WO2018001051A1 - 一种储能器件集成式光电化学水分解电池的设计方法 - Google Patents

一种储能器件集成式光电化学水分解电池的设计方法 Download PDF

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WO2018001051A1
WO2018001051A1 PCT/CN2017/087373 CN2017087373W WO2018001051A1 WO 2018001051 A1 WO2018001051 A1 WO 2018001051A1 CN 2017087373 W CN2017087373 W CN 2017087373W WO 2018001051 A1 WO2018001051 A1 WO 2018001051A1
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energy storage
storage device
type semiconductor
battery
designing
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刘岗
甄超
陈润泽
成会明
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中国科学院金属研究所
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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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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  • the invention relates to the field of photoelectrochemical cells, in particular to a design method of an integrated energy storage electrochemical cell water decomposition battery.
  • Photoelectrochemical water-decomposition batteries use solar energy to decompose water to release hydrogen, and the solar energy is fixedly converted in the form of hydrogen bonds, which is one of the effective ways for solar energy conversion and storage.
  • Photoelectrochemical water decomposition full battery includes n-type semiconductor photoanode and p-type semiconductor photocathode. Constructing high-efficiency photoelectrochemical water-decomposing all-cell is the key to realize spontaneous decomposition of water under solar illumination.
  • the basic principle of photoelectrochemical water decomposition of a full cell is similar to the Z-type charge transfer mechanism. High-energy photogenerated electrons and holes migrate to the photocathode and photoanode surface, respectively, to induce water decomposition, while low-energy photogenerated electrons and holes directly Composite in the outer circuit. The entire process generates a pair of effective photogenerated electrons and holes for absorbing two photons, so the utilization efficiency of solar energy is significantly impaired.
  • the object of the present invention is to provide a design method of an integrated energy storage device for a photoelectrochemical device, and a significant improvement in solar energy utilization efficiency can be achieved by designing an integrated device.
  • An energy storage device integrated photoelectrochemical water-decomposing battery design method wherein an n-type semiconductor photoanode is connected to an anode of an energy storage device, a p-type semiconductor photocathode is connected to a positive electrode of the energy storage device, and a proton exchange membrane is used to isolate the electrode in different electrolytes.
  • the integrated photoelectrochemical water-splitting battery constituting the energy storage device.
  • the n-type semiconductor photoanode is preferably a composite material of one or more of TiO 2 , WO 3 , BiVO 4 , Fe 2 O 3 , Ta 3 N 5 , and TaON.
  • the p-type semiconductor photocathode is preferably a composite material of one or more of Cu 2 O, GaP, WSe 2 , and InP.
  • the energy storage device is a variety of electrochemical energy storage devices.
  • the energy storage device is preferably a capacitor, a redox couple to a liquid flow battery or a lithium sulfur battery.
  • the electrolyte solution is an aqueous electrolyte or an organic electrolyte, and the pH of the electrolyte is 0 to 14; wherein the n-type semiconductor photoanode is preferably immersed in an electrolyte having a pH of 7 to 14, and the p-type semiconductor photocathode is preferably immersed. In an electrolyte having a pH of 0 to 7.
  • the n-type semiconductor photoanode is modified by a cocatalyst for producing oxygen by Co(OH) 2 , Co 3 O 4 , Co-Pi or NiO x , and the modification process is as follows: using solution ion reaction method, atomic layer deposition method, and excitation
  • the electrodeposition film method, the electrodeposition method, the sol spin coating method or the thermal spray method is carried on the surface of the n-type semiconductor photoanode to deposit nanoparticles or films of the above oxygen generating promoter.
  • the p-type semiconductor photocathode is modified by a promoter of hydrogen production of Pt, RuO 2 or MoS 2 , and the modification process is as follows: using solution ion reaction method, atomic layer deposition method, lasing coating method, electrodeposition method, sol rotation A coating or thermal spraying method is carried on the surface of the p-type semiconductor photoanode to deposit nanoparticles or films on which the hydrogen-promoting promoter is deposited.
  • the present invention proposes the concept of integrated photoelectrochemical hydrolyzed full cell of energy storage device. While high-energy photogenerated electrons and holes induce water reduction and oxidation, respectively, low-energy photogenerated holes and electrons are not simply combined directly, but are stored in the positive and negative electrodes of the energy storage device, respectively, in the form of electrical energy. Under illumination, the photoanode oxidation water releases oxygen while charging the negative electrode of the energy storage device, while the photocathode reduces hydrogen production while charging the positive electrode of the energy storage device. After the light is connected to the positive and negative electrodes of the energy storage device by wires, current is generated and constructed into a classical electrochemical energy storage system.
  • the invention realizes simultaneous storage of solar energy to chemical energy (hydrogen) and electric energy by integrating the electrochemical energy storage device in the photoelectrochemical water decomposition battery system.
  • the absorption of two photons produces two pairs of photogenerated electrons and holes, one pair is used for the decomposition of water, and the pair is stored in the form of electric energy, which effectively improves the efficiency of solar energy conversion.
  • FIG. 1 Photocurrent response of photoelectrochemical half-cells with Ta 3 N 5 photoanode and capacitor graphite cathodes in dark state and alternating illumination; X-axis is time (seconds/s) and Y-axis is photocurrent density (mA ⁇ Cm -2 ).
  • FIG. 1 Photocurrent response of photoelectrochemical half-cells with Cu 2 O photocathode and capacitor graphite cathodes in dark state and alternating illumination; X-axis is time (seconds/s) and Y-axis is photocurrent density (mA ⁇ cm) -2 ).
  • Figure 4 Cu 2 O photocathode and capacitor graphite cathode.
  • FIG. 7 Volt-ampere curve of photoelectrochemical half-cell illumination with Ta 3 N 5 photoanode and Br - /BrO 3 - redox couple (positive liquid flow cell); X-axis is applied voltage (volts / V), The Y axis is the photocurrent density (mA ⁇ cm -2 ).
  • Figure 8 Short-circuit photocurrent density-time curve of a photoelectrochemical half-cell under the illumination of a Ta 3 N 5 photoanode and a Br - /BrO 3 - redox couple (liquid flow cell positive); the X-axis is time (seconds) /s), the Y-axis is the photocurrent density (mA ⁇ cm -2 ).
  • the energy storage device integrated photoelectrochemical water-decomposing battery of the present invention connects an anode of the energy storage device with an n-type semiconductor photoanode, and connects the anode of the energy storage device with a p-type semiconductor photocathode, and isolates the electrode by using a proton exchange membrane.
  • an integrated photoelectrochemical water-splitting battery for the energy storage device is constructed. Under illumination, the photoanode oxidation water releases oxygen while charging the negative electrode of the energy storage device, while the photocathode reduces hydrogen production while charging the positive electrode of the energy storage device. details as follows:
  • n-type semiconductor photoanode comprising various n-type semiconductors (eg, TiO 2 , WO 3 , BiVO 4 , Fe 2 O 3 , Ta 3 N 5 , TaON, etc.) and composite materials thereof.
  • various n-type semiconductors eg, TiO 2 , WO 3 , BiVO 4 , Fe 2 O 3 , Ta 3 N 5 , TaON, etc.
  • the p-type semiconductor photocathode comprises various p-type semiconductors (eg, Cu 2 O, GaP, WSe 2 , InP, etc.) and composite materials thereof.
  • the energy storage device includes various electrochemical energy storage devices (such as capacitors, redox-to-liquid flow batteries, lithium-sulfur batteries, etc.).
  • the electrolyte solution includes an aqueous system and an organic electrolyte solution, and has a pH of 0 to 14.
  • the Ta 3 N 5 nanorods are modified with Co(OH) 2 (the modification process of the present embodiment means that Co(OH) 2 is supported on the Ta 3 N 5 nanorods by a continuous ion layer adsorption reaction method.
  • the surface of the array is characterized in that the Ta 3 N 5 nanorod array film is alternately impregnated in a solution containing Co ions and OH - ions, and the surface-adsorbed ions are reacted to form Co(OH) 2 to form an oxygen generating cocatalyst Co ( OH) 2 will be evenly distributed on the surface of the Ta 3 N 5 nanorod array, which is beneficial to increase its photocatalytic oxygen production activity.
  • the array photoanode link capacitor graphite anode is used, and the two electrodes are separated in the two electrolytes by proton exchange membrane.
  • the Ta 3 N 5 photoanode was immersed in an aqueous solution of NaOH (molar concentration 1 M), and the cathode of the capacitor graphite was immersed in an aqueous solution of NaSO 4 (0.2 M), and the two electrodes were connected by an external circuit to construct a two-electrode mode.
  • the photogenerated holes generated in the Ta 3 N 5 photoanode diffuse to the surface to oxidize water to release oxygen.
  • the photogenerated electrons are transferred through an external circuit and stored in the cathode of the capacitor graphite.
  • the negative potential of the cathode of the capacitor graphite is negatively transferred to achieve the charging process.
  • the surface modification refers to: in-situ growth of a ZnO array film on the surface of a Cu 2 O film by a solvothermal method, which is characterized by an n-type ZnO film and a p-type Cu 2 O film.
  • the pn junction is beneficial to the separation of photogenerated carriers, thereby increasing its photoelectrocatalytic activity.
  • the Cu 2 O photocathode link capacitor graphite cathode is separated by two proton exchange membranes in the two electrolytes.
  • the Cu 2 O photocathode was immersed in an aqueous solution of NaSO 4 (0.2 M), and the cathode of the capacitor graphite was also immersed in an aqueous solution of NaSO 4 (0.2 M), and the two electrodes were connected by an external circuit to construct a two-electrode mode.
  • the photogenerated electrons generated in the Cu 2 O photocathode diffuse to the surface to reduce the water and release hydrogen.
  • the photogenerated holes are transferred by the external circuit and stored in the cathode of the capacitor graphite.
  • the positive electrode potential of the capacitor graphite is positively shifted to realize the charging process.
  • the Co(OH) 2 modification (the modification process of the present embodiment is the same as the embodiment 1)
  • Ta 3 N 5 nanorod array photoanode is immersed in an aqueous solution of NaOH (1M), and the graphite felt is immersed in potassium ferricyanide.
  • the redox electricity is used as the negative electrode of the liquid flow battery, and the two electrodes are separated by the proton exchange membrane.
  • the Ta 3 N 5 photoanode and the graphite felt are linked by an external circuit to form a two-electrode mode.
  • the photogenerated holes generated in the Ta 3 N 5 photoanode diffuse to the surface to oxidize water to release oxygen, and the photogenerated electrons are transferred to the graphite felt through an external circuit to oxidize the potassium ferricyanide redox couple to achieve a redox couple. Charging of the negative electrode of the liquid flow battery.
  • the photogenerated holes Ta 3 N 5 photoanode generated diffuses into the surface of Br - is oxidized to BrO 3, photoinduced electron transfer through an external circuit to the Pt mesh electrodes - reduction of water releases hydrogen, to achieve the redox liquid Charging of the positive battery of the mobile battery.
  • the n-type semiconductor photoanode is used instead of the p-type semiconductor photocathode to realize the charging process of the positive electrode of the flow battery, and only the position of the electrode in the two electrolytes needs to be exchanged to achieve the same purpose. Therefore, in the flow battery integrated photoelectrochemical water decomposition battery system, there are various conversion modes.
  • the photocurrent is continuously generated under illumination to achieve continuous charging of the positive electrode of the flow battery.
  • the results of the embodiment show that the n-type semiconductor photoanode is connected to the negative electrode of the energy storage device, and the p-type semiconductor photocathode is connected to the positive electrode of the energy storage device.
  • the proton exchange membrane is used to isolate the electrode in different electrolytes to form an integrated energy storage device.
  • Chemical water decomposition battery The photo-generated hole generated by the n-type semiconductor photoanode is excited by the light to diffuse to the surface to oxidize water to release oxygen, and the photogenerated electron is transferred to the negative electrode of the energy storage device through the external circuit to charge the negative electrode; the photo-generated photon of the p-type semiconductor photocathode is excited by the light.
  • the electrons reduce the water to release hydrogen, and the photogenerated holes are transferred to the positive electrode of the energy storage device through an external circuit to achieve positive charge.

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Abstract

一种储能器件集成式光电化学水分解电池的设计方法。以n型半导体光阳极连接储能器件负极，p型半导体光阴极连接储能器件正极，利用质子交换膜将电极隔离在不同电解液中，构成储能器件集成式光电化学水分解电池。n型半导体光阳极受光激发产生的光生空穴扩散至表面将水氧化释放出氧气，而光生电子则通过外电路转移至储能器件负极实现对负极充电；p型半导体光阴极受光激发产生的光生电子将水还原释放氢气，而光生空穴通过外电路转移至储能器件正极实现正极充电。所述方法将传统光电化学电池中在外电路直接复合的光生电荷以电能形式储存在储能器件中，有效提高了太阳能的转化利用效率。

Description

一种储能器件集成式光电化学水分解电池的设计方法 技术领域
本发明涉及光电化学电池领域，具体为一种储能器件集成式光电化学水分解电池的设计方法。
背景技术
光电化学水分解电池利用太阳能将水分解释放氢气，将太阳能以氢键的形式固定转化，是太阳能转化和存储的有效途径之一。光电化学水分解全电池包括n型半导体光阳极和p型半导体光阴极，构筑高效的光电化学水分解全电池是实现水在太阳光照下自发全分解的关键。
光电化学水分解全电池的基本原理类似于Z型电荷转移机制，高能量的光生电子和空穴分别迁移至光阴极和光阳极表面，诱导水的分解反应，而低能量的光生电子和空穴直接在外电路复合。整个过程为吸收两个光子产生一对有效光生电子和空穴，因此太阳能的利用效率显著折损。
发明内容
本发明的目的在于提出一种储能器件集成式光电化学水分解电池的设计方法，通过集成式器件的设计，可实现太阳能利用效率的显著提升。
本发明的技术方案是：
一种储能器件集成式光电化学水分解电池的设计方法，以n型半导体光阳极连接储能器件负极，p型半导体光阴极连接储能器件正极，利用质子交换膜将电极隔离在不同电解液中，构成储能器件集成式光电化学水分解电池。
所述的n型半导体光阳极，优选TiO2、WO3、BiVO4、Fe2O3、Ta3N5、TaON之一或两种以上的复合材料。
所述的p型半导体光阴极，优选Cu2O、GaP、WSe2、InP之一或两种以上的复合材料。
所述的储能器件为各种电化学储能器件。
所述的储能器件，优选电容器、氧化还原电对液体流动电池或锂硫电池。
所述的电解液为水系电解液或有机系电解液，电解液的pH值0～14；其中，n型半导体光阳极优选浸入pH值7～14的电解液中，p型半导体光阴极优选浸入pH值0～7的电解液中。
所述的n型半导体光阳极，以Co(OH)2、Co3O4、Co-Pi或NiOx产氧的助催化剂修饰，修饰过程如下：利用溶液离子反应法、原子层沉积法、激射镀膜法、电沉积法、溶胶旋涂法或 热喷涂法，在n型半导体光阳极表面担载沉积上述产氧助催化剂的纳米颗粒或薄膜。
所述的p型半导体光阴极，以Pt、RuO2或MoS2产氢的助催化剂修饰，修饰过程如下：利用溶液离子反应法、原子层沉积法、激射镀膜法、电沉积法、溶胶旋涂法或热喷涂法，在p型半导体光阳极表面担载沉积上述产氢助催化剂的纳米颗粒或薄膜。
本发明的设计思想是：
为了进一步提高太阳能的转化利用效率，本发明提出储能器件集成式光电化学水分解全电池的概念。在高能光生电子和空穴分别诱导水的还原和氧化的同时，低能量的光生空穴和电子不是简单直接复合，而是以电能形式分别存储在储能器件的正极和负极中。光照下，光阳极氧化水释放氧气的同时将储能器件负极充电，而光阴极还原水产氢的同时将储能器件正极充电。光照后利用导线连接储能器件的正极和负极则会产生电流，构建成经典电化学储能体系。
本发明的优点及有益效果是：
本发明通过将电化学储能器件集成在光电化学水分解电池体系中，可实现太阳能至化学能(氢气)和电能的同时存储。吸收两个光子产生两对光生电子与空穴，一对用于水的分解，一对以电能形式储存，有效提高太阳能转化利用效率。
附图说明
图1.Ta3N5光阳极与电容器石墨负极组建的光电化学半电池在暗态和光照交替下的光电流响应；X轴为时间(秒/s)，Y轴为光电流密度(mA·cm-2)。
图2.Ta3N5光阳极与电容器石墨负极组建的光电化学半电池中，电容器石墨负极在暗态和光照交替下的电位变化；X轴为时间(秒/s)，Y轴为电位(伏/V)。
图3.Cu2O光阴极与电容器石墨正极组建的光电化学半电池在暗态和光照交替下的光电流响应；X轴为时间(秒/s)，Y轴为光电流密度(mA·cm-2)。
图4.Cu2O光阴极与电容器石墨正极组建的光电化学半电池中，电容器石墨正极在暗态和光照交替下的电位变化；X轴为时间(秒/s)，Y轴为电位(伏/V)。
图5.Ta3N5光阳极与铁氰化钾氧化还原电对(液体流动电池负极)组建的光电化学半电池暗态下和光照下的伏安测试曲线；X轴为外加电压(伏/V)，Y轴为光电流密度(mA·cm-2)。
图6.Ta3N5光阳极与铁氰化钾氧化还原电对(液体流动电池负极)组建的光电化学半电池光照下的短接光电流密度-时间曲线；X轴为时间(秒/s)，Y轴为光电流密度(mA·cm-2)。
图7.Ta3N5光阳极与Br-/BrO3 -氧化还原电对(液体流动电池正极)组建的光电化学半电池光照下的伏安曲线；X轴为外加电压(伏/V)，Y轴为光电流密度(mA·cm-2)。
图8.Ta3N5光阳极与Br-/BrO3 -氧化还原电对(液体流动电池正极)组建的光电化学半电池光照下的短接光电流密度-时间曲线；X轴为时间(秒/s)，Y轴为光电流密度(mA·cm-2)。
具体实施方式
在具体实施过程中，本发明储能器件集成式光电化学水分解电池，以n型半导体光阳极连接储能器件负极，p型半导体光阴极连接储能器件正极，利用质子交换膜将电极隔离在不同电解液中，构成储能器件集成式光电化学水分解电池。光照下，光阳极氧化水释放氧气的同时将储能器件负极充电，而光阴极还原水产氢的同时将储能器件正极充电。具体如下：
1、所述n型半导体光阳极，包括各种n型半导体(如：TiO2、WO3、BiVO4、Fe2O3、Ta3N5、TaON等)及其复合材料。
2、所述p型半导体光阴极，包括各种p型半导体(如：Cu2O、GaP、WSe2、InP等)及其复合材料。
3、所述的储能器件，包括各种电化学储能器件(如：电容器、氧化还原电对液体流动电池、锂硫电池等)。
4、所述的电解液，包括水系和有机系电解液，pH值0～14。
下面结合实施例和附图对本发明进一步详细阐述。
实施例1
本实施例中，以Co(OH)2修饰Ta3N5纳米棒(本实施例的修饰过程是指：通过连续离子层吸附反应方法将Co(OH)2担载在Ta3N5纳米棒阵列表面，其特点是将Ta3N5纳米棒阵列薄膜在含Co离子和OH-离子的溶液中交替浸渍，利用表面吸附的离子反应生成Co(OH)2，生成的产氧助催化剂Co(OH)2会均匀分布在Ta3N5纳米棒阵列表面，有利于提高其光电催化产氧活性)阵列光阳极链接电容器石墨负极，两电极利用质子交换膜隔离在两种电解液中。Ta3N5光阳极浸在NaOH(摩尔浓度1M)水溶液中，电容器石墨负极浸在NaSO4(0.2M)水溶液中，两电极通过外电路链接构建双电极模式。光照下，Ta3N5光阳极中产生的光生空穴扩散到表面将水氧化释放氧气，光生电子通过外电路转移并储存在电容器石墨负极中，电容器石墨负极电位负移实现充电过程。
如图1所示，在暗态下，无电流流经外电路；光照下，产生光电流流经外电路至电容器石墨负极，实现对电容器的负极充电。
如图2所示，光照后，电容器石墨负极的电位负移，实现充电过程；光照停止后，电容器石墨负极电位正移实现放电过程。
实施例2
本实施例中，以表面修饰(本实施例的修饰过程是指：利用溶剂热方法在Cu2O薄膜表面原位生长ZnO阵列薄膜，其特点是n型ZnO薄膜与p型Cu2O薄膜构成pn结，有利于光生载流子的分离，进而提高其光电催化活性)的Cu2O光阴极链接电容器石墨正极，两电极利用质子交换膜隔离在两个电解液中。Cu2O光阴极浸在NaSO4(0.2M)水溶液中，电容器石墨正极也浸在NaSO4(0.2M)水溶液中，两电极通过外电路链接构建双电极模式。光照下，Cu2O光阴极中产生的光生电子扩散到表面将水还原释放氢气，光生空穴通过外电路转移并储存在电容器石墨正极中，电容器石墨正极电位正移实现充电过程。
如图3所示，在暗态下，无电流流经外电路；光照下，产生光电流流经外电路至电容器石墨正极，实现对电容器的正极充电。
如图4所示，光照后，电容器石墨正极的电位正移，实现充电过程；光照停止后，电容器石墨正极电位负移实现放电过程。
实施例3
本实施例中，将Co(OH)2修饰(本实施例的修饰过程同实施例1)Ta3N5纳米棒阵列光阳极浸在NaOH(1M)水溶液中，石墨毡浸在铁氰化钾氧化还原电对碱性水溶液作为液体流动电池的负极，两种电极利用质子交换膜隔离开。Ta3N5光阳极与石墨毡通过外电路链接构建双电极模式。光照下，Ta3N5光阳极中产生的光生空穴扩散到表面将水氧化释放氧气，光生电子通过外电路转移至石墨毡将铁氰化钾氧化还原电对氧化，实现对氧化还原电对液体流动电池负极的充电。
如图5所示，在暗态下，无电流流经外电路；光照下，产生光生空穴流经外电路至石墨毡正极，将铁氰化钾氧化还原电对氧化，实现对液流电池的负极充电。
如图6所示，两电极短接时，光照下持续产生光电流，实现对液流电池负极的持续充电。
实施例4
本实施例中，以Co(OH)2修饰(本实施例的修饰过程同实施例1)Ta3N5纳米棒阵列光阳浸在Br-/BrO3 -氧化还原电对水溶液作为液体流动电池的正极，将Pt网电极浸在NaSO4(0.2M)水溶液中，两种电极利用质子交换膜隔离开。Ta3N5光阳极与Pt网电极通过外电路链接构建双电极模式。光照下，Ta3N5光阳极中产生的光生空穴扩散到表面将Br-氧化为BrO3，光生电子通过外电路转移至Pt网电极将-水还原释放氢气，实现对氧化还原电对液体流动电池正极的充电。这里利用n型半导体光阳极替代p型半导体光阴极实现对液流电池正极的充电过程，只需要交换一下电极在两种电解液中位置，达到同种目的。因此，在液流电池集成的光电化学水分解电池体系中，有多种变换模式。
如图7所示，在暗态下，无电流流经外电路；光照下，产生光生电子流经外电路至Pt网电极，将水还原为氢气的同时，Ta3N5光阳极中产生的光生空穴扩散到表面将Br-氧化为BrO3，实现对液流电池的正极充电。
如图8所示，两电极短接时，光照下持续产生光电流，实现对液流电池正极的持续充电。
实施例结果表明，本发明以n型半导体光阳极连接储能器件负极，p型半导体光阴极连接储能器件正极，利用质子交换膜将电极隔离在不同电解液中，构成储能器件集成式光电化学水分解电池。n型半导体光阳极受光激发产生的光生空穴扩散至表面将水氧化释放出氧气，而光生电子则通过外电路转移至储能器件负极实现对负极充电；p型半导体光阴极受光激发产生的光生电子将水还原释放氢气，而光生空穴通过外电路转移至储能器件正极实现正极充电。通过将储能器件集成在光电化学水分解电池体系中，可实现太阳能至化学能(氢气)和电能的同时存储，有效提高了太阳能的转化利用效率。

Claims (8)

  1. 一种储能器件集成式光电化学水分解电池的设计方法，其特征在于：以n型半导体光阳极连接储能器件负极，p型半导体光阴极连接储能器件正极，利用质子交换膜将电极隔离在不同电解液中，构成储能器件集成式光电化学水分解电池。
  2. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的n型半导体光阳极，优选TiO2、WO3、BiVO4、Fe2O3、Ta3N5、TaON之一或两种以上的复合材料。
  3. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的p型半导体光阴极，优选Cu2O、GaP、WSe2、InP之一或两种以上的复合材料。
  4. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的储能器件为各种电化学储能器件。
  5. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的储能器件，优选电容器、氧化还原电对液体流动电池或锂硫电池。
  6. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的电解液为水系电解液或有机系电解液，电解液的pH值0～14；其中，n型半导体光阳极优选浸入pH值7～14的电解液中，p型半导体光阴极优选浸入pH值0～7的电解液中。
  7. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的n型半导体光阳极，以Co(OH)2、Co3O4、Co-Pi或NiOx产氧的助催化剂修饰，修饰过程如下：利用溶液离子反应法、原子层沉积法、激射镀膜法、电沉积法、溶胶旋涂法或热喷涂法，在n型半导体光阳极表面担载沉积上述产氧助催化剂的纳米颗粒或薄膜。
  8. 按照权利要求1所述的储能器件集成式光电化学水分解电池的设计方法，其特征在于：所述的p型半导体光阴极，以Pt、RuO2或MoS2产氢的助催化剂修饰，修饰过程如下：利用溶液离子反应法、原子层沉积法、激射镀膜法、电沉积法、溶胶旋涂法或热喷涂法，在p型半导体光阳极表面担载沉积上述产氢助催化剂的纳米颗粒或薄膜。
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