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

doi: 10.13801/j.cnki.fhclxb.20210223.005

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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- 被引次数: 0
出版历程
- 收稿日期: 2020-11-16
- 录用日期: 2021-02-12
- 网络出版日期: 2021-02-23
- 刊出日期: 2021-11-01

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

ZENG Qingle^1
,,
LIU Xiaochao^1
,,
LIU Chao^1
,,
QI Xiaopeng^{1
, ,}

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

HTML全文

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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参考文献(45)

[1]	JIA Y, JIANG K, WANG H, et al. The role of defect sites in nanomaterials for electrocatalytic energy conversion[J]. Chem,2019,5(6):1371-1397. doi: 10.1016/j.chempr.2019.02.008
[2]	CAI Z, BU X, WANG P, et al. Simple and cost effective fabrication of 3D porous core-shell Ni nanochains@NiFe layered double hydroxide nanosheet bifunctional electrocatalysts for overall water splitting[J]. Journal of Materials Chemistry A,2019,7(38):2172221729.
[3]	CHEN J, ZENG Q, QI X, et al. High-performance bifunctional Fe-doped molybdenum oxide-based electrocatalysts with in situ grown epitaxial heterojunctions for overall water splitting[J]. International Journal of Hydrogen Energy,2020,45(46):24828-24839. doi: 10.1016/j.ijhydene.2020.06.283
[4]	CAI Z, BU X, WANG P, et al. Recent advances in layered double hydroxide electrocatalysts for the oxygen evolution reaction[J]. Journal of Materials Chemistry A,2019,7(10):5069-5089. doi: 10.1039/C8TA11273H
[5]	HAN X, YU C, YANG J, et al. Mass and charge transfer coenhanced oxygen evolution behaviors in CoFe-layered double hydroxide assembled on graphene[J]. Advanced Materials Interfaces,2016,3(7):1500782. doi: 10.1002/admi.201500782
[6]	ZHANG W, WU Y, QI J, et al. A thin nife hydroxide film formed by stepwise electrodeposition strategy with significantly improved catalytic water oxidation efficiency[J]. Advanced Energy Materials,2017,7(9):1602547. doi: 10.1002/aenm.201602547
[7]	YOUN D H, PARK Y B, KIM J Y, et al. One-pot synthesis of NiFe layered double hydroxide/reduced graphene oxide composite as an efficient electrocatalyst for electrochemical and photoelectrochemical water oxidation[J]. Journal of Power Sources,2015,294:437-443. doi: 10.1016/j.jpowsour.2015.06.098
[8]	WU J, REN Z, DU S, et al. A highly active oxygen evolution electrocatalyst: Ultrathin CoNi double hydroxide/CoO nanosheets synthesized via interface-directed assembly[J]. Nano Research,2016,9(3):713-725. doi: 10.1007/s12274-015-0950-4
[9]	ZHU S, LI J, DENG X, et al. Ultrathin-nanosheet-induced synthesis of 3D transition metal oxides networks for lithium ion battery anodes[J]. Advanced Functional Materials,2017,27(9):1605017. doi: 10.1002/adfm.201605017
[10]	LI H, MUSHARAVATI F, ZALENEZHAD E, et al. Electrodeposited Ni Co layered double hydroxides on titanium carbide as a binder-free electrode for supercapacitors[J]. Electrochimica Acta,2018,261:178-187. doi: 10.1016/j.electacta.2017.12.139
[11]	SUN H, YAN Z, LIU F, et al. Self-supported transition-metal-based electrocatalysts for hydrogen and oxygen evolution[J]. Advanced Materials,2019,32(3):e1806326.
[12]	LIU T, LI P, YAO N, et al. Self-sacrificial template-directed vapor-phase growth of MOF assemblies and surface vulcanization for efficient water splitting[J]. Advanced Materials,2019,31(21):1806672. doi: 10.1002/adma.201806672
[13]	LYU Y, WANG R, TAO L, et al. In-situ evolution of active layers on commercial stainless steel for stable water splitting[J]. Applied Catalysis B: Environmental,2019,248:277-285. doi: 10.1016/j.apcatb.2019.02.032
[14]	LEE M, JEE M S, LEE S Y, et al. Sloughing a precursor layer to expose active stainless steel catalyst for water oxidation[J]. ACS Applied Materials & Interfaces,2018,10(29):24499-24507. doi: 10.1021/acsami.8b04871
[15]	BALOGUN M S, QIU W, HUANG Y, et al. Cost-effective alkaline water electrolysis based on nitrogen- and phosphorus-doped self-supportive electrocatalysts[J]. Advanced Materials,2017,29(34):1702095. doi: 10.1002/adma.201702095
[16]	BALRAM A, ZHANG H, SANTHANAGOPALAN S. Enhanced oxygen evolution reaction electrocatalysis via electrodeposited amorphous alpha-phase nickel-cobalt hydroxide nanodendrite forests[J]. ACS Applied Materials & Interfaces,2017,9(34):28355-28365. doi: 10.1021/acsami.7b05735
[17]	WANG F, QI X, QIN Z, et al. Construction of hierarchical Prussian Blue Analogue phosphide anchored on Ni₂P@MoOx nanosheet spheres for efficient overall water splitting[J]. International Journal of Hydrogen Energy,2020,45(24):13353-13364. doi: 10.1016/j.ijhydene.2020.03.064
[18]	WANG F, CHEN J, QI X, et al. Increased nucleation sites in nickel foam for the synthesis of MoP@Ni₃P/NF nanosheets for bifunctional water splitting[J]. Applied Surface Science,2019,481:1403-1411. doi: 10.1016/j.apsusc.2019.03.200
[19]	SUN H, TIAN C, LI Y, et al. Coupling NiCo alloy and CeO₂ to enhance electrocatalytic hydrogen evolution in alkaline solution[J]. Advanced Sustainable Systems,2020,4(11):2000122. doi: 10.1002/adsu.202000122
[20]	CHEN J, WANG F, QI X, et al. A simple strategy to construct cobalt oxide-based high-efficiency electrocatalysts with oxygen vacancies and heterojunctions[J]. Electrochimica Acta,2019,326:134979. doi: 10.1016/j.electacta.2019.134979
[21]	ZHAN C, LIU Z, ZHOU Y, et al. Triple hierarchy and double synergies of NiFe/Co₉S₈/carbon cloth: A new and efficient electrocatalyst for the oxygen evolution reaction[J]. Nanoscale,2019,11(7):3378-3385. doi: 10.1039/C8NR09740B
[22]	ZHENG Z, DU X, WANG Y, et al. Efficient and stable NiCo₂O₄/VN nanoparticle catalyst for electrochemical water oxidation[J]. ACS Sustainable Chemistry & Engineering,2018,6(9):11473-11479.
[23]	CHEN S, YANG G, JIA Y, et al. Three-dimensional NiCo₂O₄@ NiWO4 core–shell nanowire arrays for high performance supercapacitors[J]. Journal of Materials Chemistry A,2017,5(3):1028-1034. doi: 10.1039/C6TA08578D
[24]	LIANG C, ZOU P, NAIRAN A, et al. Exceptional performance of hierarchical Ni–Fe oxyhydroxide@NiFe alloy nanowire array electrocatalysts for large current density water splitting[J]. Energy & Environmental Science,2020,13(1):86-95.
[25]	ZHANG X, KLAVER P, VAN SANTEN R, et al. Oxygen evolution at hematite surfaces: The impact of structure and oxygen vacancies on lowering the overpotential[J]. The Journal of Physical Chemistry C,2016,120(32):18201-18208. doi: 10.1021/acs.jpcc.6b07228
[26]	XIAO Y, HU T, ZHAO X, et al. Thermo-selenizing to rationally tune surface composition and evolve structure of stainless steel to electrocatalytically boost oxygen evolution reaction[J]. Nano Energy,2020,75:104949. doi: 10.1016/j.nanoen.2020.104949
[27]	ZHANG X, LI X, LI R, et al. Highly active core-shell carbon/nico₂o₄ double microtubes for efficient oxygen evolution reaction: Ultralow overpotential and superior cycling stability[J]. Small,2019,15(42):1903297. doi: 10.1002/smll.201903297
[28]	ZHOU X, LIU Z, WANG Y, et al. Facet effect of Co₃O₄ nanocrystals on visible-light driven water oxidation[J]. Applied Catalysis B: Environmental,2018,237:74-84. doi: 10.1016/j.apcatb.2018.05.067
[29]	ZHANG Y, DING F, DENG C, et al. Crystal plane-dependent electrocatalytic activity of Co₃O₄ toward oxygen evolution reaction[J]. Catalysis Communications,2015,67:78-82. doi: 10.1016/j.catcom.2015.04.012
[30]	ZHANG L, GAO Z, LIU C, et al. Synthesis of TiO₂ decorated Co₃O₄ acicular nanowire arrays and their application as an ethanol sensor[J]. Journal of Materials Chemistry A,2015,3(6):2794-2801. doi: 10.1039/C4TA06440B
[31]	HU L, WU L, LIAO M, et al. Electrical transport properties of large, individual NiCo₂O₄ nanoplates[J]. Advanced Functional Materials,2012,22(5):998-1004. doi: 10.1002/adfm.201102155
[32]	LI J, CHU D, DONG H, et al. Boosted oxygen evolution reactivity by igniting double exchange interaction in spinel oxides[J]. Journal of the American Chemical Society,2020,142(1):50-54. doi: 10.1021/jacs.9b10882
[33]	HA Y, SHI L, YAN X, et al. Multifunctional electrocatalysis on a porous N-Doped NiCo₂O₄@C nanonetwork[J]. ACS Applied Materials & Interfaces,2019,11(49):45546-45553.
[34]	CHU W, SHI Z, HOU Y, et al. Trifunctional of phosphorus-doped NiCo₂O₄ nanowire materials for asymmetric supercapacitor, oxygen evolution reaction, and hydrogen evolution reaction[J]. ACS Applied Materials & Interfaces,2020,12(2):2763-2772.
[35]	CHEN Z, ZHAO B, HE Y C, et al. NiCo₂O₄ nanoframes with a nanosheet surface as efficient electrocatalysts for the oxygen evolution reaction[J]. Materials Chemistry Frontiers,2018,2(6):1155-1164. doi: 10.1039/C8QM00027A
[36]	YUAN Y, SUN L, LI Y, et al. Synergistic modulation of active sites and charge transport: N/S Co-doped C encapsulated NiCo₂O₄/NiO hollow microrods for boosting oxygen evolution catalysis[J]. Inorganic Chemistry,2020,59(6):4080-4089. doi: 10.1021/acs.inorgchem.0c00089
[37]	MAHALA C, BASU M. Nanosheets of NiCo₂O₄/NiO as efficient and stable electrocatalyst for oxygen evolution reaction[J]. ACS Omega,2017,2(11):7559-7567. doi: 10.1021/acsomega.7b00957
[38]	KANG Z, GUO H, WU J, et al. Engineering an earth-abundant element-based bifunctional electrocatalyst for highly efficient and durable overall water splitting[J]. Advanced Functional Materials,2019,29(9):1807031.1-1807031.10.
[39]	SHINAGAWA T, GARCIA-ESPARZA A T, TAKANABE K. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion[J]. Scientific Reports,2015,5:13801. doi: 10.1038/srep13801
[40]	ZHANG G, WANG H, YANG J, et al. Temperature effect on Co-based catalysts in oxygen evolution reaction[J]. Inorganic Chemistry,2018,57(5):2766-2772. doi: 10.1021/acs.inorgchem.7b03168
[41]	YAN D, LI Y, HUO J, et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions[J]. Advanced Materials,2017,29(48):1606459. doi: 10.1002/adma.201606459
[42]	WANG Y, ZHOU T, JIANG K, et al. Reduced mesoporous Co₃O₄ nanowires as efficient water oxidation electrocatalysts and supercapacitor electrodes[J]. Advanced Energy Materials,2014,4(16):1400696. doi: 10.1002/aenm.201400696
[43]	ZHAO D, DAI M, LIU H, et al. Constructing high performance hybrid battery and electrocatalyst by heterostructured NiCo₂O₄@NiWS nanosheets[J]. Crystal Growth & Design,2019,19(3):1921-1929.
[44]	YUE Q, SUN J, CHEN S, et al. Hierarchical mesoporous MXene–NiCoP electrocatalyst for water-splitting[J]. ACS Applied Materials & Interfaces,2020,12(16):18570-18577.
[45]	JIANG R, BAKER D R, TRAN D T, et al. Multimetallic FeCoNiOx nanoparticles covered with nitrogen-doped graphene layers as trifunctional catalysts for hydrogen evolution and oxygen reduction and evolution[J]. ACS Applied Nano Materials,2020,3(7):7119-7129. doi: 10.1021/acsanm.0c01434