电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍...电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍铁羟基/氢氧化物(NiFe(oxy)hydroxides)是近期研究的热点,其在碱性条件下具有极低的OER过电位,部分材料性能甚至超过了贵金属基催化剂,如IrO_(2)和RuO_(2).然而,NiFe(oxy)hydroxides的长期催化稳定性,尤其是在大电流下的长期催化稳定性,成为限制其实际应用的主要问题,这主要是由于铁元素的严重流失导致的.因此,如何有效控制和利用电化学溶解/沉积动力学成为稳定铁位点的关键.为克服该挑战,本文提出了一种大电流极化重构方法来固定活性铁位点.通过在大电流(1.5 A cm^(-2))下对材料进行表面快速极化重构,成功制备了FeOOH@NiOOH(eFNO_(L))电催化剂.eFNO_(L)不仅具有稳定的铁位点,还暴露出高指数晶面,因此eFNO_(L)同时展现出较好的OER催化活性和稳定性.同时,密度泛函理论计算结果表明,与具有低指数晶面的FeNiOOH相比,大电流极化工程制备的分相eFNO_(L)对铁位点表现出更高的结合能,可以有效抑制OER过程中的铁流失,且高指数晶面在改变速率决定步骤和减少吸附能垒上具有更大的优势.电化学测试结果表明,经过优化后的eFNO_(L)催化剂在产生100和500 mA cm^(-2)大电流密度仅需234和27 mV的过电位,并且具有较小的Tafel斜率(35.2 mV dec^(-1)).由于铁位点结合能的提高,eFNO_(L)催化剂在500 mA cm^(-2)的电流密度下能够稳定催化超过100 h,且仅有1.5%的性能衰减,优于近期报道的大多数镍铁基OER催化剂.综上,本文为开发高活性和高稳定性能的催化剂提供了一种有效的大电流电化学重构策略,在电解水制氢领域实现其工业化的大规模应用方面显示出巨大潜力,有望降低可持续电解水制氢成本.展开更多
以石墨烯、Ni SO4、K2S2O8(饱和)、氨水、蒸馏水为反应物,经过常温回流制备得到Ni OOH/Ni(OH)2含量不同的石墨烯/Ni OOH/Ni(OH)2复合材料。扫描电子显微镜法(SEM)表征显示,Ni(OH)2/Ni OOH在石墨烯表面上形成多孔结构,负载了多孔Ni OOH/N...以石墨烯、Ni SO4、K2S2O8(饱和)、氨水、蒸馏水为反应物,经过常温回流制备得到Ni OOH/Ni(OH)2含量不同的石墨烯/Ni OOH/Ni(OH)2复合材料。扫描电子显微镜法(SEM)表征显示,Ni(OH)2/Ni OOH在石墨烯表面上形成多孔结构,负载了多孔Ni OOH/Ni(OH)2的石墨烯又进行了层层堆积。电化学性能测试显示,电极材料GP/Ni-5性能最佳,其在电流密度为100 m A/g时,首次可逆比容量为1 287.4 m Ah/g,80次循环后比容量保持在830 m Ah/g,而纯Ni OOH/Ni(OH)2首次可逆比容量为2 400.6 m Ah/g,80次循环后比容量已降至405.9 m Ah/g,表明石墨烯的加入大大提高了材料的稳定性。展开更多
NiOOH was prepared by chemical oxidation of β Ni(OH) 2. The physical characteristics and the chemical composition of the product were characterized by XRD, TG/DTA and ICP measurements. β NiOOH and the mixed samples ...NiOOH was prepared by chemical oxidation of β Ni(OH) 2. The physical characteristics and the chemical composition of the product were characterized by XRD, TG/DTA and ICP measurements. β NiOOH and the mixed samples of β NiOOH with γ MnO 2 in different ratios were charged/discharged in constant current, the results show that the addition of γ MnO 2 improves the discharge voltage plateau of nickel electrode and the optimum ratio of γ MnO 2 in the electrode is 25%. The cut off voltage of nickel electrode should be above 0 V( vs .Hg/HgO).展开更多
NiOOH was prepared by one-step electrolysis of spherical Ni（OH）2 and the effects of electrolysis parameters were examined. The highly pure NiOOH was obtained after electrolysis at a current density of 60mA.g^-1 and...NiOOH was prepared by one-step electrolysis of spherical Ni（OH）2 and the effects of electrolysis parameters were examined. The highly pure NiOOH was obtained after electrolysis at a current density of 60mA.g^-1 and 30℃ with anodic potential controlled in the range of 1.73-1.85V （vs. Zn/ZnO） for 360min. The NiOOH samriles were characterized bv X-ray oowder diffraction （XRD） and scanning electron microscope （SEM） analysis.Resuits indicate that the electrolysis product is spherical NiOOH doped with graphite. Charge and discharge tests show that the prepared NiOOH offers a discharge capacity of over 270mAh·g^-1 at current density of 30mA·g^-1 and can be directly used as cathode material of alkaline Zn/NiOOH batteries. Galvanostatic charge/discharge and cyclic voltammetry （CV） tests reveal good cycling reversibility, of the NiOOH electrode.展开更多
文摘电解水技术是制取高纯度氢气的有效途径,为传统的氢气生产提供了一种可持续的替代方案.其中,开发性能优异的电催化材料是降低电解水制氢成本的关键.析氧反应(OER)由于涉及多个电子转移而导致的动力学缓慢,是克服高过电位的主要挑战.镍铁羟基/氢氧化物(NiFe(oxy)hydroxides)是近期研究的热点,其在碱性条件下具有极低的OER过电位,部分材料性能甚至超过了贵金属基催化剂,如IrO_(2)和RuO_(2).然而,NiFe(oxy)hydroxides的长期催化稳定性,尤其是在大电流下的长期催化稳定性,成为限制其实际应用的主要问题,这主要是由于铁元素的严重流失导致的.因此,如何有效控制和利用电化学溶解/沉积动力学成为稳定铁位点的关键.为克服该挑战,本文提出了一种大电流极化重构方法来固定活性铁位点.通过在大电流(1.5 A cm^(-2))下对材料进行表面快速极化重构,成功制备了FeOOH@NiOOH(eFNO_(L))电催化剂.eFNO_(L)不仅具有稳定的铁位点,还暴露出高指数晶面,因此eFNO_(L)同时展现出较好的OER催化活性和稳定性.同时,密度泛函理论计算结果表明,与具有低指数晶面的FeNiOOH相比,大电流极化工程制备的分相eFNO_(L)对铁位点表现出更高的结合能,可以有效抑制OER过程中的铁流失,且高指数晶面在改变速率决定步骤和减少吸附能垒上具有更大的优势.电化学测试结果表明,经过优化后的eFNO_(L)催化剂在产生100和500 mA cm^(-2)大电流密度仅需234和27 mV的过电位,并且具有较小的Tafel斜率(35.2 mV dec^(-1)).由于铁位点结合能的提高,eFNO_(L)催化剂在500 mA cm^(-2)的电流密度下能够稳定催化超过100 h,且仅有1.5%的性能衰减,优于近期报道的大多数镍铁基OER催化剂.综上,本文为开发高活性和高稳定性能的催化剂提供了一种有效的大电流电化学重构策略,在电解水制氢领域实现其工业化的大规模应用方面显示出巨大潜力,有望降低可持续电解水制氢成本.
文摘以石墨烯、Ni SO4、K2S2O8(饱和)、氨水、蒸馏水为反应物,经过常温回流制备得到Ni OOH/Ni(OH)2含量不同的石墨烯/Ni OOH/Ni(OH)2复合材料。扫描电子显微镜法(SEM)表征显示,Ni(OH)2/Ni OOH在石墨烯表面上形成多孔结构,负载了多孔Ni OOH/Ni(OH)2的石墨烯又进行了层层堆积。电化学性能测试显示,电极材料GP/Ni-5性能最佳,其在电流密度为100 m A/g时,首次可逆比容量为1 287.4 m Ah/g,80次循环后比容量保持在830 m Ah/g,而纯Ni OOH/Ni(OH)2首次可逆比容量为2 400.6 m Ah/g,80次循环后比容量已降至405.9 m Ah/g,表明石墨烯的加入大大提高了材料的稳定性。
文摘NiOOH was prepared by chemical oxidation of β Ni(OH) 2. The physical characteristics and the chemical composition of the product were characterized by XRD, TG/DTA and ICP measurements. β NiOOH and the mixed samples of β NiOOH with γ MnO 2 in different ratios were charged/discharged in constant current, the results show that the addition of γ MnO 2 improves the discharge voltage plateau of nickel electrode and the optimum ratio of γ MnO 2 in the electrode is 25%. The cut off voltage of nickel electrode should be above 0 V( vs .Hg/HgO).
文摘NiOOH was prepared by one-step electrolysis of spherical Ni（OH）2 and the effects of electrolysis parameters were examined. The highly pure NiOOH was obtained after electrolysis at a current density of 60mA.g^-1 and 30℃ with anodic potential controlled in the range of 1.73-1.85V （vs. Zn/ZnO） for 360min. The NiOOH samriles were characterized bv X-ray oowder diffraction （XRD） and scanning electron microscope （SEM） analysis.Resuits indicate that the electrolysis product is spherical NiOOH doped with graphite. Charge and discharge tests show that the prepared NiOOH offers a discharge capacity of over 270mAh·g^-1 at current density of 30mA·g^-1 and can be directly used as cathode material of alkaline Zn/NiOOH batteries. Galvanostatic charge/discharge and cyclic voltammetry （CV） tests reveal good cycling reversibility, of the NiOOH electrode.
