Research Progress on Nickel-Based Electrode Catalysts for Alkaline Water Electrolysis to Produce Hydrogen AITranslate
Abstract AITranslate
The white paper "China's Energy Development in the New Era" directly pointed out that energy saving，low-carbon，and a diversified new type of clean enterprise system is a major development orientation for the future，promising to achieve China's carbon neutrality goal by 2060. Within this strategic framework，clean power becomes more and more important，with hydrogen being a noteworthy efficient and clean energy carrier at home and abroad. Among clean energy technologies，the production of hydrogen from water electrolysis is attractive because it is sustainable and can be used on a massive scale. The key is electrode preparation technology，determining the high rate and low cost of the whole hydrogen production process. By researching the hydrogen adsorption free energy （ΔGH*）of electrode materials，researchers have concluded that precious metal-based electrodes （Pt，Rh，Re，Pd and Ir）are excellent for hydrogen evolution efficiency，with Pt being the best material. However，due to limited reserves and high costs，their wide application is restricted. As a result，non-precious metal catalysts have attracted attention in recent years. Ni is also considered as a non-precious metal material，due to its better reserves，relatively low price and high performance for alkaline water hydrogen production. Currently，common methods for preparing hydrogen evolution reaction （HER）electrodes include liquid-phase synthesis，chemical vapor deposition （CVD），electrodeposition，plasma spraying，magnetron sputtering，high-energy ball milling，and powder sintering，etc. 1）Liquid-phase synthesis technology：This includes solvothermal/hydrothermal methods，redox reaction methods，sol-gel processes，hydrolysis reactions，and precipitation （including direct precipitation，co-precipitation，and homogeneity precipitation）. Disadvantages are also obvious：the operation is complicated，requires higher control of reaction conditions，and may take too long. 2）CVD：The chemical composition in CVD process is complex，often involving a combination of gas-phase and surface reactions. Volatile precursors are delivered to the reaction zone using carrier gas and/or diffusion，and precursors can react with each other or decompose in the gas phase （homogeneous reactions），or adsorb upon a substrate surface and react with reactive gases （heterogeneous reactions）. Both reactions produce solid films and gas-state by-products on the substrate. This chemical process differentiates CVD from other physical deposition processes like evaporation，sputtering，and molecular beam epitaxy，with advantages like simple equipment operation and maintenance，and control over coating density. However，it has disadvantages like high reaction temperature，complex preparation process，frequent cleaning of the deposition chamber，and potential environmental pollution from exhaust gas requiring proper disposal. 3）Electrochemical deposition：Electrodeposition is a straightforward and low-cost catalyst layer preparation method，which features strong catalytic activity，simple operation，good controllability，and fast deposition rate for obtaining non-equilibrium structures. However，it requires large electrical energy consumption，and the high internal stress in the coating layer often leads to poor performance of the finished product. 4）Plasma spraying：Depending on the environment，it includes vacuum plasma spraying （VPS），low-pressure plasma spraying （LPPS），and atmospheric plasma spray （APS）. It offers good bonding strength and high efficiency and quality，but has low powder usage efficiency and expensive equipment. Under the action of an electric field，water molecules in the solution decompose to form hydrogen ions （H+）and hydroxyl ions （OH−）through a redox reaction between the anode and cathode. Hydrogen is produced at the cathode and oxygen at the anode. Hydrogen ions receive electrons to reduce into hydrogen at the cathode，while hydroxyl ions release electrons to oxidize into oxygen and water at the anode. Electrochemical hydrogen evolution occurs in three steps：Volmer step，Heyrovsky step and Tafel step. HER kinetics includes two steps：the hydrolysis of hydroxyl ions （OH−）and adsorption of hydrogen atoms is called Volmer step，consisting of electron reduction on catalyst surface M for example adsorption H+，producing adsorbed hydrogen atoms （H*）where basic electrolytes contain H2O as proton source，while acidic electrolytes contain H3O+. The next step is the production of H2 by Heyrovsky manner，Tafel step，or a combination of both. The formation and conversion of adsorbed hydrogen is key to HER，involving both chemical adsorption and desorption due to hydrogen adsorption free energy. This free energy describes HER reaction rate performance，with a perfect HER catalyst having moderate hydrogen adsorption free energy to ensure efficient and smooth step processes. If the free energy is higher than zero，the reaction rate is lower，a negative value helps binding and facilitates Volmer step. Too strong negative forces inhibit further reaction （Heyrovsky or Tafel steps）. Tafel slope，associated with the rate-controlling step，relates to electrode reaction rate and overpotential. In basic HER，Volmer step is typically the slowest link，influencing the total reaction rate. Controlling reaction conditions or using appropriate catalysts to lower hydrogen adsorption free energy near 0 accelerates Volmer step，improving HER rate. While non-precious metals like cobalt and mammothine have advantages in hydrogen adsorption free energy compared to nickel，storage capacity and price restrict large-scale application. Ni-based electrodes have progressed in HER research and widely studied. Future trends include combining methods to construct heterojunction interfaces or synthesize composite catalysts. Machine learning technology applied to catalytic materials design and discovery has accelerated this field，significantly contributing to the development and optimization of non-PGM （Platinum-group metals）catalysts.
KeyWords AITranslate
［1］（王露，冯天意，崔鹏媛，沈庆峰，林艳，俞小花. 废旧锂离子电池正极材料中有价金属离子分离回收技术的研究现状 ［J］. 有色金属科学与工程，2023，14（6）：791.）
L Wang，T Y Feng，P Y Cui，Q F Shen，Y Lin，X H Yu. Status of technological research on the separation and recovery of valuable metal ions in cathode materials from spent lithium-ion battery ［J］. Nonferrous Metals Science and Engineering，2023，14（6）：791.
［2］（李业冰，赵兰玲，王俊，张一鸣，窦一川，李瑞丰，刘峣. Li-O2电池过渡金属硫族化合物催化剂最新研究进展 ［J］. 铜业工程，2024，（1）：129.）
Y B Li，L L Zhao，J Wang，Y M Zhang，Y C Dou，R F Li，Y Liu. Recent research progress of transition metal chalcogenide catalysts in Li-O2 batteries ［J］. Copper Engineering，2024，（1）：129.
［3］（徐啟斌，李建平，高标，郭鑫博，王学林. 铂族废催化剂湿法分离回收技术 ［J］. 稀有金属，2023，47（12）：1689.）
Q B Xu，J P Li，B Gao，X B Guo，X L Wang. Hydrometallurgy separation and recovery technology for platinum group spent catalysts ［J］. Chinese Journal of Rare Metals，2023，47（12）：1689.
［4］（郁丰善，张文洁，王春霞，温嘉玮，黄国勇. 二次资源中钌的提取回收技术进展 ［J］. 稀有金属，2024，48（5）：728.）
F S Yu，W J Zhang，C X Wang，J W Wen，G Y Huang. Technical process of extraction and recovery of ruthenium from secondary resources ［J］. Chinese Journal of Rare Metals，2024，48（5）：728.
［5］Kumar S S，Himabindu V. Hydrogen production by PEM water electrolysis–a review ［J］. Materials Science for Energy Technologies，2019，2（3）：442.
［6］Serov A，Artyushkova K，Niangar E，Wang C，Dale N，Jaouen F，Sougratic M T，Jia Q，Mukerjee S，Atanassov P. Nano-structured non-platinum catalysts for automotive fuel cell application ［J］. Nano Energy，2015，16：293.
［7］Dubouis N，Grimaud A. The hydrogen evolution reaction：from material to interfacial descriptors ［J］. Chemical Science，2019，10（40）：9165.
［8］Chen Z J，Duan X G，Wei W，Wang S B，Ni B J. Recent advances in transition metal-based electrocatalysts for alkaline hydrogen evolution ［J］. Journal of Materials Chemistry A，2019，7（25）：14971.
［9］Quaino P，Arce M D，Santos E，Schmickler W. A first principles study of the hydrogen reaction in alkaline media：OH effect ［J］. International Journal of Hydrogen Energy，2012，37（19）：14796.
［10］Yang Y J，Yu Y H，Li J，Chen Q R，Du Y L，Rao P，Li R S，Jia J M，Kang K Y，Deng P L，Shen Y J，Tian X L. Engineering ruthenium-based electrocatalysts for effective hydrogen evolution reaction ［J］. Nano-Micro Letters，2021，13：1.
［11］Zheng Y，Jiao Y，Zhu Y H，Li L H，Han Y，Chen Y，Jaroniec M，Qiao S Z. High electrocatalytic hydrogen evolution activity of an anomalous ruthenium catalyst ［J］. Journal of the American Chemical Society，2016，138（49）：16174.
［12］Mohammed I J，Sun X M. Recent progress on earth abundant electrocatalysts for hydrogen evolution reaction （HER）in alkaline medium to achieve efficient water splitting-a review ［J］. Journal of Energy Chemistry，2019，34：111.
［13］Ursua A，Gandia L M，Sanchis P. Hydrogen production from water electrolysis：current status and future trends ［J］. Proceedings of the IEEE，2012，100（2）：410.
［14］Smolinka T，Bergmann H，Garche J，Kusnezoff M. Electrochemical Power Sources：Fundamentals，Systems，and Applications.Chapter 4-The History of Water Electrolysis From its Beginnings to the Present ［M］. Elsevier，2022. 83.
［15］Balat M. Potential importance of hydrogen as a future solution to environmental and transportation problems ［J］. International Journal of Hydrogen Energy，2008，33（15）：4013.
［16］Zhang J，Wang T，Liu P，Liao Z Q，Liu S H，Zhuang X D，Chen M W，Zschech E，Feng X L. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics ［J］. Nature communications，2017，8（1）：15437.
［17］Zhu J，Hu L S，Hu L S，Zhao P X，Lee L Y S，Wong K Y. Recent advances in electrocatalytic hydrogen evolution using nanoparticles ［J］. Chemical Reviews，2019，120（2）：851.
［18］Zou X X，Zhang Y. Noble metal-free hydrogen evolution catalysts for water splitting ［J］. Chemical Society Reviews，2015，44（15）：5148.
［19］Razmjooei F，Liu T K，Azevedo D A，Hadjixenophontos E，Reissner R，Schiller G，Ansar S A，Friedrich K A. Improving plasma sprayed Raney-type nickel-molybdenum electrodes towards high-performance hydrogen evolution in alkaline medium ［J］. Scientific Reports，2020，10（1）：10948.
［20］Raoof J B，Ojani R，Esfeden S A，Nadimi S R. Fabrication of bimetallic Cu/Pt nanoparticles modified glassy carbon electrode and its catalytic activity toward hydrogen evolution reaction ［J］. International Journal of Hydrogen Energy，2010，35（9）：3937.
［21］Döner A，Solmaz R，Kardaş G. Enhancement of hydrogen evolution at cobalt-zinc deposited graphite electrode in alkaline solution ［J］. International Journal of Hydrogen Energy，2011，36（13）：7391.
［22］（沈培康，魏子栋，宋树芹，聂吴梅. PtPd-WC/C催化剂上的析氢反应 ［J］. 武汉理工大学学报，2006，6：109.）
P K Shen，Z D Wei，S Q Song，W M Nie. Hydrogen evolution reaction on PtPd-WC/C electrocatalyst ［J］. Journal of Wuhan University of Technology，2006，6：109.
［23］（马忠华. 高效析氢低铂电催化剂的制备与性能研究 ［D］. 上海：东华大学，2021. 1.）
Z H Ma. Preparation and Research of High Efficiency Electrocatalyst for Hydrogen Evolution with Low Content of Platinum ［D］. Shanghai：Donghua University，2021. 1.
［24］（王春华. 纳米阵列载体负载超细铂催化剂析氢性能研究 ［D］. 长沙：湖南大学，2019. 1.）
C H Wang. The Study on Evolution Performance of Ultrafine Platinum Catalyst Supported by Nanoarray ［D］. Changsha：Hunan University，2019. 1.
［25］Zhang J Y，Dang J，Zhu X D，Ma J G，Ouyang M，Yang F Y. Ultra-low Pt-loaded catalyst based on nickel mesh for boosting alkaline water electrolysis ［J］. Applied Catalysis B：Environmental，2023，325：122296.
［26］Pletcher D，Li X H. Prospects for alkaline zero gap water electrolysers for hydrogen production ［J］. International Journal of Hydrogen Energy，2011，36（23）：15089.
［27］（钮东方，丁勇，马智兴，王明辉，刘洲，张博文，张新胜. 纳米碳纤维的表面改性对水电解析氢反应催化活性的影响 ［J］. 化学学报，2015，73（7）：729.）
D F Niu，Y Ding，Z X Ma，M H Wang，Z Liu，B W Zhang，X S Zhang. Effects of surface modification of carbon nanofibers on their electrocatalytic activity for hydrogen evolution reaction of water electrolysis ［J］. SIOC Journals，2015，73（7）：729.
［28］Lin L，Yang Z X，Chen K，Wang C D，Xiong R J. 2D layered double hydroxides for oxygen evolution reaction：from fundamental design to application ［J］. Advanced Energy Materials，2019，9（17）：1803358.
［29］Zhao J，Zhang J J，Li Z Y，Bu X H. Recent progress on NiFe‐based electrocatalysts for the oxygen evolution reaction ［J］. Small，2020，16（51）：2003916.
［30］Kuznetsov V V，Gamburg Y，Zhulikov V V，Krutskikh V M，Filatova E A，Trigub A L，Belyakova O A. Electrodeposited NiMo，CoMo，ReNi，and electroless NiReP alloys as cathode materials for hydrogen evolution reaction ［J］. Electrochimica Acta，2020，354：136610.
［31］Hua Z S，Wu X B，Zhu Z L，He J W，He S W，Liu H，Xu L，Yang Y X，Zhao Z. One-step controllable fabrication of 3D structured self-standing Al3Ni2/Ni electrode through molten salt electrolysis for efficient water splitting ［J］. Chemical Engineering Journal，2022，427 131743.
［32］（张婕. 纳米镍基多元合金电极的制备及碱性电解水析氢/氧性能研究 ［D］. 烟台：烟台大学，2024. 1.）
J Zhang. Preparation of Nano Nickel-Based Polyalloy Electrodes and Hydrogen/Oxygen Precipitation Performance of Alkaline Water Electrolysis ［D］. Yantai：Yantai University，2024.1.
［33］Wen D F，Mao Y，Xia Y，Mai W S，Zhang Z Q，Zhang W T，Peng W D，Hu W，Tian L H. CoP nanoplates dotted with porous Ni3S2 nanospheres for the collaborative enhancement of hydrogen production via urea-water electrolysis ［J］. Applied Surface Science，2022，586：152736.
［34］Zhang J T，Zhang Z，Yao Y J，Ma X Z，Yang Y B，Chen Y，Cheng Z D. In situ construction of Ni enriched porous NiAl as long-lived electrode for hydrogen evolution at high current densities ［J］. Applied Surface Science，2019，489：435.
［35］Zhou J B，Wang C，Lu K H. The effect of cobalt complex on the activity of the nickel electrode ［J］. International Journal of Hydrogen Energy，2016，41（36）：16009.
［36］（姜媛媛，陈传霞，倪朋娟，逯一中. 负载于三维镍网上的磷化钴纳米珠链阵列的高效水电解性能研究 ［J］. 分析化学，2018，46（4）：550.）
Y Y Jiang，C X Chen，P J Ni，Y Z Lu. Efficient water splitting catalyzed by cobalt phosphide nanobead-chain like nanoarrays supported on three dimensional nickel foam ［J］. Chinese Journal of Analytical Chemistry，2018，46（4）：550.
［37］Liu Y，Xing Y Y，Zheng X Y，Xu S J，Li D，Jiang D L. Synergistically enhancing electrocatalytic activity of Co2P by Cr doping and P vacancies for overall water splitting ［J］. Applied Surface Science，2022，600：154099.
［38］Chen H P，Qiao S Z，Yang J，Du X W. NiMo/NiCo2O4 as synergy catalyst supported on nickel foam for efficient overall water splitting ［J］. Molecular Catalysis，2022，518：112086.
［39］Hwang J Y，Kim J Y，Youn D H. In-situ construction of Mo2C–MoC heterostructure on Ni foam for efficient hydrogen evolution in alkaline media ［J］. International Journal of Hydrogen Energy，2023，2（49）：58.
［40］（杨格. 电解海水用镍合金析氢阴极材料的研究 ［D］. 湘潭：湘潭大学，2020. 1.）
G Yang. Study on Nickel Alloy Cathodes for Hydrogen Evolution Reaction from Seawater Electrolysis ［D］. Xiangtan：Xiangtan University，2020. 1.
［41］Zhou X Y，Yang T T，Zi Y J，Li T，Yang J，Tang J J. Self-supporting NiMo-Fe-P nanowire arrays as bifunctional catalysts for efficient overall water splitting ［J］. Dalton Transactions，2023，52（11）：3508.
［42］（刘彬. 过渡金属磷化物在电催化中的应用探索 ［D］. 济南：齐鲁工业大学，2024. 1.）
B Liu. Application of Transition Metal Phosphide in Electrocatalysis ［D］. Jinan：Qilu University of Technology，2024. 1.
［43］Xu Z X，Jin S，Seo M H，Wang X L. Hierarchical Ni-Mo2C/N-doped carbon Mott-Schottky array for water electrolysis ［J］. Applied Catalysis B：Environmental，2021，292：120168.
［44］Zuo P，Ji X，Lu J，Chai Y，Jiao W，Wang R. N，P co-doped Ni/Mo-based multicomponent electrocatalysts in situ decorated on Ni foam for overall water splitting ［J］. Journal of Colloid and Interface Science，2023，645（1）：895.
［45］Liu M S，Chen T，Zhang W X，Wei S，Cheng Y J，Liu J Q. In situ construction of pollen-petal-like hetero structured Co3O4-CeO2 on 3D FeNi3 foam as a bifunctional catalyst for overall water splitting ［J］. Sustainable Energy & Fuels，2021，5（7）：2181.
［46］Khalil M，Dincer I. An investigation of hydrogen production using 3D-printed cathodes for alkaline water electrolysis ［J］. Energy Conversion and Management，2024，302：118169.
［47］Yu L P，Zhang J，Dang Y L，He J K，Tobin Z，Kerns P，Dou Y H，Jiang Y，He Y H，Suib S. In situ growth of Ni2P-Cu3P bimetallic phosphide with bicontinuous structure on self-supported NiCuC substrate as an efficient hydrogen evolution reaction electrocatalyst ［J］. ACS Catalysis，2019，9（8）：6919.
［48］Chen W，Fan Z L，Zeng G F，Lai Z P. Layer-dependent supercapacitance of graphene films grown by chemical vapor deposition on nickel foam ［J］. Journal of Power Sources，2013，225：251.
［49］Frei M，Köhler C，Dietel L，Martin J，Wiedenmann F，Zengerle R，Kerzenmacher S. Pulsed electrodeposition of highly porous Pt alloys for use in methanol，formic acid，and glucose fuel cells ［J］. ChemElectroChem，2018，5（7）：10133.
［50］Zou X L，He Y Y，Sun P，Zhao J，Cui G F. A novel dealloying strategy for fabricating nanoporous silver as an electrocatalyst for hydrogen peroxide detection ［J］. Applied Surface Science，2018，447：542.
［51］Kellenberger A，Vaszilcsin N，Brandl W，Duteanu N. Kinetics of hydrogen evolution reaction on skeleton nickel and nickel-titanium electrodes obtained by thermal arc spraying technique ［J］. International Journal of Hydrogen Energy，2007，32（15）：3258.
［52］Giarratano F，Arzac G M，Godinho V，Hufschmidt D，De Haro M J，Montes O，Fernández A. Nanoporous Pt-based catalysts prepared by chemical dealloying of magnetron-sputtered Pt-Cu thin films for the catalytic combustion of hydrogen ［J］. Applied Catalysis B：Environmental，2018，235：168.
［53］Ren J T，Wu X M，Liu T，Chen L，Hao R，Song Y J，Liu Y P，Yuan Z Y. Interfacing nickel with molybdenum oxides as monolithic catalyst to accelerate alkaline hydrogen electrocatalysis with robust stability ［J］. Applied Catalysis. B，Environmental，2022，317：121786.
［54］（纪晓阳.过渡金属磷化物的合成及其电解水析氢性能的研究 ［D］. 青岛：青岛科技大学，2022. 1.）
X Y Ji. The Study on Preparation of Transition Metal Phosphide and Their Hydrogen Evolution Performance for Water Electrolysis ［D］. Qingdao：Qingdao University of Science & Technology，2022. 1.
［55］Amirabad T N，Ensafi A A，Mousaabadi K Z，Rezaei B，Demir M. Binder-free engineering design of Ni-MOF ultrathin sheet-like grown on PANI@GO decorated nickel foam as an electrode for in hydrogen evolution reaction and asymmetric supercapacitor ［J］. International Journal of Hydrogen Energy，2023，48（76）：29471.
［56］Frederiksen M L，Kragh-Schwarz M V，Bentien A，Nielsen L P，Lu P. Performance of Co-Co（OH）2 coated nickel foam as catalysts for the hydrogen evolution reaction under industrially relevant conditions ［J］. International Journal of Hydrogen Energy，2023，49：668.
［57］Ali Z，Mehmood M，Ghazi Z A. Herring bone graphitic nanofibers grown on NiFe-silica nanocomposites by CVD method for HER activity in alkaline media ［J］. Materials Letters，2021，305：130838.
［58］Liu H R，Ouyang D，Zhou Q，Feng C C. Successional heterostructure MoS2-Ni3S2 nanospheres based on 3D nano-porous Ni：an efficient electrocatalyst for overall water splitting ［J］. Journal of Alloys and Compounds，2022，920：165243.
［59］Kublanovsky V S，Yapontseva Y S. Electrocatalytic properties of Co-Mo alloys electrodeposited from a citrate-pyrophosphate electrolyte ［J］. Electrocatalysis，2014，5（4）：372.
［60］Kuznetsov V V，Kalinkina A A，Pshenichkina T V，Balabaev V V. Electrocatalytic properties of cobalt-molybdenum alloy deposits in the hydrogen evolution reaction ［J］. Russian Journal of Electrochemistry，2008，44（12）：1350.
［61］Gojgić J D，Petričević A M，Rauscher T，Bernäcker C I，Weißgärber T，Pavko L，Vasilić R，Pajić M N，Jović V D. Hydrogen evolution at Ni foam electrodes and Ni-Sn coated Ni foam electrodes ［J］. Applied Catalysis A：General，2023，663：119312.
［62］Shen Y，Wu P，Wang C，Yuan W，Yang W L，Shang X. Electrodeposition of amorphous Ni-Fe-Mo composite as a binder-free and high-performance electrocatalyst for hydrogen generation from alkaline water electrolysis ［J］. International Journal of Hydrogen Energy，2023，48（85）：33130.
［63］（邓子华，钟霆峰，左赵宏，刘渝萍. 电解水析氢催化剂NiCu/Ni（OH）2的综合实验设计 ［J］. 实验科学与技术，2024，22（3）：87.）
Z H Deng，T F Zhogn，Z H Zuo，Y P Liu. Comprehensive experiment design on NiCu/Ni（OH）2 electrocatalysts for the alkaline hydrogen evolution reaction ［J］. Experiment Science and Technology，2024，22（3）：87.
［64］Xing L H，Meng F X，Hao Y G，Shi X T，Wang Y X. Electrodeposited Ni/C-SnO2 composite electrode materials for hydrogen evolution reaction in alkaline electrolyte ［J］. International Journal of Electrochemical Science，2023，18（4）：100089.
［65］Ren J T，Wang Y S，Song Y J，Chen L，Yuan Z Y. Interface engineering of in-situ formed nickel hydr（oxy）oxides on nickel nitrides to boost alkaline hydrogen electrocatalysis ［J］. Applied Catalysis B：Environmental，2022，309：121279.
［66］Kuang P Y，Tong T，Fan K，Yu J G. In situ fabrication of Ni-Mo bimetal sulfide hybrid as an efficient electrocatalyst for hydrogen evolution over a wide pH range ［J］. ACS Catalysis，2017，7（9）：6179.
［67］Ahmad Y H，Mohamed A M，Golden T D，D'Souza N. Electrodeposition of nanocrystalline Ni-Mo alloys from alkaline glycinate solutions ［J］. International Journal of Electrochemical Science，2014，9（11）：6438.
［68］Zheng Y，Jiao Y，Vasileff A，Qiao S Z. Hydrogen evolution reaction in alkaline solution：from theory，single crystal models，to practical electrocatalysts ［J］. Angewandte Chemie International Edition，2017，57（26）：7568.
［69］Wang L，Weissbach T，Reissner R，Ansar A，Gago A S，Holdcroft S，Friedrich K A. High performance anion exchange membrane electrolysis using plasma-sprayed，non-precious-metal electrodes ［J］. ACS Applied Energy Materials，2019，2（11）：7903.
［70］Schiller G，Henne R，Borck V. Vacuum plasma spraying of high-performance electrodes for alkaline water electrolysis ［J］. Journal of Thermal Spray Technology，1995，4：185.
［71］Kraglund M R，Carmo M，Schiller G，Ansar S A，Aili D，Christensen E，Jensen J O. Ion-solvating membranes as a new approach towards high rate alkaline electrolyzers ［J］. Energy & Environmental Science，2019，12（11）：3313.
［72］Bhole S D，Nemade J B，Collins L，Liu C. Effect of nickel and molybdenum additions on weld metal toughness in a submerged arc welded HSLA line-pipe steel ［J］. Journal of Materials Processing Technology，2006，173（1）：92.
［73］Liang X H，Wu X，Li X Q，Mao J，Gai Q X. Preparation of NiAl coated nickel foam cathode for alkaline water electrolysis using atmospheric plasma spraying ［J］. International Journal of Electrochemical Science，2020，15（6）：5916.
［74］Kim J E，Bae K K，Park C S，Jeong S U，Baik K H，Kim J W，Kang K S，Lee K B，Kim Y H. Electrochemical characterization of Raney nickel electrodes prepared by atmospheric plasma spraying for alkaline water electrolysis ［J］. Journal of Industrial and Engineering Chemistry，2019，70：160.
［75］Aghasibeig M，Dolatabadi A，Wuthrich R，Moreau C. Three-dimensional electrode coatings for hydrogen production manufactured by combined atmospheric and suspension plasma spray ［J］. Surface and Coatings Technology，2016，291：348.
［76］（宋嘉薇. 具有梯度结构的碱式电解水电极研究 ［D］. 沈阳：沈阳工业大学，2022. 1.）
J W Song. Study on Alkaline Water Electrolysis Electrode with Gradient Structure ［D］. Shenyang：Shenyang University of Technology，2022. 1.
Basic Information:
DOI：10.13373/j.cnki.cjrm.XY24060005
Chinese Library Classification Number:TQ426.8
Citation Information:
The white paper "China's Energy Development in the New Era" directly pointed out that energy saving，low-carbon，and a diversified new type of clean enterprise system is a major development orientation for the future，promising to achieve China's carbon neutrality goal by 2060. Within this strategic framework，clean power becomes more and more important，with hydrogen being a noteworthy efficient and clean energy carrier at home and abroad. Among clean energy technologies，the production of hydrogen from water electrolysis is attractive because it is sustainable and can be used on a massive scale. The key is electrode preparation technology，determining the high rate and low cost of the whole hydrogen production process. By researching the hydrogen adsorption free energy （ΔGH*）of electrode materials，researchers have concluded that precious metal-based electrodes （Pt，Rh，Re，Pd and Ir）are excellent for hydrogen evolution efficiency，with Pt being the best material. However，due to limited reserves and high costs，their wide application is restricted. As a result，non-precious metal catalysts have attracted attention in recent years. Ni is also considered as a non-precious metal material，due to its better reserves，relatively low price and high performance for alkaline water hydrogen production. Currently，common methods for preparing hydrogen evolution reaction （HER）electrodes include liquid-phase synthesis，chemical vapor deposition （CVD），electrodeposition，plasma spraying，magnetron sputtering，high-energy ball milling，and powder sintering，etc. 1）Liquid-phase synthesis technology：This includes solvothermal/hydrothermal methods，redox reaction methods，sol-gel processes，hydrolysis reactions，and precipitation （including direct precipitation，co-precipitation，and homogeneity precipitation）. Disadvantages are also obvious：the operation is complicated，requires higher control of reaction conditions，and may take too long. 2）CVD：The chemical composition in CVD process is complex，often involving a combination of gas-phase and surface reactions. Volatile precursors are delivered to the reaction zone using carrier gas and/or diffusion，and precursors can react with each other or decompose in the gas phase （homogeneous reactions），or adsorb upon a substrate surface and react with reactive gases （heterogeneous reactions）. Both reactions produce solid films and gas-state by-products on the substrate. This chemical process differentiates CVD from other physical deposition processes like evaporation，sputtering，and molecular beam epitaxy，with advantages like simple equipment operation and maintenance，and control over coating density. However，it has disadvantages like high reaction temperature，complex preparation process，frequent cleaning of the deposition chamber，and potential environmental pollution from exhaust gas requiring proper disposal. 3）Electrochemical deposition：Electrodeposition is a straightforward and low-cost catalyst layer preparation method，which features strong catalytic activity，simple operation，good controllability，and fast deposition rate for obtaining non-equilibrium structures. However，it requires large electrical energy consumption，and the high internal stress in the coating layer often leads to poor performance of the finished product. 4）Plasma spraying：Depending on the environment，it includes vacuum plasma spraying （VPS），low-pressure plasma spraying （LPPS），and atmospheric plasma spray （APS）. It offers good bonding strength and high efficiency and quality，but has low powder usage efficiency and expensive equipment. Under the action of an electric field，water molecules in the solution decompose to form hydrogen ions （H+）and hydroxyl ions （OH−）through a redox reaction between the anode and cathode. Hydrogen is produced at the cathode and oxygen at the anode. Hydrogen ions receive electrons to reduce into hydrogen at the cathode，while hydroxyl ions release electrons to oxidize into oxygen and water at the anode. Electrochemical hydrogen evolution occurs in three steps：Volmer step，Heyrovsky step and Tafel step. HER kinetics includes two steps：the hydrolysis of hydroxyl ions （OH−）and adsorption of hydrogen atoms is called Volmer step，consisting of electron reduction on catalyst surface M for example adsorption H+，producing adsorbed hydrogen atoms （H*）where basic electrolytes contain H2O as proton source，while acidic electrolytes contain H3O+. The next step is the production of H2 by Heyrovsky manner，Tafel step，or a combination of both. The formation and conversion of adsorbed hydrogen is key to HER，involving both chemical adsorption and desorption due to hydrogen adsorption free energy. This free energy describes HER reaction rate performance，with a perfect HER catalyst having moderate hydrogen adsorption free energy to ensure efficient and smooth step processes. If the free energy is higher than zero，the reaction rate is lower，a negative value helps binding and facilitates Volmer step. Too strong negative forces inhibit further reaction （Heyrovsky or Tafel steps）. Tafel slope，associated with the rate-controlling step，relates to electrode reaction rate and overpotential. In basic HER，Volmer step is typically the slowest link，influencing the total reaction rate. Controlling reaction conditions or using appropriate catalysts to lower hydrogen adsorption free energy near 0 accelerates Volmer step，improving HER rate. While non-precious metals like cobalt and mammothine have advantages in hydrogen adsorption free energy compared to nickel，storage capacity and price restrict large-scale application. Ni-based electrodes have progressed in HER research and widely studied. Future trends include combining methods to construct heterojunction interfaces or synthesize composite catalysts. Machine learning technology applied to catalytic materials design and discovery has accelerated this field，significantly contributing to the development and optimization of non-PGM （Platinum-group metals）catalysts.
quote
| GB/T 7714-2015 | [1] Yueping Tang, Yuebin Lin, Shanshan Li, et al. Research Progress on Nickel-Based Electrode Catalysts for Alkaline Water Electrolysis to Produce Hydrogen[J]. Chinese Journal of Rare Metals, 2025, 49(6): 918-933. DOI:10.13373/j.cnki.cjrm.XY24060005. |
| MLA | [1] Yueping Tang, et al., "Research Progress on Nickel-Based Electrode Catalysts for Alkaline Water Electrolysis to Produce Hydrogen." Chinese Journal of Rare Metals, vol. 49, no. 6, 2025, pp. 918-933, https://doi.org/10.13373/j.cnki.cjrm.XY24060005. |
| APA | [1] Yueping Tang, Yuebin Lin, Shanshan Li, Penglin Zhang, Shuxian Zhuang, Chengshuang He, Meng Ma, Lei Han, Puyu Du, & Qinghe Yu. (2025). Research Progress on Nickel-Based Electrode Catalysts for Alkaline Water Electrolysis to Produce Hydrogen. Chinese Journal of Rare Metals, 49(6), 918-933. https://doi.org/10.13373/j.cnki.cjrm.XY24060005 |
| IEEE | [1] Yueping Tang, Yuebin Lin, Shanshan Li, Penglin Zhang, Shuxian Zhuang, Chengshuang He, Meng Ma, Lei Han, Puyu Du, and Qinghe Yu, "Research Progress on Nickel-Based Electrode Catalysts for Alkaline Water Electrolysis to Produce Hydrogen," Chinese Journal of Rare Metals, vol. 49, no. 6, pp. 918-933, 2025, doi: 10.13373/j.cnki.cjrm.XY24060005. keywords: {alkaline water electrolysis for hydrogen production;electrocatalyst;Ni-base electrode} |