WO2017084589A1 - 基于三电极体系的两步法电解水制氢的方法及装置 - Google Patents

基于三电极体系的两步法电解水制氢的方法及装置 Download PDF

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WO2017084589A1
WO2017084589A1 PCT/CN2016/106143 CN2016106143W WO2017084589A1 WO 2017084589 A1 WO2017084589 A1 WO 2017084589A1 CN 2016106143 W CN2016106143 W CN 2016106143W WO 2017084589 A1 WO2017084589 A1 WO 2017084589A1
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electrode
hydrogen
oxygen
evolution catalytic
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王永刚
夏永姚
陈龙
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Fudan University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention belongs to the technical field of electrolyzed water, and in particular relates to a novel method and device for hydrogen production by electrolysis of water in a two-step method based on a three-electrode system.
  • Electrolytic water preparation of hydrogen is relatively simple, the technology is relatively mature, and the hydrogen production process is not polluted, which is an important means to achieve large-scale production of hydrogen.
  • alkaline water electrolysis technology is industrialized early, the technology is mature, and the equipment cost is low. Therefore, alkaline water electrolysis plays a dominant role in the water electrolysis industry.
  • the conventional electrolyzed water technology generates hydrogen and oxygen at the same time as the anode and cathode in the electrode process, which will easily lead to the mixing of hydrogen and oxygen, resulting in impure gas production, and subsequent purification will be greatly increased. Large preparation costs.
  • ion-selective membrane to separate the hydrogen produced by the hydrogen evolution catalytic electrode and the oxygen produced by the oxygen evolution catalytic electrode is an effective solution, but the use of ion-selective membranes also greatly increases the cost.
  • the hydrogen production rate and oxygen production rate are different.
  • the membrane loss is also very serious, which further increases the cost.
  • the selective ion exchange membrane further increases the internal resistance of the electrolytic cell and increases energy consumption.
  • the mainstream work is to improve or prepare a new type of diaphragm, in order to reduce the internal resistance, while taking into account the hydrophilicity, ion permeability and the ability to completely separate hydrogen and oxygen.
  • many new membranes have been explored, the effects are still not very significant.
  • the invention provides a two-step method for electrolyzing water to produce hydrogen by a three-electrode system, wherein the electrolysis cell comprises three electrodes: a hydrogen evolution catalytic electrode which catalyzes the generation of hydrogen by electrolyzing water, and has oxygen for electrolyzing water.
  • a hydrogen evolution catalytic electrode which catalyzes the generation of hydrogen by electrolyzing water, and has oxygen for electrolyzing water.
  • the cathode In the hydrogen production step, the cathode is connected to the hydrogen evolution catalytic electrode, and the anode is connected to the nickel hydroxide electrode; in the oxygen production step, the cathode is connected to the nickel hydroxide electrode, and the anode is connected to the oxygen evolution catalytic electrode.
  • the method for the two-step method for electrolyzing water to produce hydrogen based on the three-electrode system provided by the invention has the following specific steps:
  • Hydrogen production step ie, step of generating hydrogen from electrolyzed water:
  • the water molecule is electrochemically reduced to hydrogen on the surface of the hydrogen evolution catalytic electrode as a cathode, that is, H 2 O+e - ⁇ 1/2H 2 + OH - ; and the Ni(OH) 2 electrode as an anode is electrochemically oxidized to a NiOOH electrode. , that is, Ni(OH) 2 + OH - -e - ⁇ NiOOH + H 2 O, in which electrons flow from the Ni(OH) 2 electrode to the hydrogen evolution catalytic electrode through an external circuit;
  • Oxygen production step ie, step of generating oxygen from electrolyzed water
  • NiOOH electrode as a cathode is electrochemically reduced to a Ni(OH) 2 electrode, that is, NiOOH + H 2 O + e - ⁇ Ni(OH) 2 + OH - ; and the hydroxide ion is on the surface of the oxygen evolution catalytic electrode as an anode. It is electrochemically oxidized to oxygen, that is, 2OH - -2e - ⁇ 1/2O 2 + H 2 O; in this process, electrons flow from the oxygen evolution catalytic electrode to the NiOOH electrode through the external circuit.
  • the step (1) and the step (2) are alternately cycled.
  • the two steps are alternately cycled to realize the recycling of Ni(OH) 2 , and at the same time, the electrolysis of hydrogen and electrolysis to produce oxygen at different times is effectively realized, and finally the hydrogen and oxygen mixing is effectively prevented, thereby achieving the purpose of high-purity hydrogen production. .
  • the hydrogen evolution catalytic electrode has a catalytic effect on hydrogen generation from electrolyzed water, and the catalytic electrode material is:
  • a simple substance or a compound based on a transition metal such as Ni, Co, Fe, such as Ni, a Ni-Mo alloy, a Ni-Cr-Fe alloy, CoO, Co 2 O 3 , CoSe 2 , FeP;
  • W-based compounds such as WC, W 2 C, WS 2 ; or
  • Mo-based compounds such as MoS 2 , MoB, Mo 2 S; or
  • a compound such as C 3 N 4 is a compound such as C 3 N 4 .
  • the oxygen evolution catalytic electrode has a catalytic effect on the generation of oxygen by the electrolyzed water, and the catalytic electrode material is:
  • a compound based on a noble metal such as Ru, Ir, such as IrO x , RuO 2 ; or
  • Elemental or compound based on transition metals such as Ni, Co, Fe, Mn, such as NiFeO x , NiCoO x , CoFeO x , CoO x , NiCuO x , NiO x , SrNb 0.1 Co 0.7 Fe 0.2 O 3-x , MnO x , CoMn 2 O 4 ; or
  • a bioelectrochemical catalyst such as a laccase or the like.
  • the nickel hydroxide electrode is a nickel hydroxide electrode used in a conventional nickel-hydrogen battery, which is composed of an active material Ni(OH) 2 and other additive components, and the added components are nickel powder, Co(OH) 2 , carbon. One or more of powder and binder.
  • the binder is polytetrafluoroethylene.
  • Ni(OH) 2 active material and the additive component are pressed or coated on the metal current collector to form a Ni(OH) 2 electrode by mixing into a film or slurry.
  • the metal current collector includes: a nickel mesh, a foamed nickel, a stainless steel mesh, a titanium mesh, or the like.
  • the electrolyte of the technique for electrolyzing water of the present invention must be an alkaline aqueous solution, and the alkaline aqueous solution is potassium hydroxide or sodium hydroxide.
  • the most notable feature of the electrolyzer designed in accordance with the present invention is that no separator is required to separate the hydrogen and oxygen produced by the electrolysis.
  • the purity of the hydrogen and oxygen produced by the test showed that although there was no separator, hydrogen and oxygen did not mix.
  • the invention adopts a two-step constant current electrolysis method, and the electrolysis curve is shown in Fig. 2, which exhibits excellent electrolyzed water performance: repeating 20 times of two-step electrolysis hydrogen production and oxygen production, when 200 mA constant current electrolysis,
  • the average hydrogen production voltage is about 1.6V
  • the average oxygen production voltage is about 0.5V.
  • those skilled in the art can reasonably select an appropriate voltage range according to the selection of the electrode material and the electrolysis current.
  • the average voltage range of the hydrogen production may be 1.0-3.0 V
  • the oxygen generation voltage range may be 0.2-1.5 V. .
  • the invention is intended to be illustrative only and not to limit the scope of the invention.
  • the electrolysis device of the present invention can use different driving voltages to generate hydrogen and oxygen, and in particular, sustainable energy sources such as solar energy and wind energy can be used to produce hydrogen more efficiently.
  • the hydrogen production or oxygen production step can be selectively performed according to the change of the sunlight intensity, and the utilization rate of the raw energy can be increased; or the hydrogen can be prepared by using excess electric energy at night, and the solar energy can be used to generate oxygen during the day.
  • the two-step electrolysis water hydrogen production method based on the three-electrode system proposed by the present invention is characterized in that hydrogen is electrolyzed by water and oxygen is electrolyzed in two steps.
  • the nickel hydroxide (Ni(OH) 2 ) electrode is electrochemically oxidized into a NiOOH electrode during the preparation of hydrogen in electrolyzed water; it is electrochemically reduced to Ni(OH) 2 during the subsequent electrolysis of water to oxygen. .
  • the nickel hydroxide (Ni(OH) 2 ) electrode acts as a proton and electron buffer, separating the two steps of hydrogen production and oxygen production.
  • the apparatus for electrolyzing water to produce hydrogen by a two-step method based on a three-electrode system of the present invention comprises a hydrogen generating electrode pair and an oxygen generating electrode
  • the hydrogen generation electrode pair includes the hydrogen evolution catalytic electrode and a nickel hydroxide electrode
  • the oxygen generation electrode pair includes the oxygen evolution catalytic electrode and a nickel hydroxide electrode.
  • the nickel hydroxide electrode is oxidized to a NiOOH electrode.
  • the NiOOH electrode is electrochemically reduced to a Ni(OH) 2 electrode.
  • the pair of hydrogen producing electrodes and the pair of oxygen generating electrodes are arranged to operate simultaneously or at different times, preferably at different times.
  • the cyclic electrochemical oxidation-reduction process of the nickel hydroxide electrode divides the conventional electrolyzed water process into two steps of continuous or separate, thereby realizing the preparation of high purity by separately preparing hydrogen and oxygen at different time periods. hydrogen.
  • this method of segmentation also allows the device to eliminate the need for ion-selective membranes to separate hydrogen and oxygen, thus greatly reducing manufacturing costs.
  • Figure 1 shows the working diagram of a three-electrode system two-step electrolysis water electrolysis cell.
  • Figure 2 shows a schematic diagram of a three-electrode system two-step electrolysis water hydrogen/oxygen cycle.
  • the term “about” means that the value can vary by no more than 1% from the recited value.
  • the expression “about 100” includes all values between 99 and 101 and (eg, 99.1, 99.2, 99.3, 99.4, etc.).
  • the terms "containing” or “including” may be open, semi-closed, and closed. In other words, the terms also include “consisting essentially of,” or “consisting of.”
  • system As used herein, the terms “system,” “device,” and “system” have the same meaning and are used interchangeably.
  • hydrofluorescence As used herein, the terms “hydrogen production”, “hydrogen production” have the same meaning and are used interchangeably.
  • the hydrogen and oxygen generated by the electrolyzed water device of the present invention are not mixed and have high safety.
  • the electrolyzed water device of the present invention can still perform high-efficiency electrolysis to generate hydrogen gas and oxygen under unstable voltage output conditions.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolyzer uses a platinum electrode, the catalytic electrode for electrolysis to generate oxygen is ruthenium oxide, and the nickel hydroxide electrode is commercially available with commercially available nickel hydroxide electrode.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol/L potassium hydroxide solution using a constant current of 200 mA. First, the cathode is connected to the platinum electrode, and the anode is connected to the nickel hydroxide electrode. The current is electrolyzed at 200 mA for 600 seconds, and the average voltage is about 1.6 V. Hydrogen is generated on the platinum electrode.
  • the cathode was connected to nickel hydroxide, and the anode was connected to the ruthenium oxide electrode, and the current was electrolyzed at a current of 200 mA until the voltage was raised to 1 V for 600 seconds, and the average voltage was 0.5 V.
  • Oxygen was generated on the ruthenium oxide electrode. No gas is formed on the nickel hydroxide throughout the process. With this cycle 20 times, the curve is stable as shown in Figure 1, and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolytic cell uses a platinum electrode, the catalytic electrode for electrolyzing oxygen is a mixed electrode of CoO and carbon, and the nickel hydroxide electrode is a commercially available nickel hydroxide electrode commercially available.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA.
  • the cathode is connected to the platinum electrode, the anode is connected to the nickel hydroxide electrode, and the electrolysis time is 200 mA.
  • the electrolysis time is 600 seconds, the average voltage is about 1.6 V, and hydrogen gas is generated on the platinum electrode.
  • the cathode is connected to nickel hydroxide, the anode is connected to the CoO and the carbon composite electrode, and the current is electrolyzed at a current of 200 mA until the voltage is raised to 1 V for 600 seconds.
  • the average voltage is about 0.55 V, and oxygen is generated on the mixed electrode of CoO and carbon. No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolyzer uses a single layer of MoS 2 and graphene composite electrodes, the catalytic electrode for electrolysis of oxygen is ruthenium oxide, and the nickel hydroxide electrode is commercially available as a commercially available nickel hydroxide electrode.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA.
  • the cathode is connected to the MoS 2 /graphene composite electrode
  • the anode is connected to the nickel hydroxide electrode
  • the electrolysis time is 600 mA.
  • the electrolysis time is 600 seconds, and the average voltage is about 1.65 V.
  • Hydrogen is generated on the MoS 2 /graphene composite electrode. Then, the cathode was connected to a nickel hydroxide electrode, and the anode was connected to a ruthenium oxide electrode, and the same was electrolyzed at a current of 200 mA until the voltage was raised to 1 V for 600 seconds. The average voltage was about 0.5 V, and oxygen was generated on the ruthenium oxide. No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolyzer uses a platinum electrode, the catalytic electrode for electrolysis to generate oxygen is ruthenium oxide, and the nickel hydroxide electrode is a composite electrode synthesized by in situ growth of nickel hydroxide and carbon nanotubes.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA. First, the cathode is connected to the platinum electrode, the anode is connected to the nickel hydroxide electrode, and the electrolysis is performed at 200 mA constant current for 600 seconds.
  • the average voltage is about 1.62 V, and hydrogen gas is generated on the platinum electrode.
  • the cathode was connected to a nickel hydroxide electrode, and the anode was connected to a ruthenium oxide electrode, and the same was electrolyzed at a current of 200 mA until the voltage was raised to 1 V for 600 seconds.
  • the average voltage was about 0.53 V, and oxygen was generated on the ruthenium oxide electrode. No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolytic cell uses a C 3 N 4 and graphene composite electrode, the catalytic electrode for electrolysis to generate oxygen is ruthenium oxide, and the nickel hydroxide electrode is commercially available for purchase of a commercial nickel hydroxide electrode.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA.
  • the cathode is connected to the C 3 N 4 /graphene composite electrode, the anode is connected to the nickel hydroxide electrode, and the electrolysis time is 200 mA, the electrolysis time is 600 seconds, the average voltage is about 1.67 V, and the C 3 N 4 /graphene composite electrode Hydrogen is generated on it.
  • the cathode was connected to a nickel hydroxide electrode, and the anode was connected to a ruthenium oxide electrode, and the same was electrolyzed at a current of 200 mA until the voltage was raised to 1 V for 600 seconds.
  • the average voltage was about 0.5 V, and oxygen was generated on the ruthenium oxide. No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolyzer uses a single-layer MoS 2 /graphene composite electrode, the catalytic electrode for electrolysis of oxygen is a CoO/carbon composite electrode, and the nickel hydroxide electrode is commercially available for commercial nickel hydroxide electrode. .
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA. First, the cathode is connected to the MoS 2 /graphene composite electrode, the anode is connected to the nickel hydroxide electrode, and the 200 mA constant current electrolysis is performed.
  • the electrolysis time is 600 seconds, the average voltage is about 1.65 V, and hydrogen gas is generated on the MoS 2 /graphene composite electrode.
  • the cathode is connected to the nickel hydroxide electrode, the anode is connected to the CoO/carbon composite electrode, and the current is electrolyzed at a current of 200 mA until the voltage is raised to 1 V for about 600 seconds.
  • the average voltage is about 0.55 V, and oxygen is generated on the CoO/carbon composite electrode. No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolytic cell uses a platinum electrode, the catalytic electrode for electrolyzing oxygen is a mixed electrode of MnO x and carbon, and the nickel hydroxide electrode is a commercially available nickel hydroxide electrode commercially available.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA. First, the cathode is connected to the platinum electrode, the anode is connected to the nickel hydroxide electrode, and the electrolysis time is 200 mA. The electrolysis time is 600 seconds, and the average voltage voltage is about 1.6 V. Hydrogen is generated on the platinum electrode.
  • the cathode is connected with nickel hydroxide, the anode is connected with MnO x and the carbon composite electrode, and the same current is electrolyzed at 200 mA until the voltage is raised to 1 V for 600 seconds, the average voltage is about 0.58 V, and oxygen is generated on the mixed electrode of MnO x and carbon. . No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.
  • the catalytic electrode for electrolysis of hydrogen in the three-electrode electrolyzer uses a platinum electrode, the catalytic electrode for electrolyzing oxygen is a nitrogen-doped mesoporous carbon electrode, and the nickel hydroxide electrode is a commercially available nickel hydroxide electrode commercially available.
  • the three electrodes have an area of 20 square centimeters.
  • the electrolytic solution was electrolyzed using a 1 mol per liter potassium hydroxide solution using a constant current of 200 mA. First, the cathode is connected to the platinum electrode, the anode is connected to the nickel hydroxide electrode, and the electrolysis time is 200 mA. The electrolysis time is 600 seconds, and the average voltage voltage is about 1.6 V. Hydrogen is generated on the platinum electrode.
  • the cathode is connected with nickel hydroxide, the anode is connected with MnO x and the carbon composite electrode, and the same current is electrolyzed at 200 mA until the voltage is raised to 1 V for 600 seconds, and the average voltage is about 0.58 V, which is formed on the nitrogen-doped mesoporous carbon electrode. oxygen. No gas is formed on the nickel hydroxide throughout the process. By this cycle 20 times, the cycle is stable and the gas is stably generated. Purity identification confirmed that no mixing of hydrogen and oxygen occurred.

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Abstract

一种基于三电极体系的两步法电解水制氢的方法及装置。该装置电解槽包含析氢催化电极、析氧催化电极和氢氧化镍电极。该方法为先水分子在析氢催化电极表面被电化学还原成氢气，同时Ni(OH) 2电极被电化学氧化为NiOOH电极，此过程中电子由Ni(OH) 2电极通过外电路流向析氢催化电极；再NiOOH电极被电化学还原成为Ni(OH) 2电极，同时氢氧根离子在析氧催化电极表面被电化学氧化成为氧气，此过程中电子由析氧催化电极通过外电路流向NiOOH电极。该装置及方法有效地将常规电解水中同时发生的产氢和产氧步骤分割，由于产氢和产氧步骤的完全分离，这一电解装置可在不采用任何隔膜的条件下，制备出高纯的氢气，进一步降低了电解水制氢的成本。

Description

[根据细则37.2由ISA制定的发明名称]　基于三电极体系的两步法电解水制氢的方法及装置 技术领域
本发明属于电解水技术领域，具体涉及一种新型的基于三电极体系的两步法电解水制氢的方法及装置。
背景技术
能源是发展国民经济、提高人民生活质量的重要物质基础，是直接影响经济发展的重要制约因素，同时也是国家战略安全保障的基础之一。新世纪的到来，人类社会对能源数量、质量的需要会越来越多、越来越高，但是由于无止境的开采、挖掘，使人类赖以生存的能源资源正在日益减少，而作为主要能源的石油、煤的贮量也正日益枯竭。同时，传统的能源结构和大量能源消耗，对人类生存环境造成了严重污染，人类呼唤着替代传统能源的清洁能源。为解决经济发展与能源短缺及环境污染之间日益加剧的矛盾，开发清洁、高效、可持续发展的新能源动力技术已成为十分紧迫的任务。发展可再生能源和能源的清洁高效利用将是当今国际社会所面临的重要现实问题，对整个世界经济的可持续发展具有重要意义。氢能源作为高效、洁净和理想的二次能源已经受到了全世界的广泛重视。大规模、廉价地生产氢气是开发和利用氢能的重要环节之一。
电解水制备氢气操作相对简单，技术相对成熟，而且制氢过程没有污染，是实现大规模生产氢气的重要手段。在当前的制氢工业生产中，碱性水电解技术工业化早、技术成熟、设备成本低，因此碱性水电解在水电解行业中占主导地位。但因为其能耗较高，限制了它的广泛应用。更为重要的是，常规的电解水技术在电极过程中阴阳极同时电极生成氢气和氧气，这将很容易导致氢气和氧气的混合，致使所制备的气体不纯，后续的提纯则将大大增大制备成本。采用离子选择性膜隔开在析氢催化电极产生的氢气和析氧催化电极产生的氧气是一种有效的解决方案，但是离子选择性膜的使用也大大增加了成本。此外，由于电化学析氢和析氧自身的动力学过程不同，造成产氢和产氧速度有所差异，当离子选择性膜两边压力不同时，膜的损耗也非常严重，这进一步增大了成本。此外，选择性离子交换膜近一步增大了电解槽内阻，增加了能耗。目前主流的工作在于改进或者制备新型的隔膜，以期降低内阻的同时，又兼顾亲水性，离子透过性以及能够完全隔开氢气和氧气。虽然已经有很多新型隔膜被研究探索，但是效果仍然并不是十分显著。
发明内容
本发明的目的在于提供一种无需隔膜的基于三电极体系的两步法电解水制氢的方法及装置。
本发明所提供的基于三电极体系的两步法电解水制氢的装置，该装置中的电解槽包含三个电极：对电解水生成氢气具有催化作用的析氢催化电极、对电解水生成氧气具有催化作用的析氧催化电极和氢氧化镍(Ni(OH)2)电极。
在产氢气步骤，阴极连接析氢催化电极，阳极连接氢氧化镍电极；在产氧气步骤，阴极连接氢氧化镍电极，阳极连接析氧催化电极。
本发明所提供的基于三电极体系的两步法电解水制氢的方法，具体步骤如下:
(一)产氢气步骤(即电解水生成氢气步骤)：
水分子在作为阴极的析氢催化电极表面被电化学还原成氢气，即H2O+e-→1/2H2+OH-；同时作为阳极的Ni(OH)2电极被电化学氧化为NiOOH电极，即Ni(OH)2+OH--e-→NiOOH+H2O，在此过程中电子由Ni(OH)2电极通过外电路流向析氢催化电极；
(二)产氧气步骤(即电解水生成氧气步骤)：
作为阴极的NiOOH电极被电化学还原成为Ni(OH)2电极，即NiOOH+H2O+e-→Ni(OH)2+OH-；同时氢氧根离子在作为阳极的析氧催化电极表面被电化学氧化成为氧气，即2OH--2e-→1/2O2+H2O；在此过程中电子由析氧催化电极通过外电路流向NiOOH电极。
所述步骤(一)和步骤(二)交替循环进行。
两个步骤交替循环进行，实现了Ni(OH)2的循环利用，同时有效实现了在不同时段电解制氢气和电解制备氧气，并最终有效防止了氢氧混合，实现了高纯度制氢的目的。
本发明中，所述析氢催化电极对电解水生成氢气具有催化作用，该具有催化作用的电极材料为：
基于金属铂(Pt)等贵金属以及其与碳的复合物；或
基于Ni、Co、Fe等过渡金属的单质或化合物，如Ni、Ni-Mo合金、Ni-Cr-Fe合金、CoO、Co2O3、CoSe2、FeP；或
基于Cu的化合物；或
基于W的化合物，如WC、W2C、WS2；或
基于Mo的化合物，如MoS2、MoB、Mo2S；或
C3N4等化合物。
本发明中，所述析氧催化电极对电解水生成氧气具有催化作用，该具有催化作用的电极材料为：
基于Ru、Ir等贵金属的化合物，如IrOx、RuO2；或
基于Ni、Co、Fe、Mn等过渡金属的单质或化合物，如NiFeOx、NiCoOx、CoFeOx、CoOx、NiCuOx、NiOx、SrNb0.1Co0.7Fe0.2O3-x、MnOx、CoMn2O4；或
N、S、P等掺杂的碳；或
生物电化学催化剂，如漆酶等化合物。
本发明中，所述氢氧化镍电极为常规镍氢电池使用的氢氧化镍电极，其由活性物质Ni(OH)2和其他添加成分组成，添加成分为镍粉、Co(OH)2、碳粉及粘结剂中的一种或者几种。
所述粘结剂为聚四氟乙烯。
所述Ni(OH)2活性物质和添加成分通过混合成膜或者成浆料的方式，压制或者涂覆在金属集流体上构成Ni(OH)2电极。
所述金属集流体包括：镍网、泡沫镍、不锈钢网、钛网等。
本发明电解水的技术的电解液必须是碱性水溶液，碱性水溶液为氢氧化钾或氢氧化钠等。
本发明设计的电解装置最显著的特点是不需要隔膜用以隔开电解产生的氢气和氧气。经测试制取的氢气与氧气的纯度，结果表明，虽然没有隔膜，但是氢气与氧气并没有发生混合。
本发明采用两步恒电流电解方法，电解曲线如图2所示，其展示出了优异的电解水性能：重复了20次两步法电解制氢和制氧，当200毫安恒流电解时，制氢的平均电压约为1.6V，制氧的平均电压约为0.5V。进一步地，本领域技术人员可以根据电极材料、电解电流的选择，而合理选择适当的电压范围，例如，制氢的平均电压范围可以为1.0-3.0V，制氧电压范围可以为0.2-1.5V。本发明仅作示例性说明，不作为对本发明保护范围的限定。
进一步地，本发明所述的电解装置可以采用不同的驱动电压以产生氢气和氧气，尤其是可采用太阳能、风能等可持续能源，以更高效地制氢。例如，可以根据太阳光强度的变化，有选择地进行产氢或产氧步骤，提升可在生能源的利用率；也可以选择在夜间通过多余的电能制备氢气，白天通过太阳能风能来产氧等。综上所述，本发明提出的基于三电极体系下的两步法电解水制氢方法，其工作特点在于分先后两步分别电解水制氢气和电解水制氧气。氢氧化镍(Ni(OH)2)电极在电解水制备氢气的过程中，被电化学氧化成为NiOOH电极；在后续的电解水制氧的过程中，又被电化学还原成为Ni(OH)2。该氢氧化镍(Ni(OH)2)电极作为质子和电子缓冲器，将产氢和产氧两个步骤拆分开来。
本发明的基于三电极体系的两步法电解水制氢的装置，包括制氢电极对和制氧电极 对，所述制氢电极对包括所述析氢催化电极和氢氧化镍电极，所述制氧电极对包括所述析氧催化电极和氢氧化镍电极。
所述制氢电极对中，氢氧化镍电极被氧化为NiOOH电极。所述制氧电极对中，NiOOH电极被电化学还原成为Ni(OH)2电极。
所述制氢电极对和制氧电极对设置成同时或不同时工作，较佳地为不同时工作。
换言之，该氢氧化镍电极的循环电化学氧化还原过程，将传统的电解水过程分为了连续的或单独的两步，因此实现了在不同时段分别制备氢气和氧气，从而能制备出高纯度的氢气。此外，这种分段制备的方法也使得该装置无需使用离子选择性膜来分隔氢气和氧气，因此大大降低了制备成本。
附图说明
图1显示了三电极体系两步法电解水电解槽工作示意图。
图2显示了三电极体系两步法电解水制氢/制氧循环示意图。
具体实施方式
除非另外定义，否则本文中所用的全部技术与科学术语均具有如本发明所属领域的普通技术人员通常理解的相同含义。
如本文所用，在提到具体列举的数值中使用时，术语“约”意指该值可以从列举的值变动不多于1％。例如，如本文所用，表述“约100”包括99和101和之间的全部值(例如，99.1、99.2、99.3、99.4等)。
如本文所用，术语“含有”或“包括(包含)”可以是开放式、半封闭式和封闭式的。换言之，所述术语也包括“基本上由…构成”、或“由…构成”。
如本文所用，术语“系统”、“装置”、“体系”具有相同含义，可互换使用。
如本文所用，术语“制氢”、“制氢氧”具有相同含义，可互换使用。
本发明的主要优点在于：
1.本发明的电解水制氢装置中，分步产生氢气和氧气，无需使用隔膜来隔开电解产生的氢气和氧气。
2.本发明的电解水装置产生的氢气和氧气不会发生混杂，安全性高。
3.本发明的电解水装置在不稳定的电压输出条件下，仍然可以进行高效电解，产生氢气和氧气。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数是重量百分比和重量份数。
以下实施例中所用的实验材料和试剂如无特别说明均可从市售渠道获得。
实施例1:
三电极电解槽电解生成氢气的催化电极采用铂电极，电解生成氧气的催化电极采用氧化铱，氢氧化镍电极采用市场可以购买到商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔/升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接铂电极，阳极连接氢氧化镍电极，200毫安电流电解，时间为600秒，平均电压约为1.6V，铂电极上生成氢气。然后阴极连接氢氧化镍，阳极连接氧化铱电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压为0.5V，氧化铱电极上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，曲线如图1循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例2：
三电极电解槽电解生成氢气的催化电极采用铂电极，电解生成氧气的催化电极采用CoO与炭的混合电极，氢氧化镍电极采用市场可以购买的商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接铂电极，阳极连接氢氧化镍电极，200毫安恒流电解，电解时间为600秒，平均电压约为1.6V，铂电极上生成氢气。然后阴极连接氢氧化镍，阳极连接CoO与碳复合电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压约为0.55V，CoO与碳的混合电极上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例3：
三电极电解槽电解生成氢气的催化电极采用单层MoS2与石墨烯复合物电极，电解生成氧气的催化电极采用氧化铱，氢氧化镍电极采用市场可以购买的商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接MoS2/石墨烯复合电极，阳极连接氢氧化镍电极， 200毫安恒流电解，电解时间为600秒，平均电压约为1.65V，MoS2/石墨烯复合电极上生成氢气。然后阴极连接氢氧化镍电极，阳极连接氧化铱电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压约为0.5V，氧化铱上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例4:
三电极电解槽电解生成氢气的催化电极采用铂电极，电解生成氧气的催化电极采用氧化铱，氢氧化镍电极采用氢氧化镍与碳纳米管原位生长合成的复合电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接铂电极，阳极连接氢氧化镍电极，200毫安恒流电解，时间为600秒，平均电压约为1.62V，铂电极上生成氢气。然后阴极连接氢氧化镍电极，阳极连接氧化铱电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压约为0.53V，氧化铱电极上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例5:
三电极电解槽电解生成氢气的催化电极采用C3N4与石墨烯复合物电极，电解生成氧气的催化电极采用氧化铱，氢氧化镍电极采用市场可以购买商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接C3N4/石墨烯复合物电极，阳极连接氢氧化镍电极，200毫安恒流电解,电解时间为600秒，平均电压约为1.67V，C3N4/石墨烯复合物电极上生成氢气。然后阴极连接氢氧化镍电极，阳极连接氧化铱电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压约为0.5V，氧化铱上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例6:
三电极电解槽电解生成氢气的催化电极采用单层MoS2/石墨烯复合物电极，电解生成氧气的催化电极采用CoO/碳的复合电极，氢氧化镍电极采用市场可以购买商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接MoS2/石墨烯复合电极，阳极连接氢氧 化镍电极，200毫安恒流电解，电解时间为600秒，平均电压约为1.65V，MoS2/石墨烯复合电极上生成氢气。然后阴极连接氢氧化镍电极，阳极连接CoO/碳复合电极，同样200毫安电流电解直至电压升至1V，时间约为600秒，平均电压约为0.55V，CoO/碳复合电极上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例7：
三电极电解槽电解生成氢气的催化电极采用铂电极，电解生成氧气的催化电极采用MnOx与炭的混合电极，氢氧化镍电极采用市场可以购买的商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接铂电极，阳极连接氢氧化镍电极，200毫安恒流电解，电解时间为600秒，平均电压电压约为1.6V，铂电极上生成氢气。然后阴极连接氢氧化镍，阳极连接MnOx与碳复合电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压约为0.58V，MnOx与炭的混合电极上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
实施例8：
三电极电解槽电解生成氢气的催化电极采用铂电极，电解生成氧气的催化电极采用氮掺杂的介孔炭电极，氢氧化镍电极采用市场可以购买的商业化氢氧化镍电极。三个电极面积均为20平方厘米。电解液使用1摩尔每升的氢氧化钾溶液，采用200毫安恒定电流进行电解。首先阴极连接铂电极，阳极连接氢氧化镍电极，200毫安恒流电解，电解时间为600秒，平均电压电压约为1.6V，铂电极上生成氢气。然后阴极连接氢氧化镍，阳极连接MnOx与碳复合电极，同样200毫安电流电解直至电压升至1V，时间为600秒，平均电压约为0.58V，氮掺杂的介孔炭电极上生成氧气。整个过程氢氧化镍上没有任何气体生成。以此循环20次，循环稳定，气体稳定生成。进行纯度鉴定证明氢氧没有发生混合。
表1.采用不同电极组装的电解槽200毫安恒电流电解水性能比较。
Figure PCTCN2016106143-appb-000001
Figure PCTCN2016106143-appb-000002
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (15)

  1. 一种基于三电极体系的两步法电解水制氢的装置，其特征在于，该装置中的电解槽包含三个电极：对电解水生成氢气具有催化作用的析氢催化电极、对电解水生成氧气具有催化作用的析氧催化电极和氢氧化镍(Ni(OH)2)电极。
  2. 如权利要求1所述的装置，其特征在于，所述析氢催化电极对电解水生成氢气具有催化作用，该具有催化作用的电极材料为：
    基于金属铂以及其与碳的复合物；或
    基于Ni、Co或Fe过渡金属的单质或化合物；或
    基于Cu的化合物；或
    基于W的化合物；或
    基于Mo的化合物；或
    C3N4化合物。
  3. 如权利要求1所述的装置，其特征在于，所述析氧催化电极对电解水生成氧气具有催化作用，该具有催化作用的电极材料为：
    基于Ru或Ir贵金属的化合物；或
    基于Ni、Co、Fe或Mn过渡金属的单质或化合物；或
    N、S、P掺杂的碳；或
    生物电化学催化剂。
  4. 如权利要求2所述的装置，其特征在于：
    所述基于Ni、Co或Fe过渡金属的单质或化合物为Ni、Ni-Mo合金、Ni-Cr-Fe合金、CoO、Co2O3、CoSe2或FeP；
    所述基于W的化合物为WC、W2C或WS2；或
    所述基于Mo的化合物为MoS2、MoB或Mo2S。
  5. 如权利要求3所述的装置，其特征在于：
    所述基于Ru或Ir贵金属的化合物为IrOx或RuO2；
    所述基于Ni、Co、Fe、Mn过渡金属的单质或化合物为NiFeOx、NiCoOx、CoFeOx、CoOx、NiCuOx、NiOx、SrNb0.1Co0.7Fe0.2O3-x、MnOx或CoMn2O4；
    所述生物电化学催化剂为漆酶等化合物。
  6. 如权利要求1所述的装置，其特征在于，所述氢氧化镍电极为由Ni(OH)2活性物质和其他添加成分组成，所述添加成分为镍粉、Co(OH)2、碳粉及粘结剂中的一种或者几种。
  7. 如权利要求6所述的装置，其特征在于，所述粘结剂为聚四氟乙烯。
  8. 如权利要求6所述的装置，其特征在于，所述Ni(OH)2活性物质和添加成分通过混合成膜或者成浆料的方式，压制或者涂覆在金属集流体上构成Ni(OH)2电极；所述金属集流体包括：镍网、泡沫镍、不锈钢网或钛网。
  9. 如权利要求2所述的装置，其特征在于，所述电解水的技术的电解液是碱性水溶液，碱性水溶液为氢氧化钾或氢氧化钠。
  10. 如权利要求1所述的装置，其特征在于，所述装置中不包括隔膜装置。
  11. 一种基于三电极体系的两步法电解水制氢的装置，其特征在于，所述装置包括制氢电极对和制氧电极对，所述制氢电极对包括所述析氢催化电极和氢氧化镍电极，所述制氧电极对包括所述析氧催化电极和氢氧化镍电极。
  12. 如权利要求11所述的装置，其特征在于，所述制氢电极对和制氧电极对设置成不同时工作。
  13. 如权利要求11所述的装置，其特征在于，所述制氢电极对的工作电压范围为1.0-3.0V。
  14. 如权利要求11所述的装置，其特征在于，所述制氧电极对的工作电压范围为0.2-1.5V。
  15. 如权利要求11所述的装置，其特征在于，所述装置中不包含隔膜装置。16.基于权利要求1～10任一所述装置的两步法电解水制氢的方法，其特征在于具体步骤如下:
    (一)产氢气步骤：
    水分子在作为阴极的析氢催化电极表面被电化学还原成氢气，即H2O+e-→1/2H2+OH-；同时作为阳极的Ni(OH)2电极被电化学氧化为NiOOH电极，即Ni(OH)2+OH--e-→NiOOH+H2O，在此过程中电子由Ni(OH)2电极通过外电路流向析氢催化电极；
    (二)产氧气步骤：
    作为阴极的NiOOH电极被电化学还原成为Ni(OH)2电极，即NiOOH+H2O+e-→Ni(OH)2+OH-；同时氢氧根离子在作为阳极的析氧催化电极表面被电化学氧化成为氧气，即2OH--2e-→1/2O2+H2O；在此过程中电子由析氧催化电极通过外电路流向NiOOH电极；
    所述步骤(一)和步骤(二)交替循环进行。
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