CN112531192A - Zinc-manganese single flow battery - Google Patents
Zinc-manganese single flow battery Download PDFInfo
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- CN112531192A CN112531192A CN202110134593.0A CN202110134593A CN112531192A CN 112531192 A CN112531192 A CN 112531192A CN 202110134593 A CN202110134593 A CN 202110134593A CN 112531192 A CN112531192 A CN 112531192A
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- single flow
- flow battery
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- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000746 purification Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000123 paper Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011087 paperboard Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- -1 at least one of SP Substances 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000013543 active substance Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
-
- 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
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a zinc-manganese single flow battery, which comprises a battery jar, a positive plate, a negative plate, a circulation tank, a liquid inlet, a liquid outlet and a purification tank, wherein the circulation tank is connected with the battery jar through the liquid inlet, the liquid outlet is positioned at the bottom of the battery jar and is connected with the purification tank, the purification tank is also connected with the circulation tank, and a filtering device is arranged between the liquid outlet and the purification tank. The flow battery can solve the problems that manganese dioxide falls off and active ions in electrolyte can not completely generate reversible reaction or are consumed by side reaction in the prior art, has the advantages of simple manufacturing process, low cost, safety, environmental protection and the like, is stable in circulation and high in coulombic efficiency, can replace positive and negative pole pieces inserted into a battery jar according to the battery condition, and is suitable for being applied to the field of energy storage to realize large-scale application and industrial production.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a zinc-manganese single flow battery.
Background
Along with the continuous expansion of social progress and development demand, the demand on energy and energy is increased, the traditional fossil energy such as coal and petroleum is consumed increasingly and brings serious environmental pollution, the economic concept of low-carbon development is not accorded with the current, and the renewable energy such as wind energy and solar energy has the defects of discontinuity, instability, uncontrollable and the like, an advanced energy storage technology is required to be used as a necessary and important support, the liquid flow energy storage battery is used as a novel and efficient electrochemical energy storage device, and the liquid flow energy storage battery has the advantages of high efficiency, long service life, good safety, independent design of power and capacity, very large flexibility, extremely strong expandability and the like.
The most important characteristic of the flow battery is that the active substance exists in the electrolyte in an ionic form, that is, the content, concentration and state change of the electrolyte affect the performance of the battery, and it is very important to maintain the stable state of the electrolyte. In the zinc-manganese flow battery, the active substances of the positive electrode and the negative electrode are respectively Mn in the electrolyte2+And Zn2+Charging stage Mn2+Manganese dioxide is generated by deposition of lost electrons on the positive electrode, the manganese dioxide is taken as a positive electrode active material in a discharging stage, and the manganese dioxide can drop slightly under the flow impact of a solution to cause the loss of the battery capacity, and active Zn2+Can react with hydroxyl and acid radicals in the electrolyte to generate a byproduct of basic zinc salt, and the fallen manganese dioxide and the generated byproduct can pollute the electrolyte environment, settle at the bottom of the battery and even contact with a pole piece, thereby seriously affecting the capacity and the cycle performance of the battery.
Disclosure of Invention
The invention aims to provide a zinc-manganese single flow battery, which solves the problems that manganese dioxide falls off, active ions in electrolyte can not completely generate reversible reaction or are consumed by side reaction, solid matters pollute the electrolyte environment, electrode reaction is influenced, and capacity loss and rapid cycle attenuation are caused in the prior art.
In order to solve the problems, the invention adopts the following technical scheme:
the utility model provides a zinc-manganese single flow battery, includes battery jar, positive plate, negative pole piece, circulation pond, inlet, liquid outlet, purification tank, the circulation pond passes through the inlet with the battery jar links to each other, the liquid outlet is located the battery jar bottom, with the purification tank links to each other, the purification tank still with the circulation pond links to each other, the liquid outlet with there is filter equipment between the purification tank.
Furthermore, a clamping point is arranged in the battery jar and used for fixing the positive plate and the negative plate, and the clamping point is not in contact with the bottom of the battery jar, so that the bottoms of the positive plate and the negative plate are not in contact with the bottom of the battery jar.
Further, the positive plate is a sheet, net or hole-shaped stainless steel band or foil, the surface of which is coated with a carbon material, and the carbon material comprises at least one of SP, acetylene black, graphene, carbon nanotubes and carbon fibers.
Further, the positive plate is a non-conductive substrate made of foamed metal, carbon paper, carbon cloth, carbon felt or carbon-coated materials, the non-conductive substrate comprises foamed plastic, honeycomb paper boards, dust-free paper and pulp layer paper, and the carbon materials comprise at least one of SP, acetylene black, graphene, carbon nanotubes and carbon fibers.
Further, the negative plate is a pure zinc foil, a zinc alloy or a zinc powder load current collector, and the zinc alloy comprises, by mass, 93-95%: 4-5%: 0.02-0.05%: 0.8-1.2% of zinc, aluminum, indium and bismuth, and the current collector is foamed nickel or a tin-plated copper net.
Further, the surface of the negative plate is provided with a coating material, the coating material is alumina, kaolin or graphene, and the thickness of the coating material is 5-20 μm.
Further, the battery jar is equipped with the detector, the liquid outlet is equipped with the valve, when the detector detects electrolyte content in the battery jar reaches the setting value, the valve is opened.
Further, the battery jar still links to each other with the fluid infusion pond through fluid infusion mouth.
Further, the detector can also detect the concentration of the electrolyte in the battery jar, and when the content or the concentration of the electrolyte is different from a set value, the electrolyte in the fluid infusion pool is input into the battery jar from the fluid infusion port through the pump.
Further, the electrolyte is an aqueous electrolyte and comprises 0.1-3 mol/L of zinc sulfate, zinc nitrate or zinc acetate, 0.1-3 mol/L of manganese sulfate, manganese nitrate or manganese acetate and a low-temperature additive, the low-temperature additive is lithium chloride, DMSO or EG, the addition amount of the lithium chloride is 0.1-4 mol/L, and the mass percentage of the DMSO or EG to water is 20-70% to 30-80%.
Compared with the prior art, the invention has at least the following beneficial effects:
1. according to the zinc-manganese single flow battery provided by the invention, the electrolyte circularly flows among the circulating pool, the battery tank and the purifying pool, solid substances are intercepted and filtered by the filtering device, the purified electrolyte passes through the purifying pool and then returns to the circulating pool, a good and stable state is ensured to be kept in the circulating process of the electrolyte, the positive and negative pole pieces are not influenced by side reaction products, and active substances existing in an ion form can fully react on the surfaces of the positive and negative poles.
2. The zinc-manganese single flow battery provided by the invention consumes Zn due to the shedding of the active material manganese dioxide in the charging stage and the side reaction products2+The concentration of active ions is reduced, the electrolyte content is lost in the process of discharging solid matters and the process of operating the battery, the active ions are supplemented for the zinc-manganese single flow battery through the detector and the liquid supplementing battery, the circulation stability of the battery is favorably maintained, and the capacity retention rate of the battery is more than 90% after the battery is circulated for thousands of times.
3. According to the zinc-manganese single flow battery provided by the invention, the surface of the positive plate is coated with the carbon material with large specific surface area, and a large number of sites are provided for active ions Mn in the electrolyte2+In addition, the carbon material also enhances the conductivity of the positive plate and provides protection and support for the positive plate substrate.
4. The surface coating of the zinc-manganese single flow battery provided by the invention effectively guides Zn2+The electrodeposition action on the negative electrode eliminates the formation and growth of zinc dendrites, so that the negative electrode shows excellent dendrite-free zinc stripping/plating action, and the aluminum, indium and bismuth in the zinc alloy negative electrode can effectively reduce the generation of side reaction products, particularly prevent the formation of side reaction productsThe generation of irreversible side reaction products is stopped.
5. According to the zinc-manganese single flow battery provided by the invention, the low-temperature additive is added into the electrolyte, the freezing point of the electrolyte is reduced, and Zn is realized under the low-temperature condition2+The capacity of the battery is kept stable due to the content of the electrolyte, particularly the content and the state of the ionic active substances, and the battery is favorable for being suitable for the outdoor environment with large-scale energy storage and complex application.
6. The zinc-manganese single flow battery provided by the invention has the advantages of simple manufacturing process, low cost, safety, environmental protection and the like, is stable in circulation and high in coulomb efficiency, and positive and negative pole pieces inserted into a battery jar can be replaced according to the battery condition, so that the zinc-manganese single flow battery is suitable for being applied to the field of energy storage to realize large-scale application and industrial production.
Drawings
Fig. 1 is a schematic structural diagram of a zinc-manganese single flow battery of the present invention.
Fig. 2 is a curve of capacity retention rate of the zinc-manganese single flow battery of example 1 in the present invention.
Fig. 3 is a coulombic efficiency curve of the zinc-manganese single flow battery of example 1 of the present invention.
Fig. 4 is a cycle curve of the zinc-manganese single flow battery of example 2 of the present invention.
Fig. 5 is a curve of capacity retention rate of the zinc-manganese single flow battery of example 2 of the present invention.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
The invention is further described below with reference to fig. 1.
As shown in fig. 1, the zinc-manganese single flow battery includes a battery jar 1, a positive plate 2, a negative plate 3, a clamping point 4, a circulation tank 5, a pump 61, a pump 62, a pump 63, a pump 64, a liquid inlet 7, a liquid outlet 8, a purification tank 9, a filtering device 10, a detector 11, a liquid replenishing tank 12, a liquid replenishing port 13, and a valve 14.
Electrolyte in the circulation pool 5 is input into the battery jar 1 from the liquid inlet 7 through the pump 61, when the detector 11 detects that the content of the electrolyte in the battery jar 1 reaches a set value, the valve 14 is opened, the electrolyte passes through the pump 62 from the battery jar 1, sequentially passes through the liquid outlet 8 and the filtering device 10 and is input into the purification pool 9, and then is input into the circulation pool 5 from the purification pool 9 through the pump 63, so that complete circulation flow is formed, and the electrolyte in the liquid supplementing pool 12 is supplemented into the battery jar 1 through the pump 64.
Example 1
The positive plate is a stainless steel foil, the surface of the positive plate is coated with SP, the negative plate is a zinc foil, the surface of the negative plate is coated with a 10-micron aluminum oxide coating, and the electrolyte comprises 1mol/L zinc sulfate, 1mol/L manganese sulfate and 0.1mol/L lithium chloride as a low-temperature additive.
The curve of capacity retention rate of the zinc-manganese single flow battery in example 1 is shown in FIG. 2, and 15mA/cm2The capacity retention rate is more than 90 percent when the battery is cycled for 100 circles, and as shown in figure 3, the coulombic efficiency is more than 90 percent.
Example 2
The positive plate is a punched stainless steel strip, the surface of the positive plate is coated with graphene, and the positive plate comprises 94.75% of zinc, aluminum, indium and bismuth in percentage by mass: 4%: 0.05%: 1.2 percent of zinc alloy is taken as a negative plate, a 5 mu m aluminum oxide coating is coated on the surface of the zinc alloy negative plate, electrolyte comprises 0.1mol/L zinc sulfate, 0.5mol/L manganese sulfate and EG which is taken as a low-temperature additive, and the mass percentage of EG to water is 70 percent to 30 percent.
As shown in FIGS. 4 and 5, the zinc-manganese single flow battery of example 2 was operated at 5mA/cm2The current density of the discharge tube is discharged, and the specific discharge capacity of the first circle is about 3.4mAh/cm2After 1000 cycles, the specific discharge capacity is about 2.5mAh/cm2The capacity retention was about 75%.
Example 3
The positive plate is carbon cloth, the zinc powder loaded foam nickel is used as a negative plate, a 15-micron kaolin coating is coated on the surface of the negative plate, and the electrolyte comprises 3mol/L zinc sulfate, 3mol/L manganese sulfate and 4mol/L lithium chloride as a low-temperature additive.
Example 4
The positive plate is made of dust-free paper, the surface of the positive plate is coated with a carbon nano tube, the surface of the negative plate is coated with a graphene coating with the thickness of 20 mu m, the electrolyte comprises 1mol/L zinc sulfate and 0.1mol/L manganese sulfate, DMSO is used as a low-temperature additive, and the mass percentage of the DMSO to water is 20% to 80%.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The utility model provides a zinc-manganese single flow battery, includes battery jar, positive plate, negative pole piece, circulation pond, inlet, liquid outlet, purification tank, its characterized in that, the circulation pond passes through the inlet with the battery jar links to each other, the liquid outlet is located the battery jar bottom, with the purification tank links to each other, the purification tank still with the circulation pond links to each other, the liquid outlet with there is filter equipment between the purification tank.
2. The zinc-manganese single flow battery according to claim 1, wherein said battery container has a locking point, said locking point fixes said positive plate and said negative plate, and said locking point does not contact with the bottom of said battery container, so that the bottoms of said positive plate and said negative plate do not contact with the bottom of said battery container.
3. The zinc-manganese single flow battery according to claim 1, wherein said positive electrode sheet is a sheet-like, mesh-like or porous stainless steel strip or foil, and is coated with a carbon material including at least one of SP, acetylene black, graphene, carbon nanotubes and carbon fibers.
4. The zinc-manganese single flow battery according to claim 1, wherein said positive plate is a non-conductive substrate of foamed metal, carbon paper, carbon cloth, carbon felt or carbon coated material, said non-conductive substrate comprises foamed plastic, honeycomb paper board, dust-free paper, pulp paper, and said carbon material comprises at least one of SP, acetylene black, graphene, carbon nanotubes and carbon fibers.
5. The zinc-manganese single flow battery of claim 1, wherein the negative plate is a pure zinc foil, a zinc alloy or a zinc powder load current collector, and the zinc alloy comprises, by mass, 93-95%: 4-5%: 0.02-0.05%: 0.8-1.2% of zinc, aluminum, indium and bismuth, and the current collector is foamed nickel or a tin-plated copper net.
6. The zinc-manganese single flow battery according to claim 1, wherein the surface of the negative plate is coated with a coating material, and the coating material is alumina, kaolin or graphene, and has a thickness of 5-20 μm.
7. The zinc-manganese single flow battery according to claim 1, wherein said battery container is provided with a detector, said liquid outlet is provided with a valve, and said valve is opened when said detector detects that the electrolyte content in said battery container reaches a set value.
8. The zinc-manganese single flow battery according to claim 7, wherein a fluid replenishing battery is provided, and the fluid replenishing battery is connected with the battery jar through a fluid replenishing port.
9. The zinc-manganese single flow battery according to claim 8, wherein the detector is further capable of detecting the concentration of the electrolyte in the battery container, and when the concentration or the content of the electrolyte is different from a set value, the electrolyte in the fluid replenishing battery is input into the battery container from the fluid replenishing port through the pump.
10. The zinc-manganese single flow battery according to any one of claims 1 to 9, wherein the electrolyte is an aqueous electrolyte comprising 0.1 to 3mol/L of zinc sulfate, zinc nitrate or zinc acetate, 0.1 to 3mol/L of manganese sulfate, manganese nitrate or manganese acetate, and a low-temperature additive, the low-temperature additive is lithium chloride, DMSO or EG, the addition amount of the lithium chloride is 0.1 to 4mol/L, and the mass percentage of the DMSO or EG to water is 20 to 70% to 30 to 80%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110134593.0A CN112531192A (en) | 2021-02-01 | 2021-02-01 | Zinc-manganese single flow battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110134593.0A CN112531192A (en) | 2021-02-01 | 2021-02-01 | Zinc-manganese single flow battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116130672A (en) * | 2022-10-08 | 2023-05-16 | 江苏大学 | Zinc powder negative electrode of zinc-manganese quasi-solid state flow battery and semi-dry method electrode manufacturing method thereof |
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