CN113363630A - Photoelectrochemical energy storage battery - Google Patents
Photoelectrochemical energy storage battery Download PDFInfo
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- CN113363630A CN113363630A CN202010140693.XA CN202010140693A CN113363630A CN 113363630 A CN113363630 A CN 113363630A CN 202010140693 A CN202010140693 A CN 202010140693A CN 113363630 A CN113363630 A CN 113363630A
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- 238000004146 energy storage Methods 0.000 title claims abstract description 40
- 239000003792 electrolyte Substances 0.000 claims abstract description 268
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- -1 iron ions Chemical class 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011630 iodine Substances 0.000 claims abstract description 18
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims description 47
- 210000000352 storage cell Anatomy 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- 150000002505 iron Chemical class 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000001508 potassium citrate Substances 0.000 claims description 4
- 229960002635 potassium citrate Drugs 0.000 claims description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 4
- 235000011082 potassium citrates Nutrition 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 claims description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 229940039748 oxalate Drugs 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 5
- 239000013543 active substance Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002459 sustained effect Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229910007786 Li2WO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- H01M14/005—Photoelectrochemical storage cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a photoelectrochemistry energy storage battery, which comprises: the ion exchange membrane is used for separating the positive electrolyte and the negative electrolyte, the positive electrode and the photo-anode share the same positive electrolyte, and the negative electrode and the counter electrode share the same negative electrolyte. The invention uses cheap iron and iodine elements as active substances to obviously reduce the cost of the battery, and the water-phase electrolyte improves the use safety of the battery; the addition of the ligand adjusts the oxidation-reduction potential of iron ions, so that the working voltage of the flow battery can be matched with that of the solar battery, and the direct conversion and storage of solar energy are realized without external bias voltage; the photoelectrochemistry energy storage battery is constructed, so that the discharge time under a larger current density can be prolonged.
Description
Technical Field
The invention belongs to the technical field of photoelectrochemistry energy storage batteries, and particularly relates to a photoelectrochemistry energy storage battery.
Background
The inexhaustible solar energy is considered to be the most effective alternative energy of fossil energy. However, the utilization of solar energy is restricted by environmental factors such as day and night alternation and weather changes, and the conversion of solar energy into electric energy convenient for utilization attracts extensive attention of researchers. The use of external circuits to connect solar cells to lithium batteries is a simple and straightforward way of solar energy utilization and has been reported in recent years by a group of topics at home and abroad (nat. Commun.6,8103, (2015). Adv. energy Mater.7,1602105, (2017)). However, in such an energy storage system, the matching between the operating voltage and the operating current of the solar cell and the secondary cell is mainly considered, which finally causes the energy storage system to consume a large amount of energy, and has the problems of high cost, complex structure and the like.
The photoelectrochemistry energy storage battery is prepared by integrating the photovoltaic battery or the photo anode and the secondary battery into the same energy storage system, so that the structural complexity of the energy storage system can be effectively reduced. Guo et al proposed a novel integrated power system based on dye-sensitized solar cells and lithium ion batteries, but the overall discharge capacity performance of the batteries was low, only 38.89 μ A h (Nano letters,2012,12(5): 2520-2523.). In addition, because the voltage of the solar photovoltaic cell is lower, the secondary battery can not be directly charged only by a single photovoltaic cell, and the charging voltage of the lithium ion battery can be satisfied by connecting a plurality of solar cells in series, so that the cost and the volume of the battery system are increased, and the portability is reduced. Chinese patent 110676338A discloses a design of a light charging secondary battery, which is a battery system with a semiconductor as a light electrode built into the secondary battery system, the design structure is relatively simple, solid sulfur or polysulfide ion solution is used as a positive electrode, lithium metal is used as a negative electrode, under the illumination condition, the charging voltage of the battery is reduced from the original 2.48V to 1.87V, the light voltage provided by the visible light electrode is not matched with the working voltage of the secondary battery, and only a part of the charging voltage can be provided. In addition, the use of lithium metal electrodes in the battery system and the use of organic electrolyte increases the cost of the battery. High school et al proposed a directly chargeable redox flow battery with dye sensitized titanium dioxide as the photoelectrode and Li2WO4LiI is used as a negative electrode active material and a positive electrode active material, and successfully regulates the working voltage of the secondary battery to be matched with the working voltage of the photo-anode. The cell was illuminated for 10min at 0.075mA cm-2The discharge time lasts about 4min, and the discharge capacity is low. In addition, the organic system adopted by the positive electrode leads to increased cost and reduced safety (Journal of materials chemistry A,2013,1(24): 7012-.
Based on the above analysis, further research is still needed to construct a light charging secondary battery energy storage system which has low cost and good safety and can directly realize conversion and storage of sunlight. The prior light charging secondary battery system mainly has the following problems: the photovoltaic cell and the secondary cell have poor matching performance at working voltage, and cannot realize direct conversion and storage of solar energy. The constructed light charging secondary battery system only depends on light absorption of a single photoelectrode to provide charging driving force, so that the matching of a solar battery and a secondary battery on working voltage and working current is mainly considered; the cost of the battery is increased due to the high price of materials in a battery system, such as the use of organic electrolyte and the use of metal lithium; the discharge capacity is low, and the requirement of solar energy mass storage cannot be met far away.
Disclosure of Invention
In view of the defects of the prior art, the present invention provides a photoelectrochemical energy storage cell, which combines the advantages of a solar cell and a flow battery, and uses solar energy to directly charge positive electrolyte and negative electrolyte through a photoanode, so as to convert the solar energy into chemical energy, store the chemical energy in a liquid storage tank in the form of electrolyte, and output the chemical energy in the form of electric energy through the flow battery at any time.
The purpose of the invention is realized by the following technical scheme.
A photoelectrochemical energy storage cell comprising: the ion exchange membrane is used for separating the positive electrolyte and the negative electrolyte, the positive electrode and the photo anode share the same positive electrolyte, and the negative electrode and the counter electrode share the same negative electrolyte.
In the technical scheme, the photo-anode is one or more of dye-sensitized titanium dioxide, ferric oxide, bismuth vanadate, cadmium sulfide, zinc sulfide and tungsten trioxide.
In the above technical solution, the counter electrode is an electrochemically inert conductive material, preferably a platinum sheet.
In the above technical solution, the positive electrode and the negative electrode are both electrochemically inert conductive materials.
In the above technical scheme, the positive electrode is a carbon material, preferably carbon paper, carbon felt or graphite felt; the negative electrode is made of carbon materials, preferably carbon paper, carbon felt or graphite felt.
In the technical scheme, the positive electrolyte is a mixture of an iodine active substance, a first auxiliary electrolyte and water, the negative electrolyte is a mixture of an iron ion coordination compound active substance, a second auxiliary electrolyte and water, the first auxiliary electrolyte is potassium chloride, the second auxiliary electrolyte is potassium chloride, the concentration of the first auxiliary electrolyte in the positive electrolyte is 1-5 mol/L, and the concentration of the second auxiliary electrolyte in the negative electrolyte is 1-5 mol/L.
In the technical scheme, the iodine active substance is one or more of lithium iodide, sodium iodide, potassium iodide and zinc iodide, and the concentration of iodide ions of the iodine active substance in the positive electrode electrolyte is 0.1-10 mol/L.
In the technical scheme, the iron ion coordination compound is formed by mixing iron salt and a ligand, wherein during mixing, the ratio of the iron salt to the ligand is 1 (1-5) according to the parts by weight of the substances, wherein the iron salt is one or more of ferric chloride, ferric nitrate and ferric sulfate; the ligand is one or more of sodium citrate, potassium citrate, sodium oxalate, potassium oxalate, ethylene diamine tetraacetic acid disodium, ethylene diamine tetraacetic acid tetrasodium and ethylenediamine, and the concentration of the iron ion coordination compound in the cathode electrolyte is 0.1-2 mol/L.
In the above technical scheme, the active substance of the iron ion coordination compound is one or more of an iron ion-ethylenediamine coordination compound, an iron ion-citrate coordination compound, an iron ion-ethylenediamine tetraacetic acid coordination compound and an iron ion-oxalate coordination compound.
In the above technical solution, the ion exchange membrane is a cation permeable membrane, which only allows cations to pass through.
In the above technical solution, the photo anode receives light.
In the above technical solution, the method further comprises: a first container for loading photoanode and counter electrode, a second container and first pipeline ~ fourth pipeline for loading positive and negative pole, first container and second container are inclosed container, ion exchange membrane's quantity is 2, respectively installs 1 in first container and the second container ion exchange membrane the both sides of ion exchange membrane in the first container are filled with positive electrolyte and negative pole electrolyte respectively the both sides of ion exchange membrane in the second container are filled with positive electrolyte and negative pole electrolyte respectively, the part that first container and second container are used for loading positive electrolyte is anodal electrolyte pond, and the part that first container and second container are used for loading negative pole electrolyte is negative pole electrolyte pond, photoanode fixed mounting be in the anodal electrolyte pond of first container, counter electrode fixed mounting be in the negative pole electrolyte pond of first container, the anode is fixedly arranged in the anode electrolyte tank of the second container, and the cathode is fixedly arranged in the cathode electrolyte tank of the second container; the positive electrolyte tank of the first container is respectively communicated with the positive electrolyte tank of the second container through a first pipeline and a second pipeline, the second pipeline is provided with a first liquid storage tank and a first pump for storing positive electrolyte, the first pump discharges the positive electrolyte in the first liquid storage tank into the positive electrolyte tank of the first container along the second pipeline, and simultaneously discharges the positive electrolyte in the positive electrolyte tank of the second container into the first liquid storage tank, and the first pipeline is used for discharging the positive electrolyte in the positive electrolyte tank of the first container into the positive electrolyte tank in the second container; the negative electrolyte tank in the first container is respectively communicated with the negative electrolyte tank in the second container through a third pipeline and a fourth pipeline, a second pump and a second liquid storage tank for storing negative electrolyte are arranged on the fourth pipeline, the second pump is used for discharging the negative electrolyte in the second liquid storage tank into the negative electrolyte tank of the first container from the second liquid storage tank along the fourth pipeline, and simultaneously discharging the negative electrolyte of the negative electrolyte tank of the second container into the second liquid storage tank, and the third pipeline is used for discharging the negative electrolyte of the negative electrolyte tank of the first container into the negative electrolyte tank of the second container; the photo-anode and the counter electrode are connected through a first wire, the anode and the cathode are connected through a second wire, and a load is mounted on the second wire.
In the above technical solution, the method further comprises: third container, fifth pipeline and sixth pipeline, third container are inclosed container, ion exchange membrane's quantity is 1, installs in the third container ion exchange membrane the both sides of ion exchange membrane are filled with positive electrolyte and negative pole electrolyte respectively, and the part that the third container is used for loading positive electrolyte is anodal electrolyte bath, and the part that the third container is used for loading negative pole electrolyte is negative pole electrolyte bath, anodal and light anode fixed mounting be in the anodal electrolyte bath, negative pole and counter electrode fixed mounting be in the negative pole electrolyte bath, the one end of anodal electrolyte bath is passed through fifth pipeline and this anodal electrolyte bath other end intercommunication install a third pump and first liquid storage pot on the fifth pipeline, and the anodal electrolyte in the first liquid storage pot is arranged into the anodal electrolyte of third container simultaneously with the anodal electrolyte of the anodal electrolyte bath of third container along the fifth pipeline with the third pump Entering a first liquid storage tank; one end of the negative electrode electrolyte tank is communicated with the other end of the negative electrode electrolyte tank through a sixth pipeline, a fourth pump and a second liquid storage tank are mounted on the sixth pipeline, the fourth pump is used for discharging the negative electrode electrolyte in the second liquid storage tank into the negative electrode electrolyte tank of a third container from the second liquid storage tank along the sixth pipeline, and simultaneously discharging the negative electrode electrolyte in the negative electrode electrolyte tank of the third container into the second liquid storage tank; the photo-anode and the counter electrode are connected through a first wire, the anode and the cathode are connected through a second wire, and a load is mounted on the second wire.
The invention has the advantages that a photoelectrochemistry energy storage battery using iron and iodine redox couple is constructed, the battery cost is obviously reduced by using cheap iron and iodine elements as active substances, and the use safety of the battery is improved by using aqueous electrolyte; the addition of the ligand adjusts the oxidation-reduction potential of iron ions, so that the working voltage of the flow battery can be matched with that of the solar battery, and the direct conversion and storage of solar energy are realized without external bias voltage; the photoelectrochemistry energy storage battery is constructed, so that the discharge time under a larger current density can be prolonged. The invention can be scaled, is suitable for solar energy storage in different scales outdoors or outdoors, and provides reference for designing novel high-efficiency photoelectrochemical cells.
Drawings
FIG. 1 is a schematic structural diagram of a photoelectrochemical energy storage cell of the present invention;
FIG. 2 is a schematic structural diagram of a photoelectrochemical energy storage cell of the present invention;
FIG. 3 is a graph of the assembled photoelectrochemical energy storage cell of example 1 with a light exposure time of 30 minutes at a flow rate of 1.5mL/min and 0.1mA cm-2Current density of (d);
FIG. 4 is a graph of the assembled photoelectrochemical energy storage cell of example 2 illuminated for 30 minutes at a flow rate of 1.5mL/min and 0.1mA cm-2Current density of (d);
FIG. 5 is a graph of the assembled photoelectrochemical energy storage cell of example 3 with 60 minutes of light at a flow rate of 1.5mL/min and 0.05mA cm-2Current density of (a).
Wherein, 1 is a photo anode, 2 is a load, 3 is a second electric wire, 4 is a positive electrolyte, 5 is an ion exchange membrane, 6 is a negative electrolyte, 7 is a counter electrode, 8 is a negative electrode, 9 is a first container, 10 is a positive electrode, 11 is a first pipeline, 12 is a third pipeline, 13 is a first electric wire, 14 is a first pump, 15 is a second pump, 16 is a first liquid storage tank, 17 is a second liquid storage tank, 18 is a second container, 19 is a third container, 20 is a fifth pipeline, 21 is a sixth pipeline, 22 is a third pump, 23 is a fourth pump, 24 is a fourth pipeline, and 25 is a second pipeline.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
A photoelectrochemical energy storage cell comprising: the ion exchange membrane is used for separating the positive electrolyte and the negative electrolyte, the positive electrode and the photo-anode share the same positive electrolyte, the negative electrode and the counter electrode share the same negative electrolyte, and the photo-anode receives illumination.
As an implementation form of the photoelectrochemistry energy storage cell, as shown in fig. 1, the photoelectrochemistry energy storage cell further includes: a first container 9 for loading a photo-anode 1 and a counter electrode 7, a second container 18 for loading an anode 10 and a cathode 8, and first pipelines 11 to fourth pipelines 24, wherein the first container 9 and the second container 18 are both closed containers, the number of ion exchange membranes 5 is 2,1 ion exchange membrane 5 is respectively installed in the first container 9 and the second container 18, both sides of the ion exchange membrane 5 in the first container 9 are respectively filled with an anode electrolyte 4 and a cathode electrolyte 6, both sides of the ion exchange membrane 5 in the second container 18 are respectively filled with an anode electrolyte 4 and a cathode electrolyte 6, the parts of the first container 9 and the second container 18 for loading the anode electrolyte 4 are both anode electrolyte tanks, the parts of the first container 9 and the second container 18 for loading the cathode electrolyte 6 are both cathode electrolyte tanks, the photo-anode 1 is fixedly installed in the anode electrolyte tank of the first container 9, the counter electrode 7 is fixedly arranged in a negative electrolyte tank of the first container 9, the positive electrode 10 is fixedly arranged in a positive electrolyte tank of the second container 18, and the negative electrode 8 is fixedly arranged in a negative electrolyte tank of the second container 18; the positive electrolyte tank of the first container 9 is respectively communicated with the positive electrolyte tank of the second container 18 through a first pipeline 11 and a second pipeline 25, the positions of the first pipeline 11 and the second pipeline 25 communicated with the positive electrolyte tank of the first container are opposite, and the positions of the first pipeline 11 and the second pipeline 25 communicated with the positive electrolyte tank of the second container are opposite. A first liquid storage tank 16 for storing the positive electrolyte 4 and a first pump 14 are arranged on the second pipeline 25, the first pump 14 discharges the positive electrolyte 4 in the first liquid storage tank 16 into the positive electrolyte tank of the first container 9 along the second pipeline 25, simultaneously discharges the positive electrolyte in the positive electrolyte tank of the second container 18 into the first liquid storage tank 16, and the first pipeline 11 is used for discharging the positive electrolyte 4 in the positive electrolyte tank of the first container 9 into the positive electrolyte tank of the second container 18; the negative electrolyte tank in the first container 9 is respectively communicated with the negative electrolyte tank in the second container 18 through a third pipeline 12 and a fourth pipeline 24, the third pipeline 12 and the fourth pipeline 24 are opposite to the position where the negative electrolyte tank of the first container is communicated, and the third pipeline 12 and the fourth pipeline 24 are opposite to the position where the negative electrolyte tank of the second container is communicated. A second pump 15 and a second liquid storage tank 17 for storing the negative electrolyte 6 are arranged on the fourth pipeline 24, the second pump 15 is used for discharging the negative electrolyte 6 in the second liquid storage tank 17 into the negative electrolyte tank of the first container 9 from the second liquid storage tank 17 along the fourth pipeline 24, and simultaneously discharging the negative electrolyte of the negative electrolyte tank of the second container 18 into the second liquid storage tank 17, and the third pipeline 12 is used for discharging the negative electrolyte 6 of the negative electrolyte tank of the first container 9 into the negative electrolyte tank of the second container 18; the photo anode 1 and the counter electrode 7 are connected by a first wire 13, the anode 10 and the cathode 8 are connected by a second wire 3, and a load 2 is mounted on the second wire 3.
Within the first container: the photo-anode 1 in the positive electrolyte tank and the counter electrode 7 in the negative electrolyte tank are connected by a first wire 13, and at the moment, the photo-anode 1, the negative electrolyte and the ion exchange membrane together form a solar cell for a photo-charging process. In the second container: and connecting a positive electrode 10 in the positive electrolyte tank and a negative electrode 8 in the negative electrolyte tank with the load 2 by using a second wire 3, and forming a flow battery together with the positive electrolyte 4, the negative electrolyte 6 and the ion exchange membrane for a discharging process.
As another implementation form of the photoelectrochemistry energy storage cell, as shown in fig. 2, the photoelectrochemistry energy storage cell further includes: a third container 19, a fifth pipeline 20 and a sixth pipeline 21, where the third container 19 is a closed container, the number of ion exchange membranes 5 is 1, an ion exchange membrane 5 is installed in the third container 19, two sides of the ion exchange membrane 5 are respectively filled with a positive electrolyte 4 and a negative electrolyte 6, a part of the third container 19 for loading the positive electrolyte 4 is a positive electrolyte tank, a part of the third container 19 for loading the negative electrolyte 6 is a negative electrolyte tank, the positive electrode 10 and the photo-anode 1 are fixedly installed in the positive electrolyte tank, the negative electrode 8 and the counter electrode 7 are fixedly installed in the negative electrolyte tank, one end of the positive electrolyte tank is communicated with the other end of the positive electrolyte tank through the fifth pipeline 20, a third pump 22 and a first liquid storage tank 16 are installed on the fifth pipeline 20, the third pump 22 discharges the positive electrolyte 4 in the first liquid storage tank 16 into the positive electrolyte tank of the third container 19 along the fifth pipeline 20, and simultaneously discharges the positive electrolyte of the third container 19 into the positive electrolyte tank Discharging the positive electrolyte of the electrolyte solution tank into the first liquid storage tank 16; one end of the negative electrolyte tank is communicated with the other end of the negative electrolyte tank through a sixth pipeline 21, a fourth pump 23 and the second liquid storage tank 17 are installed on the sixth pipeline 21, and the fourth pump 23 is used for discharging the negative electrolyte 6 in the second liquid storage tank 17 from the second liquid storage tank 17 into the negative electrolyte tank of the third container 19 along the sixth pipeline 21 and simultaneously discharging the negative electrolyte of the negative electrolyte tank of the third container 19 into the second liquid storage tank 17; the photo anode 1 and the counter electrode 7 are connected by a first wire 13, the anode 10 and the cathode 8 are connected by a second wire 3, and a load 2 is mounted on the second wire 3. The photo-anode 1 is connected with the counter electrode 7 by a first wire 13, and then the photo-anode, the positive electrolyte, the negative electrolyte and the ion exchange membrane together form a solar cell for a photo-charging process. And connecting the anode 10 and the cathode 8 with the load 2 by using the second wire 3, and forming a flow battery together with the anode electrolyte 4, the cathode electrolyte 6 and the ion exchange membrane for a discharging process.
The photoelectrochemical energy storage cell shown in fig. 1 and 2 works according to the following principle:
when the photoelectrochemical energy storage battery works, the positive electrolyte in the first liquid storage tank 16 is conveyed to the positive electrolyte pool under the action of the first pump 14 or the third pump 22, and the negative electrolyte in the second liquid storage tank 17 is conveyed to the negative electrolyte pool under the action of the second pump 15 or the fourth pump 23. Under the illumination condition, the photoanode 1 absorbs light to generate photoproduction electrons and photoproduction holes, the photoproduction electrons flow to the counter electrode 7 through the first electric wire 13, and the negative active material Fe3+Reduction to Fe2+A reduction reaction occurs, and the photo-generated holes form a positive active material I on the photo-anode 1-Oxidation to I3 -Oxidation reaction occurs. To balance the charge, cations flow from the positive electrolyte to the negative electrode through the ion exchange membrane 5Electrolyte, in this case the conversion of solar energy to chemical energy. In the discharging process, the positive and negative active materials are in a charging state, the positive active material generates a reduction reaction on the surface of the positive electrode 10, and the negative active material I reacts with the positive active material I3 -Reduction to I-The negative electrode active material is oxidized on the surface of the negative electrode 8 to convert Fe2+Oxidation to Fe3+The cations flow from the negative electrolyte back to the positive electrolyte through the ion exchange membrane 5 in order to balance the charge. At this time, the output of chemical energy to electric energy is completed.
The structure in fig. 1 is taken as an example, and the effect of the photoelectrochemical energy storage cell of the present invention is further explained below.
The effective areas of the photo-anode, the counter electrode, the anode and the cathode are all 1.0cm2。
List of experimental reagents
List of laboratory instruments
Example 1
The photo-anode is titanium dioxide.
The ion exchange membrane is a cation permeable membrane (Nafion membrane) that allows only cations to pass through.
The counter electrode is a metal platinum sheet.
The positive electrode is carbon paper;
the negative electrode is carbon paper.
The positive electrolyte is a mixture of an iodine active substance, a first auxiliary electrolyte and water, the first auxiliary electrolyte is potassium chloride, the concentration of the first auxiliary electrolyte in the positive electrolyte is 1mol/L, the iodine active substance is potassium iodide, and the concentration of iodide ions of the iodine active substance in the positive electrolyte is 0.5 mol/L.
The negative electrode electrolyte is a mixture of an iron ion coordination compound active substance, a second auxiliary electrolyte and water, the second auxiliary electrolyte is potassium chloride, the concentration of the second auxiliary electrolyte in the negative electrode electrolyte is 1mol/L, and the concentration of the iron ion coordination compound in the negative electrode electrolyte is 0.5 mol/L. The iron ion coordination compound is formed by mixing iron salt and ligand, wherein the iron salt and the ligand are added in a ratio of 1:2 according to the parts by weight of the substances during mixing, wherein the iron salt is ferric chloride; the ligand is potassium citrate (the amount of the substance of the iron ion coordination compound in the negative electrolyte is the same as the amount of the substance of the iron salt in the negative electrolyte).
At 100mW/cm2Photo-charging the photo-anode under illumination intensity for 30 minutes at 0.1mA cm-2The current density is discharged. The discharge curve is shown in fig. 3. As can be seen from the figure, the initial voltage of the discharge is about 0.20V, and the discharge point platform is obvious between 0.20V and 0.15V and is 0.1mA cm-2The discharge can be sustained for 102min under the current density.
Example 2
The photo-anode is made of dye-sensitized titanium dioxide.
The ion exchange membrane is a cation permeable membrane (Nafion membrane) that allows only cations to pass through.
The counter electrode is a metal platinum sheet.
The positive electrode is carbon paper;
the negative electrode is carbon paper.
The positive electrolyte is a mixture of an iodine active substance, a first auxiliary electrolyte and water, the first auxiliary electrolyte is potassium chloride, the concentration of the first auxiliary electrolyte in the positive electrolyte is 2mol/L, the iodine active substance is potassium iodide, and the concentration of iodide ions of the iodine active substance in the positive electrolyte is 0.3 mol/L.
The negative electrode electrolyte is a mixture of an iron ion coordination compound active substance, a second auxiliary electrolyte and water, the second auxiliary electrolyte is potassium chloride, the concentration of the second auxiliary electrolyte in the negative electrode electrolyte is 2mol/L, and the concentration of the iron ion coordination compound in the negative electrode electrolyte is 0.6 mol/L. The iron ion coordination compound is formed by mixing iron salt and ligand, wherein the iron salt and the ligand are added in a ratio of 1:4 in parts by weight during mixing, wherein the iron salt is ferric sulfate; the ligand is potassium oxalate (the amount of the substance of the iron ion coordination compound in the negative electrode electrolyte is the same as the amount of the substance of the iron salt in the negative electrode electrolyte).
At 100mW/cm2Photo-charging the photo-anode under illumination intensity for 30 minutes at 0.1mA cm-2The discharge is performed at a current density. The discharge curve is shown in fig. 4. As can be seen from the figure, the initial voltage of the discharge is about 0.28V, and the discharge point platform is obvious between 0.28V and 0.15V and is 0.1mA cm-2The discharge can be sustained for 129min under the current density.
Example 3
The photo-anode is ferric oxide.
The ion exchange membrane is a cation permeable membrane (Nafion membrane) that allows only cations to pass through.
The counter electrode is a metal platinum sheet.
The positive electrode is carbon paper;
the negative electrode is carbon paper.
The positive electrolyte is a mixture of an iodine active substance, a first auxiliary electrolyte and water, the first auxiliary electrolyte is potassium chloride, the concentration of the first auxiliary electrolyte in the positive electrolyte is 3mol/L, the iodine active substance is potassium iodide, and the concentration of iodide ions of the iodine active substance in the positive electrolyte is 0.5 mol/L.
The negative electrode electrolyte is a mixture of an iron ion coordination compound active substance, a second auxiliary electrolyte and water, the second auxiliary electrolyte is potassium chloride, the concentration of the second auxiliary electrolyte in the negative electrode electrolyte is 3mol/L, and the concentration of the iron ion coordination compound in the negative electrode electrolyte is 1 mol/L. The iron ion coordination compound is formed by mixing iron salt and ligand, wherein during mixing, the iron salt and the ligand are added according to the mass parts, and the ratio of the iron salt to the ligand is 1: 1, wherein the ferric salt is ferric chloride; the ligand is potassium citrate (the amount of the substance of the iron ion coordination compound in the negative electrolyte is the same as the amount of the substance of the iron salt in the negative electrolyte).
At 100mW/cm2The photo-anode is charged under illumination intensity, and after 60 minutes, the current is measured at 0.05mA cm-2The current density is discharged. The discharge curve is shown in fig. 5. As can be seen from the graph, the initial voltage of the discharge was about 0.24V and between 0.24V and 0.17VShows a clear spot platform at 0.1mA cm-2The discharge can be sustained for 123min under the current density.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A photoelectrochemical energy storage cell, comprising: the ion exchange membrane is used for separating the positive electrolyte and the negative electrolyte, the positive electrode and the photo anode share the same positive electrolyte, and the negative electrode and the counter electrode share the same negative electrolyte.
2. The photoelectrochemical energy storage cell of claim 1, wherein the photoanode is one or more of dye-sensitized titanium dioxide, ferric oxide, bismuth vanadate, cadmium sulfide, zinc sulfide, and tungsten trioxide;
the counter electrode is made of an electrochemically inert conductive material, preferably a metal platinum sheet;
the positive electrode and the negative electrode are both electrochemically inert conductive materials.
3. Photoelectrochemical energy storage cell according to claim 2, wherein the positive electrode is a carbon-based material, preferably carbon paper, carbon felt or graphite felt; the negative electrode is made of carbon materials, preferably carbon paper, carbon felt or graphite felt.
4. The photoelectrochemical energy storage cell of claim 3, wherein the positive electrolyte is a mixture of an iodine active material, a first co-electrolyte and water, the negative electrolyte is a mixture of an iron ion complex active material, a second co-electrolyte and water, the first co-electrolyte is potassium chloride, the second co-electrolyte is potassium chloride, the concentration of the first co-electrolyte in the positive electrolyte is 1-5 mol/L, and the concentration of the second co-electrolyte in the negative electrolyte is 1-5 mol/L.
5. The photoelectrochemical energy storage cell of claim 4, wherein the iodine active material is one or more of lithium iodide, sodium iodide, potassium iodide and zinc iodide, and the concentration of iodide ions in the iodine active material in the positive electrolyte is 0.1-10 mol/L.
6. The photoelectrochemical energy storage cell of claim 5, wherein the iron ion coordination compound is formed by mixing iron salt and ligand, and during mixing, the ratio of the iron salt to the ligand is 1 (1-5) according to the parts by weight of the added iron salt and ligand, wherein the iron salt is one or more of ferric chloride, ferric nitrate and ferric sulfate; the ligand is one or more of sodium citrate, potassium citrate, sodium oxalate, potassium oxalate, ethylene diamine tetraacetic acid disodium, ethylene diamine tetraacetic acid tetrasodium and ethylenediamine, and the concentration of the iron ion coordination compound in the cathode electrolyte is 0.1-2 mol/L.
7. The photoelectrochemical energy storage cell of claim 6, wherein the iron ion complex active material is one or more of an iron ion-ethylenediamine complex, an iron ion-citrate complex, an iron ion-ethylenediamine tetraacetic acid complex, and an iron ion-oxalate complex.
8. The photoelectrochemical energy storage cell of claim 7, wherein the ion exchange membrane is a cation permeable membrane, allowing only cations to pass through;
the photo-anode receives illumination.
9. The photoelectrochemical energy storage cell of any one of claims 1-8, further comprising: a first container for loading photoanode and counter electrode, a second container and first pipeline ~ fourth pipeline for loading positive and negative pole, first container and second container are inclosed container, ion exchange membrane's quantity is 2, respectively installs 1 in first container and the second container ion exchange membrane the both sides of ion exchange membrane in the first container are filled with positive electrolyte and negative pole electrolyte respectively the both sides of ion exchange membrane in the second container are filled with positive electrolyte and negative pole electrolyte respectively, the part that first container and second container are used for loading positive electrolyte is anodal electrolyte pond, and the part that first container and second container are used for loading negative pole electrolyte is negative pole electrolyte pond, photoanode fixed mounting be in the anodal electrolyte pond of first container, counter electrode fixed mounting be in the negative pole electrolyte pond of first container, the anode is fixedly arranged in the anode electrolyte tank of the second container, and the cathode is fixedly arranged in the cathode electrolyte tank of the second container; the positive electrolyte tank of the first container is respectively communicated with the positive electrolyte tank of the second container through a first pipeline and a second pipeline, the second pipeline is provided with a first liquid storage tank and a first pump for storing positive electrolyte, the first pump discharges the positive electrolyte in the first liquid storage tank into the positive electrolyte tank of the first container along the second pipeline, and simultaneously discharges the positive electrolyte in the positive electrolyte tank of the second container into the first liquid storage tank, and the first pipeline is used for discharging the positive electrolyte in the positive electrolyte tank of the first container into the positive electrolyte tank in the second container; the negative electrolyte tank in the first container is respectively communicated with the negative electrolyte tank in the second container through a third pipeline and a fourth pipeline, a second pump and a second liquid storage tank for storing negative electrolyte are arranged on the fourth pipeline, the second pump is used for discharging the negative electrolyte in the second liquid storage tank into the negative electrolyte tank of the first container from the second liquid storage tank along the fourth pipeline, and simultaneously discharging the negative electrolyte of the negative electrolyte tank of the second container into the second liquid storage tank, and the third pipeline is used for discharging the negative electrolyte of the negative electrolyte tank of the first container into the negative electrolyte tank of the second container; the photo-anode and the counter electrode are connected through a first wire, the anode and the cathode are connected through a second wire, and a load is mounted on the second wire.
10. The photoelectrochemical energy storage cell of any one of claims 1-8, further comprising: third container, fifth pipeline and sixth pipeline, third container are inclosed container, ion exchange membrane's quantity is 1, installs in the third container ion exchange membrane the both sides of ion exchange membrane are filled with positive electrolyte and negative pole electrolyte respectively, and the part that the third container is used for loading positive electrolyte is anodal electrolyte bath, and the part that the third container is used for loading negative pole electrolyte is negative pole electrolyte bath, anodal and light anode fixed mounting be in the anodal electrolyte bath, negative pole and counter electrode fixed mounting be in the negative pole electrolyte bath, the one end of anodal electrolyte bath is passed through fifth pipeline and this anodal electrolyte bath other end intercommunication install a third pump and first liquid storage pot on the fifth pipeline, and the anodal electrolyte in the first liquid storage pot is arranged into the anodal electrolyte of third container simultaneously with the anodal electrolyte of the anodal electrolyte bath of third container along the fifth pipeline with the third pump Entering a first liquid storage tank; one end of the negative electrode electrolyte tank is communicated with the other end of the negative electrode electrolyte tank through a sixth pipeline, a fourth pump and a second liquid storage tank are mounted on the sixth pipeline, the fourth pump is used for discharging the negative electrode electrolyte in the second liquid storage tank into the negative electrode electrolyte tank of a third container from the second liquid storage tank along the sixth pipeline, and simultaneously discharging the negative electrode electrolyte in the negative electrode electrolyte tank of the third container into the second liquid storage tank; the photo-anode and the counter electrode are connected through a first wire, the anode and the cathode are connected through a second wire, and a load is mounted on the second wire.
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Application publication date: 20210907 |