稳定性。
- 电沉积 /
- 不锈钢 /
- 尖晶石化合物Co₂Ni₁O₄ /
- 水分解 /
- 析氧反应
Abstract: Electrolytic water includes hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), because OER is a complex 4-electron transfer process, developing highly active non-precious OER electrocatalysts with superior durability is crucial to electrolytic water. In order to reduce the cost, 304 stainless steel mesh (SS) was selected as the matrix, Co-Ni double hydroxides was prepared by electrodeposition, Co-Ni oxides were produced by vacuum calcination. The crystal structure, morphology and electrocatalytic OER performance of Co₂Ni₁O₄/ SS composite were studied by XRD, SEM, TEM, XPS and electrochemical workstation. As a result, the Co-Ni double hydroxides prepared by electrodeposition are transformed into Co-Ni oxides with spinel structure after vacuum calcination; successfully synthesized a large number of dense layered structures on the surface of stainless steel;the Co₂Ni₁O₄/SS electrode exhibits an outstanding OER catalytic activity with an overpotentials of 240 mV at 10 mA·cm⁻² and a Tafel slop as low as 53.92 mV·dec⁻¹ in 1.0 mol/L KOH. In addition, the Co₂Ni₁O₄/SS composites shows excellent stability in the alkaline electrolyte.
- electrodeposition /
- stainless steel /
- spinel compounds Co₂Ni₁O₄ /
- water splitting /
- oxygen evolution reaction

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图 1 不锈钢(SS)基 (a) 与碳布(CC)基 (b) Co₂Ni₁O₄及其前驱体的XRD图谱

Figure 1. XRD patterns of the stainless steel (SS) based (a) and the carbon cloth (CC) based (b) Co₂Ni₁O₄ and its precursors

LDHs—Layered double hydroxides

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图 2 SS ((a),(b))、Co₂Ni₁-层状双氢氧化(LDHs)/SS ((c),(d)) 和Co₂Ni₁O₄/SS ((e),(f)) 的SEM图像

Figure 2. SEM images of SS ((a),(b)), Co₂Ni₁-layered double hydroxides (LDHs)/SS ((c), (d)) and Co₂Ni₁O₄/SS ((e),(f))

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图 3 Co₂Ni₁O₄/SS的HRTEM图像 ((a), (b))，(b)中的插图为衍射图；Co₂Ni₁O₄/SS的HAADF-STEM图像 (c)、对应的EDS元素映射图像Co (d)、Ni (e)和O (f)

Figure 3. HRTEM image of Co₂Ni₁O₄/SS ((a), (b)), inset (b) shows the corresponding of diffraction image; HAADF-STEM image of Co₂Ni₁O₄/SS (c) and corresponding EDS elemental mapping images of Co (d), Ni (e) and O (f) for Co₂Ni₁O₄/SS

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图 4 Co₂Ni₁O₄/SS的总谱 (a), Co2p (b), Ni2p (c)和O1s (d)的XPS能谱

Figure 4. XPS spectra of survey spectrum (a), Co2p (b), Ni2p (c) and O1s (d) for the Co₂Ni₁O₄/SS

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图 5 Co₂Ni₁O₄/SS等在1.0 mol/L KOH溶液中线性伏安法极化曲线 (a)、在10 mA·cm⁻²和100 mA·cm⁻²的过电位 (b)、由(a)导出的Tafel斜率图 (c)、计时电势法稳定性测试前后的极化曲线对比图 (d) 和多步计时电势相应曲线(插图)

Figure 5. Co₂Ni₁O₄/SS in 1.0 mol/L KOH LSV polarization curves (a), overpotential at 10 mA·cm⁻² and 100 mA·cm⁻²(b); Tafel plots derived from (a) (c) , comparison of polarization curves before and after the chronopotentiometry stability test (d) and multistep chronopotentiometry responses curve (Inset)

η₁₀—Overpotential at current density of 10 mA·cm^-2; η₁₀₀—Overpotential at current density of 100 mA·cm^-2; OSS—Annealed stainless steel

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图 6 Co₁Ni₂-LDHs/SS、Co₂Ni₁-LDHs/SS、Co₃Ni₀-层状单氢氧化物(LSHs)/SS、Co₁Ni₂O₄/SS、Co₂Ni₁O₄/SS、Co₃Ni₀O₄/SS、SS和OSS的双层电容曲线 (a)，电化学阻抗谱 (b) 和极化曲线归一化到电化学比表面积(ECSA) (c)

Figure 6. Capacitive current densities plotted against scan rate (a) and Nyquist plots (b) of the Co₁Ni₂-LDHs/SS, Co₂Ni₁-LDHs/SS, Co₃Ni₀-layered single hydroxides (LSHs)/SS, Co₁Ni₂O₄/SS, Co₂Ni₁O₄/SS, Co₃Ni₀O₄/SS, SS and OSS and polarization curves normalized to the electrochemical specific surface area (ECSA) (c)

j—Current density; Z—Impedance values; R_s—Resistance of the solution; R_ct—Charge transfer resistance; C_PE—Capacitance

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图 7 Co₂Ni₁O₄/SS OER稳定性测试后的SEM图像

Figure 7. SEM image of Co₂Ni₁O₄/SS after OER stability test

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图 8 Co₂Ni₁O₄/SS OER稳定性测试前后的总谱(a), Co2p (b) , Ni2p (c)和O1s (d)的XPS光谱

Figure 8. XPS spectra of survey spectrum (a), Co2p (b), Ni2p (c), and O1s (d) for the Co₂Ni₁O₄/SS before and after OER test

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表 1 本工作与引用文献之间的OER性能对比

Table 1 Comparisons of OER performance between this work and the data in references

Sample	Electrolyte	Over potential (10 mA·cm⁻²)/mV	Tafel slope/(mV·dec⁻¹)	Reference
Co₂Ni₁O₄/SS	1.0 mol/L KOH	240	53.92	This work
CoFe-LDH/RGO	1.0 mol/L KOH	325	43	[5]
NiFe-LDHs/RGO	1.0 mol/L KOH	245	—	[7]
α-(Ni-Co)(OH)_X	1.0 mol/L KOH	255	—	[15]
MoS₂/rFe-NiCo₂O₄	1.0 mol/L KOH	270	39	[32]
N-NiCo₂O₄@C@NF	1.0 mol/L KOH	242	86	[33]
P-NiCo₂O₄ NWs/NF	1.0 mol/L KOH	300	120	[34]
NiCo₂O₄	1.0 mol/L KOH	290	102	[35]
NiCo₂O₄@N/S-C	1.0 mol/L KOH	285	53	[36]
NiCo₂O₄/NiO	1.0 mol/L NaOH	360	61	[37]
NiCo₂O₄@NiWS	1.0 mol/L KOH	290	95.2	[43]
Ti₃C₂@mNiCoP NS	1.0 mol/L KOH	237	104	[44]
FeCoNiO_x@NG	1.0 mol/L KOH	320	55	[45]
Note: NF, RGO, NWs, NS—Nickel foram, grephene oxide, nanowire, nanosheet.

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