氢（气）作为一种重要的化工原料以及氢燃料电池原料需求量巨大。目前利用化石燃料制备的“灰氢”占据总产量95%以上，不仅无法再生而且碳排放量巨大，不利于“双碳”目标的实现。而电解水制备的“绿氢”污染少、可持续，但受限于制氢成本较高。目前电解水制氢技术中碱性电解槽制氢技术最为成熟、成本最低但其电能转化效率较低。提升电极材料的活性能有效提高电解水的效率。镍基材料由于资源丰富、成本低、耐碱腐蚀被广泛用于制备电极，但其催化活性仍有待进一步提升。本文从改善传质、传荷、本征催化活性等方面着手，设计并制备了一系列高催化活性镍基电解水电极材料，并研究了其活性提升的机理。针对纯镍块体电极材料析氢活性较差但纳米材料稳定性较差的问题，开发了一种螺位错驱动生长策略，实现在非贵金属材料镍纳米锥上构筑具有丰富低配位活性原子的高密度台阶结构。原位电沉积带来的与基底的金属键接、纳米镍的棱锥结构以及纯镍成分保证镍纳米锥阵列的力学、化学稳定性；而螺位错结构保证其表面台阶结构稳定不易重构。该析氢电极材料兼具高活性与高稳定性。针对电解水析氧反应动力学较慢问题，通过制备具有不同尖端曲率NiFe纳米尖锥材料，系统研究了尖端曲率对碱性析氧反应动力学过程的影响，首次证明高曲率尖端的局部增强电场促进OH-在活性位点的聚集是加速碱性析氧动力学的有效机制，且该规律与材料种类无关。成分优化后尖端锋利的NiFe纳米尖锥即使与目前报道其他先进的析氧催化剂相比也具有极佳的本征活性。针对多元合金电极材料难以构筑稳定、高密度活性位点的问题，使用还原退火诱导相分离的方法实现在MoO2纳米棒阵列原位析出稳定、超高密度的NiMoFe三元合金纳米颗粒，同时该结构具备高导电性、超疏水性和超亲水性。使用该材料同时作为阴极、阳极（双功能）进行全水分解，具有极低的槽压与极佳稳定性。该原位构建致密、均匀、稳定多元合金纳米颗粒的通用方法可推广到其他体系。针对磷化物析氢催化剂活性仍有待提高的问题，通过控制镍的尺寸调控镍的热扩散从而调控产物相结构。使用纳米镍作为基底构筑均匀分布NiCoP-CoP异质结，得到的NiCoP-CoP@Ni纳米线阵列具有极佳的碱性析氢催化活性（10 mA cm-2下过电位20 mV）。高的活性位点密度以及NiCoP-CoP异质结优异碱性HER本征活性是该材料高催化活性的来源。

As an important raw material of chemical industry and hydrogen fuel cell, hydrogen (gas) is in great demand. At present, the "grey hydrogen" prepared from fossil fuels accounts for more than 95% of the total output. It is not only unsustainable but also has huge carbon emissions, which is not conducive to realizing the "Double Carbon" goal. The "green hydrogen" produced by water electrolysis is less polluted and sustainable, but limited by its high cost. Among the presently applicable technical routes, the alkaline water electrolyzer is of the lowest cost and the most mature, but its electric energy conversion efficiency is low. Improving the activity of electrode materials can effectively improve the efficiency of water electrolysis. Nickel based materials are widely used to prepare electrodes because of their abundance, low cost and alkali corrosion resistance, but their activity needs to be further improved. In this dissertation, a series of nickel based water splitting electrode materials with high catalytic activity are designed and prepared from the aspects of improving mass transfer, charge transfer and intrinsic catalytic activity. The mechanisms of performance enhancement are also studied.To solve the problem of poor hydrogen evolution activity of pure nickel bulk electrode materials but poor stability of nano nickel materials, a screw dislocation driven growth strategy is developed to build a high-density step structure with rich low coordination active atoms on non-noble metal nickel nanopyramids. The metal bonding with the substrate brought by in-situ electrodeposition, the pyramid structure of nano nickel and the single composition of pure nickel ensure the mechanical and chemical stability of nickel nano pyramid array. The screw dislocation in the nanopyramid ensures the stability of its surface step structure whose atoms are not easy to reconstruct. The electrode material has both high hydrogen evolution activity and high stability.To improve the slow kinetics of oxygen evolution reaction in electrolytic water, NiFe nanocone materials with different tip curvature are prepared, and the effect of tip curvature on the kinetics of alkaline oxygen evolution reaction is systematically studied. It is proved for the first time that the local enhanced electric field at the high curvature tip promoted the aggregation of OH- at the active site, which is an effective mechanism to accelerate the kinetics of alkaline oxygen evolution. This law is independent of the type of material. NiFe nanocone catalyst with sharp tip after composition optimization is intrinsically highly active OER catalysts.Generally, it is difficult to construct stable and high-density active sites for multicomponent alloy electrode materials. Here the reduction annealing induced phase separation method is used to precipitate stable and ultra-high-density NiMoFe ternary alloy nanoparticles in MoO2 nanorod array. The NiMoFe@MoO2 structure is also of high conductivity, super hydrophobicity and super hydrophilicity. Using this material both as the cathode and anode (bifunctional catalyst) for full water splitting, it shows very low cell pressure and excellent stability. This general method for in-situ construction of dense, uniform and stable multicomponent alloy nanoparticles can be extended to other systems.To improve the HER activity of phosphide catalyst, the phase composition of the phosphide product is regulated by controlling the size of nickel to regulate its thermal diffusion. Nano-nickel is used as the substrate to form a NiCoP-CoP heterostructure. The obtained NiCoP-CoP@Ni nanowire array is a highly active phosphide alkaline hydrogen evolution catalyst (20 mV overpotential at 10 mA cm-2). High-density active site and excellent alkaline HER intrinsic activity of NiCoP-CoP heterostructure countribute to its high catalytic activity.