研究论文

碱性电解水大电流密度电催化剂的制备及经济性研究

  • 于泽龙 ,
  • 唐春 ,
  • 饶家豪 ,
  • 郭恒 ,
  • 周莹
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  • 1.西南石油大学 新能源与材料学院, 成都 610500
    2.氢能绿色制储与高效利用川渝共建重点实验室, 成都 610500
    3.天府永兴实验室, 成都 610213
于泽龙(2000-), 男, 硕士研究生. E-mail: 18535069947@163.com
唐 春, 副研究员. E-mail: tangchun@swpu.edu.cn;
周 莹, 教授. E-mail: yzhou@swpu.edu.cn

收稿日期: 2025-01-08

  修回日期: 2025-04-06

  网络出版日期: 2025-04-27

基金资助

国家自然科学基金(22109132);四川省自然科学基金(2022NSFSC0023);中国博士后科学基金(2024M750704);天府永兴实验室科技攻关重大项目(2023KJGG15)

Preparation and Economic Analysis of High-current-density Electrocatalysts for Alkaline Water Electrolysis

  • YU Zelong ,
  • TANG Chun ,
  • RAO Jiahao ,
  • GUO Heng ,
  • ZHOU Ying
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  • 1. School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China
    2. Sichuan-Chongqing Joint Key Laboratory of Green Hydrogen Production & Storage and Efficient Utilization, Chengdu 610500, China
    3. Tianfu Yongxing Laboratory, Chengdu 610213, China
YU Zelong (2000-), male, Master candidate. E-mail: 18535069947@163.com
TANG Chun, associate professor. E-mail: tangchun@swpu.edu.cn;
ZHOU Ying, professor. E-mail: yzhou@swpu.edu.cn

Received date: 2025-01-08

  Revised date: 2025-04-06

  Online published: 2025-04-27

Supported by

National Natural Science Foundation of China(22109132);Sichuan Natural Science Foundation(2022NSFSC0023);China Postdoctoral Science Foundation(2024M750704);Key Grant Technologies Project of Tianfu Yongxing Laboratory(2023KJGG15)

摘要

碱性电解水(Alkaline Water Electrolysis, AWE)制氢由于其较低的电流密度而面临效率低和成本高的挑战, 需要开发大电流密度下稳定的高效非贵金属电催化剂。本研究在泡沫镍(Nickel Foam, NF)骨架上采用水热法结合磷化技术制备了非晶NiMoOP/NF电催化材料, 非晶针状形貌可以有效增加活性位点数量并提升电解水制氢稳定性, 在10和1000 mA·cm-2的电流密度下, 析氢过电位达到31和370 mV, 并且在1 A·cm-2的大电流密度下可以稳定运行1100 h。将NiMoOP/NF材料应用于全水解与晶硅异质结太阳能电池耦合, 太阳能到氢能的理论转换效率高达18.60%。在工业模拟条件(温度60 ℃, 30%(质量分数) KOH电解液)下, 电解电压在1.77 V可实现400 mA·cm-2的电流密度, 其制氢能耗为4.19 kWh·Nm-3(Nm3: 标准立方米)。结合光伏电解制氢经济性研究表明, 光伏离网非储能制氢系统的最低制氢成本为¥28.52 kg-1。本研究开发的非晶纳米针状结构材料有效提高了电解水制氢活性和稳定性, 为设计大电流密度下制氢催化材料提供了思路, 结合光伏电解水制绿氢经济性分析为绿氢产业发展提供了支撑。

本文引用格式

于泽龙 , 唐春 , 饶家豪 , 郭恒 , 周莹 . 碱性电解水大电流密度电催化剂的制备及经济性研究[J]. 无机材料学报, 2025 , 40(12) : 1405 -1413 . DOI: 10.15541/jim20250012

Abstract

Alkaline water electrolysis (AWE) faces challenges of low efficiency and high costs due to its relatively low current density. It is necessary to develop efficient and stable non-precious metal electrocatalysts under high current densities. In this study, an amorphous NiMoOP/NF electrocatalyst was fabricated by the hydrothermal method combined with phosphorization on a nickel foam (NF) substrate. The amorphous needle-like morphology effectively increases active sites and enhances the stability of hydrogen production through water electrolysis. At current densities of 10 and 1000 mA·cm-2, the hydrogen evolution overpotentials are 31 and 370 mV, respectively, and the catalyst stably runs for 1100 h at a high current density of 1 A·cm-2. The NiMoOP/NF material, when integrated with crystalline silicon heterojunction solar cells for overall water splitting, achieves a theoretical solar-to-hydrogen conversion efficiency of up to 18.60%. Under industrially relevant conditions (60 ℃, 30% (in mass) KOH electrolyte), the electrolysis voltage is 1.77 V, enabling a current density of 400 mA·cm-2, with a hydrogen production energy consumption of 4.19 kWh·Nm-3 (Nm3: Normal cubic meter). Economic analysis of photovoltaic-powered hydrogen production via electrolysis indicates that the minimum hydrogen production cost for an off-grid and non-storage photovoltaic hydrogen production system is ¥28.52 kg-1. The amorphous nanoneedle-like materials developed in this study significantly enhanced both hydrogen evolution activity and stability during water electrolysis, providing valuable insights for design of high-current-density hydrogen evolution catalysts. Furthermore, the combined economic analysis of photovoltaic electrolysis for green hydrogen production supports advancement of green hydrogen industry.

参考文献

[1] DONG B, YU N, WANG Q Y, et al. Double active sites promoting hydrogen evolution activity and stability of CoRuOH/Co2P by rapid hydrolysis. Chinese Chemical Letters, 2024, 35(7): 109221.
[2] ZHU Y, CHEN B, CHENG T, et al. Amorphous Nd-Ni-B/NF rare earth composites: preparation and HER electrocatalytic performance. Journal of Inorganic Materials, 2021, 36(6): 637.
[3] SUN W, WANG Y, XIANG K, et al. CoP decorated on Ti3C2Tx MXene nanocomposites as robust electrocatalyst for hydrogen evolution reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015.
[4] SUN Q, CHEN Z, YANG Z, et al. Amorphous vanadium oxide loaded by metallic nickel-copper towards high-efficiency electrocatalyzing hydrogen production. Journal of Inorganic Materials, 2022, 38(6): 647.
[5] XU S, WU Q, LU B A, et al. Recent advances and future prospects on industrial catalysts for green hydrogen production in alkaline media. Acta Physico-Chimica Sinica, 2023, 39(2): 2209001.
[6] 周莹, 饶家豪, 唐春, 等. 光伏电催化硫化氢分解制氢脱硫经济性分析. 天然气工业, 2024, 44(11): 178.
[7] 徐进, 丁显, 宫永立, 等. 电解水制氢厂站经济性分析. 储能科学与技术, 2022, 11(7): 2374.
[8] LAGADEC M F, GRIMAUD A. Water electrolysers with closed and open electrochemical systems. Nature Materials, 2020, 19(11): 1140.
[9] 夏杨红, 胡致远, 韦巍, 等. 可再生能源电解制氢宽范围运行控制策略. 太阳能学报, 2024, 45(8): 34.
[10] BLEEKER J, VAN KASTEREN C, VAN OMMEN J R, et al. Gas bubble removal from a zero-gap alkaline electrolyser with a pressure swing and why foam electrodes might not be suitable at high current densities. International Journal of Hydrogen Energy, 2024, 57: 1398.
[11] WANG X, TIAN H, YU X, et al. Advances and insights in amorphous electrocatalyst towards water splitting. Chinese Journal of Catalysis, 2023, 51: 5.
[12] SHI Y, ZHOU S, LIU J, et al. An integrated amorphous cobalt phosphoselenide electrocatalyst with high mass activity boosts alkaline overall water splitting. Applied Catalysis B: Environment and Energy, 2023, 341: 123326.
[13] CHANG Y, KONG L, XU D, et al. Mo migration-induced crystalline to amorphous conversion and formation of RuMo/ NiMoO4 heterogeneous nanoarray for hydrazine-assisted water splitting at large current density. Angewandte Chemie International Edition, 2025, 64(2): e202414234.
[14] LIU S, WANG Y, ZHAO H, et al. Amorphous W-doped iron phosphide with superhydrophilic surface to boost water-splitting under large current density. Chemical Engineering Journal, 2024, 496: 153956.
[15] RAJA D S, CHUAH X F, LU S Y. In situ grown bimetallic MOF-based composite as highly efficient bifunctional electrocatalyst for overall water splitting with ultrastability at high current densities. Advanced Energy Materials, 2018, 8(23): 1801065.
[16] JIN M, ZHANG X, NIU S, et al. Strategies for designing high- performance hydrogen evolution reaction electrocatalysts at large current densities above 1000 mA cm-2. ACS Nano, 2022, 16(8): 11577.
[17] WANG J, HU J, NIU S, et al. Crystalline-amorphous Ni2P4O12/ NiMoOx nanoarrays for alkaline water electrolysis: enhanced catalytic activity via in situ surface reconstruction. Small, 2022, 18(10): 2105972.
[18] YU L, ZHU Q, SONG S, et al. Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater electrolysis. Nature Communications, 2019, 10: 5106.
[19] ZHANG Y, LIU J, PAN Y, et al. The evolution of MoS2 properties under oxygen plasma treatment and its application in MoS2 based devices. Journal of Materials Science: Materials in Electronics, 2019, 30(19): 18185.
[20] HU H, ZHANG Z, ZHANG Y, et al. An ultra-low Pt metal nitride electrocatalyst for sustainable seawater hydrogen production. Energy & Environmental Science, 2023, 16(10): 4584.
[21] WU S, CHEN D, LI S, et al. Ru cluster incorporated NiMoO(P)4 nanosheet arrays as high-efficient bifunctional catalyst for wind/ solar-to-hydrogen generation systems. Advanced Science, 2023, 10(35): 2304179.
[22] NIU H J, HUANG C, SUN T, et al. Enhancing Ni/Co activity by neighboring Pt atoms in NiCoP/MXene electrocatalyst for alkaline hydrogen evolution. Angewandte Chemie International Edition, 2024, 63(20): e202401819.
[23] ZHANG Z, WANG H, MA M, et al. Integrating NiMoO wafer as a heterogeneous ‘turbo’ for engineering robust Ru-based electrocatalyst for overall water splitting. Chemical Engineering Journal, 2021, 420: 127686.
[24] LIANG W, ZHOU M, LIN X, et al. Nickel-doped tungsten oxide promotes stable and efficient hydrogen evolution in seawater. Applied Catalysis B: Environment and Energy, 2023, 325: 122397.
[25] LIN J, YIN D, HE W, et al. Self-supporting honeycomb coaxial carbon fibers: a new strategy to achieve an efficient hydrogen evolution reaction both in base and acid media. Chemical Engineering Journal, 2024, 488: 151195.
[26] DASTAFKAN K, SHEN X, HOCKING R K, et al. Monometallic interphasic synergy via nano-hetero-interfacing for hydrogen evolution in alkaline electrolytes. Nature Communications, 2023, 14: 547.
[27] LI J, TANG C, ZHANG H, et al. Mesoporous molybdenum carbide for greatly enhanced hydrogen evolution at high current density and its mechanism studies. Materials Reports: Energy, 2023, 3(3): 100215.
[28] LI Q, CHEN C, LUO W, et al. In situ active site refreshing of electro-catalytic materials for ultra-durable hydrogen evolution at elevated current density. Advanced Energy Materials, 2024, 14(17): 2304099.
[29] XU Y, ZHAO Y, SUN M, et al. Reconstruction of Fe sacrifice protective layer enables highly effective CoP catalyst for hydrogen evolution reaction at high current density. Chemical Engineering Journal, 2024, 490: 151697.
[30] YAN S, CHEN X, LI W, et al. Highly active and stable alkaline hydrogen evolution electrocatalyst based on Ir-incorporated partially oxidized Ru aerogel under industrial-level current density. Advanced Science, 2024, 11(7): 2307061.
[31] JIA H, WANG H, YAN F, et al. Unravelling electrocatalytic concerted diatomic-ensembles over superior hydrogen-evolution array structured by NiMo/Mo2N heteronanojunctions. Applied Catalysis B: Environment and Energy, 2024, 343: 123362.
[32] TANG Y, LIU F, LIU W, et al. Multifunctional carbon-armored Ni electrocatalyst for hydrogen evolution under high current density in alkaline electrolyte solution. Applied Catalysis B: Environment and Energy, 2023, 321: 122081.
[33] LI C, WANG Z, LIU M, et al. Ultrafast self-heating synthesis of robust heterogeneous nanocarbides for high current density hydrogen evolution reaction. Nature Communications, 2022, 13: 3338.
[34] CHEN X, ZHAO X, WANG Y, et al. Layered Ni-Co-P electrode synthesized by CV electrodeposition for hydrogen evolution at large currents. ChemCatChem, 2021, 13(16): 3619.
[35] LI Y, YU X, GAO J, et al. Structural and electronic modulation of (Fe, Ni)2P@Ni2P heterostructure for efficient overall water splitting at high current density. Chemical Engineering Journal, 2023, 470: 144373.
[36] DONG Y, DENG Z, ZHANG H, et al. A highly active and durable hierarchical electrocatalyst for large-current-density water splitting. Nano Letters, 2023, 23(19): 9087.
[37] SUN H, YAO B, HAN Y, et al. Multi-interface engineering of self- supported nickel/yttrium oxide electrode enables kinetically accelerated and ultra-stable alkaline hydrogen evolution at industrial-level current density. Advanced Energy Materials, 2024, 14(11): 2303563.
[38] DU W, SHI Y, ZHOU W, et al. Unveiling the in situ dissolution and polymerization of Mo in Ni4Mo alloy for promoting the hydrogen evolution reaction. Angewandte Chemie International Edition, 2021, 60(13): 7051.
[39] WANG Y H, LI L, SHI J, et al. Oxygen defect engineering promotes synergy between adsorbate evolution and single lattice oxygen mechanisms of OER in transition metal-based (oxy)hydroxide. Advanced Science, 2023, 10(32): 2303321.
[40] KHATUN S, SHIMIZU K, PAL S, et al. Enthralling anodic protection by molybdate on high-entropy alloy-based electrocatalyst for sustainable seawater oxidation. Small, 2024, 20(43): 2402720.
[41] WANG H, LIU X, LIU G, et al. Copper doping-induced high- valence nickel-iron-based electrocatalyst toward enhanced and durable oxygen evolution reaction. Chem Catalysis, 2023, 3(3): 100552.
[42] SINGH S, NGUYEN D C, KIM N H, et al. Interface engineering induced electrocatalytic behavior in core-shelled CNTs@NiP2/NbP heterostructure for highly efficient overall water splitting. Chemical Engineering Journal, 2022, 442: 136120.
[43] XU D, LIU S, ZHANG M, et al. Manipulating the dynamic self- reconstruction of CoP electrocatalyst driven by charge transport and ion leaching. Small, 2023, 19(33): 2300201.
[44] WANG J, HU J, LIANG C, et al. Surface reconstruction of phosphorus-doped cobalt molybdate microarrays in electrochemical water splitting. Chemical Engineering Journal, 2022, 446: 137094.
[45] CHEN M, LIU D, FENG J, et al. In-situ generation of Ni-CoOOH through deep reconstruction for durable alkaline water electrolysis. Chemical Engineering Journal, 2022, 443: 136432.
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