CN114497617B - Diaphragm for zinc-bromine flow battery and application - Google Patents
Diaphragm for zinc-bromine flow battery and application Download PDFInfo
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- CN114497617B CN114497617B CN202011261119.6A CN202011261119A CN114497617B CN 114497617 B CN114497617 B CN 114497617B CN 202011261119 A CN202011261119 A CN 202011261119A CN 114497617 B CN114497617 B CN 114497617B
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- diaphragm
- glue
- zinc
- projection area
- area
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- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000003292 glue Substances 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 230000005540 biological transmission Effects 0.000 claims abstract description 4
- 238000004026 adhesive bonding Methods 0.000 claims description 17
- 230000002093 peripheral effect Effects 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 abstract description 7
- 230000000903 blocking effect Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Hybrid Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a diaphragm for a zinc-bromine flow battery and application thereof, which can inhibit zinc from growing inwards of the diaphragm, wherein a glue coating is coated on the surface of the diaphragm at the negative electrode side, wherein zinc is easy to grow inwards of the diaphragm, and the glue coating is used for blocking an ion transmission channel, blocking a zinc growth path and inhibiting negative electrode zinc from growing inwards of the diaphragm, so that the cycle life of the battery is prolonged, and the energy density of the battery is improved.
Description
Technical Field
The invention relates to a method for inhibiting zinc from growing into a diaphragm, in particular to a diaphragm for a zinc-bromine flow battery and application of the diaphragm in the zinc-bromine flow battery.
Background
Renewable energy sources such as wind energy and solar energy have the characteristics of discontinuity and instability, and the characteristic can cause impact on a power grid in the grid connection process, so that the safe and stable operation of the power grid is affected. The energy storage technology can ensure the high-efficiency stable operation of the renewable energy power generation grid connection. The energy storage technology is mainly divided into two main types of physical energy storage and chemical energy storage. Redox flow batteries suitable for large-scale and large-capacity energy storage in chemical energy storage are receiving attention because of the advantages of independent battery power and capacity, rapid response, simple structure, easy design and the like. The zinc-bromine flow battery, which is one of redox flow batteries, has the advantages of high open-circuit voltage (1.85V), high theoretical energy density (435 Wh/kg), low price of electrolyte and diaphragm and the like besides the advantages. These advantages also make it more competitive with other flow batteries.
The zinc-bromine flow battery has the problem that zinc grows into a diaphragm along with the increase of the surface capacity in the charging process, the problem can cause the short circuit failure of the battery, so that the cycle life of the battery is influenced, and in addition, the energy density of the battery is reduced due to the limited surface capacity of the battery. Therefore, solving the problem of zinc in-growth into the separator has important effect on prolonging the service life of the battery and improving the energy density of the battery.
The invention comprises the following steps:
the invention aims to solve the problems, and provides a method for inhibiting zinc in-growth of a zinc-bromine flow battery to a diaphragm, which comprises the steps of coating a glue coating on the surface of the diaphragm at the negative electrode side, blocking an ion transmission channel through the coating, blocking a zinc growth path, and inhibiting zinc in-growth of the diaphragm, so that the cycle life of the battery is prolonged, and the energy density of the battery is improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for inhibiting zinc in-growth of zinc bromine flow battery into diaphragm is to coat glue coating on the surface of negative side diaphragm to inhibit zinc in-growth of diaphragm.
The surface of the diaphragm, facing the negative electrode, of the negative electrode on the diaphragm is projected on the surface of the diaphragm, facing the negative electrode, called the projection area,
an annular gluing area is arranged at the projection area, and the annular gluing area is positioned in the projection area and is close to the peripheral edge of the projection area.
The width of the annular gluing area positioned at the peripheral edge of the projection area is 1/100-1/20, preferably 1/50-1/30, more preferably 1/40-1/30 of the distance from the position of the peripheral edge of the corresponding projection area to the geometric center of the projection area.
The annular gluing area is formed by coating a glue coating on the corresponding position of the surface of the diaphragm.
The glue layer or glue coating of the glue area has a thickness of 50-200um, preferably 50-100um.
The glue is one or more than two of acrylic acid type, polyurethane type, silica gel type, epoxy resin type and UV curing type glue.
The membrane is PE porous membrane, and the thickness of the membrane is 200-900um.
The application of the diaphragm in the zinc-bromine flow battery.
The separator with the glue coated face was used facing the negative side.
The zinc-bromine flow battery can inhibit zinc on the cathode of the zinc-bromine flow battery from growing to one side of the diaphragm.
The beneficial results of the invention are:
the invention provides a method for inhibiting zinc from growing into a diaphragm, which solves the problem that the negative electrode zinc grows into the diaphragm to cause battery failure along with the increase of the surface capacity, and improves the cycle life and the energy density of the battery.
The invention relates to a diaphragm for a zinc-bromine flow battery and application thereof, which can inhibit zinc from growing inwards of the diaphragm, wherein a glue coating is coated on the surface of the diaphragm at the negative electrode side, wherein zinc is easy to grow inwards of the diaphragm, and the glue coating is used for blocking an ion transmission channel, blocking a zinc growth path and inhibiting negative electrode zinc from growing inwards of the diaphragm, so that the cycle life of the battery is prolonged, and the energy density of the battery is improved.
Drawings
FIG. 1 is a schematic view of a separator according to the present invention.
Fig. 2 is a graph showing the charge and discharge curves of a battery with and without a glue coating.
Fig. 3 shows the cycling performance of the glue coated battery.
Detailed Description
Example 1
Positive and negative electrolyte respectively 60ml 2mol/LZnBr 2 The single cell comprises a positive electrode end plate, a positive electrode graphite plate, a carbon felt, a diaphragm, a carbon felt, a negative electrode graphite plate and a negative electrode end plate which are sequentially laminated, wherein +3mol/LKCl+0.8M MEP. Charge-discharge current density 40mA/cm 2 . The membrane is PE membrane with average pore diameter of 0.1um and thickness of 900um. The glue is acrylic acid type glue (Shanghai Han dynasty Gao Letai glue, h 3000), and the thickness of the glue is 50um,100um,150um and 200um respectively. The width of the annular gluing area positioned at the peripheral edge of the projection area is 1/40 of the distance from the peripheral edge position of the corresponding projection area to the geometric center of the projection area.
As the thickness of the coating increases, the CE of the battery gradually increases and the VE gradually decreases, mainly because the increase of the coating hinders diffusion of bromine to the negative electrode, reducing self-discharge of the battery and increasing the membrane resistance. The battery performance is optimal when the coating thickness is 100um.
Example 2
Positive and negative electrolyte respectively 60ml 2mol/LZnBr 2 +3mol/LKCl+0.8M MEP, the single cell comprises a positive electrode end plate, a negative electrode end plate, a positive electrode,Positive graphite plate, carbon felt, diaphragm, carbon felt, negative graphite plate, negative end plate. Charge-discharge current density 40mA/cm 2 . The thickness of the diaphragm is 900um;
coating glue on the surface of a diaphragm at the negative electrode side of one battery, wherein the glue is acrylic acid type glue (Shanghai Han dynasty Gao Letai glue, h 3000), the thickness of the coating is 100um, and the width of an annular gluing area positioned at the peripheral edge of a projection area is 1/40 of the distance from the peripheral edge position of the corresponding projection area to the geometric center of the projection area; the other cell negative side separator surface was not coated with glue.
As can be seen from the charge-discharge curve (shown in fig. 2), the charge-discharge curve of the battery with the glue coating is normal, and the battery 150 has stable cycle performance and no obvious attenuation (shown in fig. 3); the battery without the glue coating has the phenomenon of reduced charging voltage when being charged for 3.4 hours, so that the battery cannot normally operate. This is mainly due to zinc ingrowth into the separator, which also results in a lower discharge voltage of the cell compared to the glue coated cell and a reduced discharge capacity. This also shows that the surface capacity of the cell with the glue coating is improved and the energy density of the cell is improved. The energy density of the battery with the glue coating can reach 70Wh/kg, and the energy density of the battery without the glue coating is 30Wh/kg.
Comparative example 1
Positive and negative electrolyte respectively 60ml 2mol/LZnBr 2 The single cell comprises a positive electrode end plate, a positive electrode graphite plate, a carbon felt, a diaphragm, a carbon felt, a negative electrode graphite plate and a negative electrode end plate which are sequentially laminated, wherein +3mol/LKCl+0.8M MEP. Charge-discharge current density 40mA/cm 2 . The thickness of the diaphragm is 900um;
coating glue on the surface of a diaphragm at the negative electrode side of one battery, wherein the glue is acrylic acid type glue (Shanghai Han dynasty Gao Letai glue, h 3000), the thickness of the coating is 100um, and the width of an annular gluing area positioned at the peripheral edge of a projection area is 1/120 of the distance from the peripheral edge position of the corresponding projection area to the geometric center of the projection area; the area of the gluing area is too small, zinc grows into the diaphragm in the battery operation process, and the battery cannot normally operate.
Comparative example 2
Positive and negative electrolyte respectively 60ml 2mol/LZnBr 2 The single cell comprises a positive electrode end plate, a positive electrode graphite plate, a carbon felt, a diaphragm, a carbon felt, a negative electrode graphite plate and a negative electrode end plate which are sequentially laminated, wherein +3mol/LKCl+0.8M MEP. Charge-discharge current density 40mA/cm 2 . The thickness of the diaphragm is 900um;
coating glue on the surface of a diaphragm at the negative electrode side of one battery, wherein the glue is acrylic acid type glue (Shanghai Han dynasty Gao Letai glue, h 3000), the thickness of the coating is 100um, and the width of an annular gluing area positioned at the peripheral edge of a projection area is 1/10 of the distance from the peripheral edge position of the corresponding projection area to the geometric center of the projection area; the area of the gluing area is overlarge, the effective area of the battery is reduced, the energy density of the battery is reduced, and when the width of the annular gluing area at the periphery of the projection area is 1/10 of the distance from the position of the periphery of the corresponding projection area to the geometric center of the projection area, the energy density of the battery is only 40Wh/kg.
Claims (8)
1. The utility model provides a zinc bromine flow battery is with diaphragm, zinc bromine flow battery includes positive pole, diaphragm, the negative pole of parallel arrangement in proper order, its characterized in that:
the surface of the diaphragm, facing the negative electrode, of the negative electrode on the diaphragm is projected on the surface of the diaphragm, facing the negative electrode, called the projection area,
the projection area is provided with an annular gluing area, the annular gluing area is positioned in the projection area and is close to the peripheral edge of the projection area, the annular gluing area can block ion transmission channels and block zinc growth paths, and the width of the annular gluing area positioned at the peripheral edge of the projection area is 1/100-1/20 of the distance from the peripheral edge of the corresponding projection area to the geometric center of the projection area.
2. The membrane of claim 1, wherein,
the width of the annular gluing area positioned at the peripheral edge of the projection area is 1/50-1/30 of the distance from the peripheral edge position of the corresponding projection area to the geometric center of the projection area.
3. The membrane of claim 1, wherein,
the annular gluing area is formed by coating a glue coating on the corresponding position of the surface of the diaphragm.
4. A membrane according to claim 1, 2 or 3, characterized in that the glue layer or glue coating of the glue area has a thickness of 50-200um.
5. The membrane of claim 4, wherein the glue is one or more of acrylic type, polyurethane type, silicone type, epoxy type, UV curable glue.
6. A membrane according to claim 1 or 3, characterized in that the membrane is a PE porous membrane, the membrane thickness being 200-900um.
7. Use of the separator of any one of claims 1-6 in a zinc bromine flow battery.
8. The use according to claim 7, wherein the separator glue coated face is used facing the negative side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011261119.6A CN114497617B (en) | 2020-11-12 | 2020-11-12 | Diaphragm for zinc-bromine flow battery and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011261119.6A CN114497617B (en) | 2020-11-12 | 2020-11-12 | Diaphragm for zinc-bromine flow battery and application |
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| Publication Number | Publication Date |
|---|---|
| CN114497617A CN114497617A (en) | 2022-05-13 |
| CN114497617B true CN114497617B (en) | 2023-11-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05109435A (en) * | 1991-05-24 | 1993-04-30 | Nippon Telegr & Teleph Corp <Ntt> | Cylinder type nonaqueous electrolytic secondary battery |
| US6815114B1 (en) * | 1999-05-28 | 2004-11-09 | Heliocentris Energiesysteme Gmbh | Membrane electrode unit for fuel cells and the like |
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| CN110144726A (en) * | 2019-05-16 | 2019-08-20 | 东华大学 | Heat cross-linking polyvinyl alcohol/Lithium polyacrylate fibre diaphragm of fast lithium ion transmission and its preparation and application |
| CN111261913A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN111477815A (en) * | 2020-04-03 | 2020-07-31 | 陈璞 | Porous diaphragm and preparation method and application thereof |
| CN111613822A (en) * | 2020-05-13 | 2020-09-01 | 长沙理工大学 | Low-cost zinc-iron flow battery pile |
-
2020
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| JPH05109435A (en) * | 1991-05-24 | 1993-04-30 | Nippon Telegr & Teleph Corp <Ntt> | Cylinder type nonaqueous electrolytic secondary battery |
| US6815114B1 (en) * | 1999-05-28 | 2004-11-09 | Heliocentris Energiesysteme Gmbh | Membrane electrode unit for fuel cells and the like |
| CN105280942A (en) * | 2014-07-01 | 2016-01-27 | 北京好风光储能技术有限公司 | Lithium double-fluid flow battery |
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| CN114497617A (en) | 2022-05-13 |
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