CN107541747B - A kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery - Google Patents
A kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000003287 optical effect Effects 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title claims abstract description 22
- 238000013461 design Methods 0.000 title claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 238000002955 isolation Methods 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 230000033116 oxidation-reduction process Effects 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003426 co-catalyst Substances 0.000 claims description 9
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000002120 nanofilm Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 229910002915 BiVO4 Inorganic materials 0.000 claims description 3
- 229910003071 TaON Inorganic materials 0.000 claims description 3
- 229910003090 WSe2 Inorganic materials 0.000 claims description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910005855 NiOx Inorganic materials 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 229910002804 graphite Inorganic materials 0.000 description 23
- 239000010439 graphite Substances 0.000 description 23
- 230000005518 electrochemistry Effects 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002084 dioxo-lambda(5)-bromanyloxy group Chemical group *OBr(=O)=O 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- -1 potassium ferricyanide Chemical compound 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910018292 Cu2In Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241001274216 Naso Species 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
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- 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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to photoelectrochemical cell field, specially a kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery.With n-type semiconductor light anode connect energy storage device cathode, p-type semiconductor photocathode connect energy storage device anode, using proton exchange membrane by electrode isolation in different electrolytes, constitute energy storage device integrating optical electro-chemical water decompose battery.The photohole that the excitation of n-type semiconductor light anode light generates diffuses to surface and water oxygen is released oxygen, and light induced electron then passes through external circuit and is transferred to the realization of energy storage device cathode to cathode charging；Water is restored release hydrogen by the light induced electron that the excitation of p-type semiconductor photocathode light generates, and photohole is transferred to energy storage device anode by external circuit and realizes anode charging.The present invention will be stored in energy storage device in the photogenerated charge of external circuit direct combination with electrical energy form in Traditional photovoltaic chemical cell, effectively increase the Transform efficiency of solar energy.
Description
Technical field
The present invention relates to photoelectrochemical cell field, specially a kind of energy storage device integrating optical electro-chemical water decomposes battery
Design method.
Background technique
Water decomposition is discharged hydrogen using solar energy by optical electro-chemistry moisture electrolytic cell, and solar energy is fixed in the form of hydrogen bond
Conversion is one of solar energy conversion and effective way of storage.Optical electro-chemistry water decomposition full battery includes n-type semiconductor light anode
With p-type semiconductor photocathode, constructing efficient optical electro-chemistry water decomposition full battery is to realize water spontaneous complete point under solar irradiation
The key of solution.
The basic principle of optical electro-chemistry water decomposition full battery is similar to Z-type charge transfer mechanism, the light induced electron of high-energy
Migrate the decomposition reaction that water is induced to photocathode and photoanode surface respectively with hole, and the light induced electron of low energy and hole
It is directly compound in external circuit.Whole process is to absorb two photons to generate a pair of effectively light induced electron and hole, therefore solar energy
Utilization efficiency significantly lose.
Summary of the invention
It is an object of the invention to propose that a kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery, lead to
The design of integrated form device is crossed, it can be achieved that the efficiency of solar energy utilization is obviously improved.
The technical scheme is that
A kind of energy storage device integrating optical electro-chemical water decomposes the design method of battery, with the connection of n-type semiconductor light anode
Energy storage device cathode, p-type semiconductor photocathode connects energy storage device anode, using proton exchange membrane by electrode isolation in different electricity
It solves in liquid, constitutes energy storage device integrating optical electro-chemical water and decompose battery.
The n-type semiconductor light anode, preferably TiO2、WO3、BiVO4、Fe2O3、Ta3N5, one of TaON or two or more
Composite material.
The p-type semiconductor photocathode, preferably Cu2O、GaP、WSe2, one of InP or two or more composite materials.
The energy storage device is various electrochemical energy storing devices.
The energy storage device, preferred capacitor, oxidation-reduction pair liquid flowing battery or lithium-sulfur cell.
The electrolyte is aqueous electrolyte or organic system electrolyte, the pH value 0~14 of electrolyte；Wherein, N-shaped is partly led
Body light anode is preferably immersed in the electrolyte of pH value 7~14, and p-type semiconductor photocathode is preferably immersed in the electrolyte of pH value 0~7
In.
The n-type semiconductor light anode, with Co (OH)2、Co3O4, Co-Pi or NiOxThe co-catalyst modification for producing oxygen, is repaired
Decorations process is as follows: utilizing solion reaction method, atomic layer deposition method, lasing coating method, electrodeposition process, colloidal sol spin-coating method or heat
Spray coating method supports the nano particle or film for depositing above-mentioned production oxygen co-catalyst in n-type semiconductor photoanode surface.
The p-type semiconductor photocathode, with Pt, RuO2Or MoS2The co-catalyst modification of hydrogen is produced, modification is as follows:
Using solion reaction method, atomic layer deposition method, lasing coating method, electrodeposition process, colloidal sol spin-coating method or hot spray process, in p
Type semiconductor optical anode surface supports the nano particle or film for depositing above-mentioned production hydrogen co-catalyst.
Design philosophy of the invention is:
In order to further increase the Transform efficiency of solar energy, the present invention proposes energy storage device integrating optical electro-chemical water
Decompose the concept of full battery.While high energy photoproduction electrons and holes induce the reduction and oxidation of water respectively, the light of low energy
Raw hole and the not simple direct combination of electronics, are respectively stored in the anode and cathode of energy storage device with electrical energy form.
Under illumination, light anode oxidation water charges energy storage device cathode while discharging oxygen, and while photocathode reduction aquatic products hydrogen
Energy storage device anode is charged.Electric current can be then generated using the anode and cathode of conducting wire connection energy storage device after illumination, is built into
Classical electrochemical energy storage system.
The invention has the advantages and beneficial effects that:
The present invention is by the way that electrochemical energy storing device to be integrated in optical electro-chemistry water decomposition battery system, it can be achieved that solar energy
It is stored while to chemical energy (hydrogen) and electric energy.It absorbs two photons and generates two pairs of light induced electrons and hole, a pair is used for water
Decomposition, a pair stored with electrical energy form, effectively improve solar energy Transform efficiency.
Detailed description of the invention
Fig. 1 .Ta3N5The optical electro-chemistry half-cell that light anode and capacitor graphite cathode are set up is in the case where dark-state and illumination replace
Photocurrent response；X-axis is time (second/s), and Y-axis is density of photocurrent (mAcm-2)。
Fig. 2 .Ta3N5In the optical electro-chemistry half-cell that light anode and capacitor graphite cathode are set up, capacitor graphite cathode exists
Potential change under dark-state and illumination alternately；X-axis is time (second/s), and Y-axis is current potential (volt/V).
Fig. 3 .Cu2The optical electro-chemistry half-cell that O photocathode and capacitor graphite anode are set up is in the case where dark-state and illumination replace
Photocurrent response；X-axis is time (second/s), and Y-axis is density of photocurrent (mAcm-2)。
Fig. 4 .Cu2In the optical electro-chemistry half-cell that O photocathode and capacitor graphite anode are set up, capacitor graphite anode exists
Potential change under dark-state and illumination alternately；X-axis is time (second/s), and Y-axis is current potential (volt/V).
Fig. 5 .Ta3N5The optical electro-chemistry that light anode and potassium ferricyanide oxidation-reduction pair (liquid flowing battery cathode) are set up
Volt-ampere test curve under half-cell dark-state and under illumination；X-axis is applied voltage (volt/V), and Y-axis is density of photocurrent (mA
cm-2)。
Fig. 6 .Ta3N5The optical electro-chemistry that light anode and potassium ferricyanide oxidation-reduction pair (liquid flowing battery cathode) are set up
Short circuit density of photocurrent-time graph under half-cell illumination；X-axis is time (second/s), and Y-axis is density of photocurrent (mAcm-2)。
Fig. 7 .Ta3N5Light anode and Br-/BrO3 -The optical electro-chemistry that oxidation-reduction pair (liquid flowing anode) is set up
Volt-ampere curve under half-cell illumination；X-axis is applied voltage (volt/V), and Y-axis is density of photocurrent (mAcm-2)。
Fig. 8 .Ta3N5Light anode and Br-/BrO3 -The optical electro-chemistry that oxidation-reduction pair (liquid flowing anode) is set up
Short circuit density of photocurrent-time graph under half-cell illumination；X-axis is time (second/s), and Y-axis is density of photocurrent (mAcm-2)。
Specific embodiment
In the specific implementation process, energy storage device integrating optical electro-chemical water of the present invention decomposes battery, with n-type semiconductor light
Anode connects energy storage device cathode, and p-type semiconductor photocathode connects energy storage device anode, using proton exchange membrane by electrode isolation
In different electrolytes, constitutes energy storage device integrating optical electro-chemical water and decompose battery.Under illumination, light anode aoxidizes water and discharges oxygen
Energy storage device cathode is charged while gas, and energy storage device anode charges while photocathode reduction aquatic products hydrogen.Specifically such as
Under:
1, the n-type semiconductor light anode, including various n-type semiconductors are (such as: TiO2、WO3、BiVO4、Fe2O3、Ta3N5、
TaON etc.) and its composite material.
2, the p-type semiconductor photocathode, including various p-type semiconductors are (such as: Cu2O、GaP、WSe2, InP etc.) and its it is multiple
Condensation material.
3, the energy storage device, including various electrochemical energy storing devices are (such as: capacitor, oxidation-reduction pair liquid flow
Dynamic battery, lithium-sulfur cell etc.).
4, the electrolyte, including water system and organic system electrolyte, pH value 0~14.
The present invention is further elaborated below with reference to embodiment and attached drawing.
Embodiment 1
In the present embodiment, with Co (OH)2Modify Ta3N5Nanometer rods (modification of the present embodiment refers to: by continuously from
Sublayer adsorption reaction method is by Co (OH)2It is supported on Ta3N5Nanometer stick array surface, its main feature is that by Ta3N5Nanometer stick array is thin
Film is in ion containing Co and OH-Alternating impregnating in the solution of ion generates Co (OH) using the ionic reaction of adsorption2, generation
It produces oxygen co-catalyst Co (OH)2Ta can be evenly distributed on3N5Nanometer stick array surface is conducive to improve the production oxygen work of its photoelectrocatalysis
Property) array photo-anode link capacitors graphite cathode, two electrodes are isolated in two kinds of electrolyte using proton exchange membrane.Ta3N5Light
Anode is immersed in NaOH (molar concentration 1M) aqueous solution, and capacitor graphite cathode is immersed in NaSO4In (0.2M) aqueous solution, two electrodes
Building bipolar electrode mode is linked by external circuit.Under illumination, Ta3N5The photohole generated in light anode is diffused into surface Jiang Shui
Oxidation release oxygen, light induced electron are transferred and stored in capacitor graphite cathode by external circuit, capacitor graphite cathode electricity
Negative move in position realizes charging process.
As shown in Figure 1, in the dark state, no current flows through external circuit；Under illumination, generates photoelectric current and flow through external circuit to capacitor
Device graphite cathode is realized and is charged to the cathode of capacitor.
As shown in Fig. 2, the current potential of capacitor graphite cathode is negative to be moved after illumination, charging process is realized；After illumination stops, electricity
Container graphite cathode current potential shuffles realization discharge process.
Embodiment 2
In the present embodiment, with surface modification, (modification of the present embodiment refers to: using solvent thermal process in Cu2O film
Surface in situ grows ZnO array film, its main feature is that N-shaped ZnO film and p-type Cu2O film constitutes pn-junction, is conducive to photoproduction load
Flow son separation, and then improve its photoelectric catalytically active) Cu2O photocathode link capacitors graphite anode, two electrodes utilize matter
Proton exchange is isolated in two electrolyte.Cu2O photocathode is immersed in NaSO4In (0.2M) aqueous solution, capacitor graphite anode
It is immersed in NaSO4In (0.2M) aqueous solution, two electrodes link building bipolar electrode mode by external circuit.Under illumination, Cu2In O photocathode
The light induced electron of generation is diffused into surface and water is restored release hydrogen, and photohole is transferred and stored by external circuit in capacitor
In graphite anode, capacitor graphite anodic potentials shuffle realization charging process.
As shown in figure 3, in the dark state, no current flows through external circuit；Under illumination, generates photoelectric current and flow through external circuit to capacitor
Device graphite anode, realizes and charges to the anode of capacitor.
As shown in figure 4, the current potential of capacitor graphite anode is shuffled after illumination, charging process is realized；After illumination stops, electricity
Negative move of container graphite anodic potentials realizes discharge process.
Embodiment 3
In the present embodiment, by Co (OH)2Modify (modification of the present embodiment is with embodiment 1) Ta3N5Nanometer stick array light
Anode is immersed in NaOH (1M) aqueous solution, and graphite felt is immersed in potassium ferricyanide oxidation-reduction pair alkaline aqueous solution and flows as liquid
The cathode of battery, two kinds of electrodes are kept apart using proton exchange membrane.Ta3N5Light anode links building by external circuit with graphite felt
Bipolar electrode mode.Under illumination, Ta3N5The photohole generated in light anode is diffused into surface and water oxygenization is discharged oxygen, photoproduction electricity
Son is transferred to graphite felt by external circuit and aoxidizes potassium ferricyanide oxidation-reduction pair, realizes and flows to oxidation-reduction pair liquid
The charging of battery cathode.
As shown in figure 5, in the dark state, no current flows through external circuit；Under illumination, generates photohole and flow through external circuit to stone
Black felt anode, potassium ferricyanide oxidation-reduction pair is aoxidized, and is realized and is charged to the cathode of flow battery.
As shown in fig. 6, persistently generating photoelectric current under illumination when two electrodes are shorted, realization continues flow battery cathode
Charging.
Embodiment 4
In the present embodiment, with Co (OH)2Modify (modification of the present embodiment is with embodiment 1) Ta3N5Nanometer stick array light
Sun is immersed in Br-/BrO3 -Pt net electrode is immersed in NaSO by anode of the oxidation-reduction pair aqueous solution as liquid flowing battery4
In (0.2M) aqueous solution, two kinds of electrodes are kept apart using proton exchange membrane.Ta3N5Light anode and Pt net electrode pass through external circuit chain
Connect building bipolar electrode mode.Under illumination, Ta3N5The photohole generated in light anode is diffused into surface for Br-It is oxidized to BrO3,
Light induced electron is transferred to Pt net electrode by external circuit will-Water reduction release hydrogen, realizes and flows to oxidation-reduction pair liquid
The charging of anode.It realizes here with n-type semiconductor light anode substitution p-type semiconductor photocathode to flow battery anode
Charging process, it is only necessary to exchange electrode position in two kinds of electrolyte, reach purpose of the same race.Therefore, in flow battery collection
At optical electro-chemistry water decomposition battery system in, there are many pattern conversion.
As shown in fig. 7, in the dark state, no current flows through external circuit；Under illumination, generates light induced electron and flow through external circuit to Pt
Net electrode, while water is reduced to hydrogen, Ta3N5The photohole generated in light anode is diffused into surface for Br-It is oxidized to
BrO3, realize and charge to the anode of flow battery.
As shown in figure 8, persistently generating photoelectric current under illumination when two electrodes are shorted, realization continues flow battery anode
Charging.
Embodiment the result shows that, the present invention with n-type semiconductor light anode connect energy storage device cathode, p-type semiconductor time
Pole connect energy storage device anode, using proton exchange membrane by electrode isolation in different electrolytes, constitute energy storage device integrated form
Optical electro-chemistry moisture electrolytic cell.The photohole that the excitation of n-type semiconductor light anode light generates diffuses to surface and releases water oxygen
Oxygen is released, and light induced electron then passes through external circuit and is transferred to the realization of energy storage device cathode to cathode charging；P-type semiconductor time
Water is restored release hydrogen by the light induced electron that light excitation in pole generates, and photohole is being transferred to energy storage device just by external circuit
Realize anode charging in pole.By energy storage device being integrated in optical electro-chemistry water decomposition battery system, it can be achieved that solar energy is extremely changed
It is stored while learning energy (hydrogen) and electric energy, effectively increases the Transform efficiency of solar energy.
Claims (8)
1. the design method that a kind of energy storage device integrating optical electro-chemical water decomposes battery, it is characterised in that: with n-type semiconductor light
Anode connects energy storage device cathode, and p-type semiconductor photocathode connects energy storage device anode, using proton exchange membrane by electrode isolation
In different electrolytes, constitutes energy storage device integrating optical electro-chemical water and decompose battery.
2. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the n-type semiconductor light anode, using TiO2、WO3、BiVO4、Fe2O3、Ta3N5, one of TaON or two or more answers
Condensation material.
3. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the p-type semiconductor photocathode, using Cu2O、GaP、WSe2, one of InP or two or more composite materials.
4. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the energy storage device is various electrochemical energy storing devices.
5. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the energy storage device, using capacitor, oxidation-reduction pair liquid flowing battery or lithium-sulfur cell.
6. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the electrolyte is aqueous electrolyte or organic system electrolyte, the pH value 0~14 of electrolyte；Wherein, n-type semiconductor light
Anode immerses in the electrolyte of pH value 7~14, and p-type semiconductor photocathode immerses in the electrolyte of pH value 0~7.
7. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the n-type semiconductor light anode, with Co (OH)2、Co3O4, Co-Pi or NiOxProduce the co-catalyst modification of oxygen, modified
Journey is as follows: utilizing solion reaction method, atomic layer deposition method, lasing coating method, electrodeposition process, colloidal sol spin-coating method or thermal spraying
Method supports the nano particle or film for depositing above-mentioned production oxygen co-catalyst in n-type semiconductor photoanode surface.
8. energy storage device integrating optical electro-chemical water described in accordance with the claim 1 decomposes the design method of battery, feature exists
In: the p-type semiconductor photocathode, with Pt, RuO2Or MoS2The co-catalyst modification of hydrogen is produced, modification is as follows: utilizing molten
Liquid ionic reaction method, atomic layer deposition method, lasing coating method, electrodeposition process, colloidal sol spin-coating method or hot spray process are partly led in p-type
Body photoanode surface supports the nano particle or film for depositing above-mentioned production hydrogen co-catalyst.
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