CN113980377A - Conductive plastic for all-vanadium redox flow battery and preparation method thereof - Google Patents
Conductive plastic for all-vanadium redox flow battery and preparation method thereof Download PDFInfo
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- CN113980377A CN113980377A CN202111345315.6A CN202111345315A CN113980377A CN 113980377 A CN113980377 A CN 113980377A CN 202111345315 A CN202111345315 A CN 202111345315A CN 113980377 A CN113980377 A CN 113980377A
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- 239000004033 plastic Substances 0.000 title claims abstract description 30
- 229920003023 plastic Polymers 0.000 title claims abstract description 30
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims abstract description 17
- 229920000098 polyolefin Polymers 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- -1 polyethylene Polymers 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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Abstract
The invention belongs to the technical field of bipolar plate materials of all-vanadium redox flow batteries, and particularly relates to conductive plastic for an all-vanadium redox flow battery and a preparation method thereof. The invention aims to provide conductive plastic for an all-vanadium redox flow battery and a preparation method thereof. The conductive plastic for the all-vanadium redox flow battery is prepared by mixing 20-40 parts of expanded graphite and 6-10 parts of maleic anhydride grafted polyolefin, then melting and blending with 50-80 parts of polyolefin, and extruding and granulating. The resistivity of the bipolar plate prepared from the conductive plastic is 108-437m omega cm, the bending strength is 33-39MPa, and the tensile strength is 27-31 MPa.
Description
Technical Field
The invention belongs to the technical field of bipolar plate materials of all-vanadium redox flow batteries, and particularly relates to conductive plastic for an all-vanadium redox flow battery and a preparation method thereof.
Background
With the global energy revolution, the utilization ratio of renewable clean energy is gradually increasing. Especially, the proposal of the 'double carbon' target requires the use of green and clean energy. Wind and solar energy are the fastest growing renewable energy sources. However, when the power generation device is used, the power generation device is limited by external environmental factors, so that the power output is unstable and discontinuous, the unstable characteristic can generate larger impact on a power grid, and the cost performance of new energy power generation is reduced. Therefore, it is necessary to configure corresponding energy storage devices in the power grid to implement peak clipping and valley filling.
The currently common energy storage technologies mainly include physical energy storage modes such as water pumping energy storage, compressed air energy storage, flywheel energy storage and the like, and chemical energy storage modes such as battery energy storage and the like. In physical energy storage, the construction of water pumping energy storage, compressed air energy storage and flywheel energy storage is seriously limited by geographical site selection and ecological environment. The chemical energy storage includes modes of sodium-sulfur battery energy storage, lithium ion battery energy storage, lead-acid battery energy storage, redox flow and the like, and each mode has characteristics. Compared with other energy storage technologies, the redox flow battery has the advantages of safety, reliability, environmental friendliness, certain overload and deep discharge capacity and the like, and has unique advantages in the energy storage technology.
The galvanic pile in the vanadium flow battery system is the core and is composed of electrodes, a flow frame, an ion exchange membrane, a bipolar plate, an end plate and the like. The bipolar plate mainly has the functions of isolating positive and negative electrolytes and forming a current path. Since the electrolyte in the all-vanadium flow battery is an acidic aqueous solution, the bipolar plate must have good acid resistance and corrosion resistance. Current research considers bipolar plates made based on graphite to be the most cost effective solution. Wherein graphite mainly provides a complete conductive path, and the plastic plays a role in physical support and corrosion resistance. Generally, a bipolar plate having a high graphite content is required for practical use, but this makes it difficult to satisfy the mechanical properties of the bipolar plate. Therefore, how to balance the conductivity and mechanical properties of the bipolar plate is a difficult problem which hinders the application of all-vanadium flow batteries at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the conductive plastic for the all-vanadium redox flow battery and the preparation method thereof, and the material has high conductivity and excellent mechanical property.
The invention solves the first technical problem of providing conductive plastic for an all-vanadium redox flow battery, which comprises the following raw materials in parts by mass: 50-80 parts of polyolefin, 6-10 parts of maleic anhydride grafted polyolefin and 20-40 parts of expanded graphite.
Wherein the polyolefin is at least one of polyethylene, polypropylene or ethylene-propylene copolymer.
The second technical problem to be solved by the invention is to provide a preparation method of the conductive plastic for the all-vanadium redox flow battery, which comprises the following steps:
mixing 20-40 parts of expanded graphite and 6-10 parts of maleic anhydride grafted polyolefin, then melting and blending with 50-80 parts of polyolefin at the temperature of 140 ℃ and 260 ℃, and extruding and granulating to obtain the composite material.
Wherein the mixing time of the expanded graphite and the maleic anhydride grafted polyolefin is 5-10 minutes.
Wherein the mixing speed of the expanded graphite and the maleic anhydride grafted polyolefin is not less than 500 rpm.
The melt blending mode is banburying mixing and single-screw extrusion granulation or double-screw mixing and single-screw extrusion granulation.
Has the advantages that: the invention firstly adopts maleic anhydride grafted polyolefin and expanded graphite to carry out high-speed mixing, and the heat generated by self-friction promotes the reaction of maleic anhydride on the maleic anhydride grafted polyolefin and active groups such as hydroxyl on the surface of the expanded graphite, thereby forming the polyolefin grafted modified expanded graphite. Therefore, the compatibility of the expanded graphite and the polyolefin is greatly improved, the expanded graphite is more uniformly dispersed in the polyolefin substrate, the formation of a conductive channel is facilitated, and the improvement of the conductivity of the material is promoted.
The expanded graphite modified by maleic anhydride grafted polyolefin has good compatibility with the base material, and the damage of the uneven distribution of rigid solid powder to the mechanical property of the base material is reduced. Meanwhile, compared with conductive fillers such as graphite, the expanded graphite has better flexibility and is beneficial to keeping the mechanical property of the base material. Therefore, the invention can obtain the bipolar plate material with excellent mechanical property.
Compared with the prior art, the bipolar plate prepared from the conductive plastic has the resistivity of 108-437m omega cm, the bending strength of 33-39MPa and the tensile strength of 27-31 MPa. The invention can reduce the consumption of the conductive filler, can realize the flow line production and has process economy.
Drawings
FIG. 1 is an electron micrograph of a sample prepared according to example 3 of the present invention.
Detailed Description
The invention firstly provides conductive plastic for an all-vanadium redox flow battery, which comprises the following raw materials in parts by mass: 50-80 parts of polyolefin, 6-10 parts of maleic anhydride grafted polyolefin and 20-40 parts of expanded graphite.
Wherein the polyolefin is at least one of polyethylene, polypropylene or ethylene-propylene copolymer.
The invention firstly adopts maleic anhydride grafted polyolefin and expanded graphite to carry out high-speed mixing, and the heat generated by self-friction promotes the reaction of maleic anhydride on the maleic anhydride grafted polyolefin and active groups such as hydroxyl on the surface of the expanded graphite, thereby forming the polyolefin grafted modified expanded graphite. Therefore, the compatibility of the expanded graphite and the polyolefin is greatly improved, the expanded graphite is more uniformly dispersed in the polyolefin substrate, the formation of a conductive channel is facilitated, and the improvement of the conductivity of the material is promoted.
The expanded graphite modified by maleic anhydride grafted polyolefin has good compatibility with the base material, and the damage of the uneven distribution of rigid solid powder to the mechanical property of the base material is reduced. Meanwhile, compared with conductive fillers such as graphite, the expanded graphite has better flexibility and is beneficial to keeping the mechanical property of the base material. Therefore, the invention can obtain the bipolar plate material with excellent mechanical property.
The invention also provides a preparation method of the conductive plastic for the all-vanadium redox flow battery, which comprises the following steps:
mixing 20-40 parts of expanded graphite and 6-10 parts of maleic anhydride grafted polyolefin at a high speed of not less than 500rpm for 5-10 minutes, then melt blending with 50-80 parts of polyolefin at the temperature of 140 ℃ and 260 ℃, and extruding and granulating.
The melt blending mode can be banburying mixing and single screw extrusion granulation, or double screw mixing and single screw extrusion granulation. The bipolar plate is prepared by conventional extrusion molding or hot press molding.
The present disclosure will be further explained and illustrated with reference to specific embodiments. The parts of materials in the following specific examples are all parts by mass.
Example 1
6 parts of maleic anhydride-grafted polyethylene and 20 parts of expanded graphite were mixed with a high-speed mixer at 600rpm for 5 minutes. And then the mixture is melted and blended with 74 parts of polyethylene at 160 ℃ by using a machine, and the mixture is cut into particles to obtain the conductive plastic for the bipolar plate.
After the conductive plastic is pressed into the bipolar plate, the resistivity of the bipolar plate is 437m omega cm, the bending strength is 33MPa, and the tensile strength is 31 MPa.
Example 2
8 parts of maleic anhydride-grafted polypropylene and 30 parts of expanded graphite were mixed for 6 minutes at 500rpm using a high-speed mixer. And then, uniformly melting and blending the mixture with 62 parts of polypropylene at 180 ℃ by using a machine, and then pelletizing to obtain the conductive plastic for the all-vanadium redox flow battery.
After the conductive plastic is pressed into the bipolar plate, the resistivity of the bipolar plate is 285m omega cm, the bending strength is 36MPa, and the tensile strength is 30 MPa.
Example 3
10 parts of maleic anhydride-grafted polyethylene and 40 parts of expanded graphite were mixed with a high-speed mixer at 700rpm for 7 minutes. And then, uniformly melting and blending the mixture with 50 parts of polyethylene at 200 ℃ by using a machine, and then pelletizing to obtain the conductive plastic for the all-vanadium redox flow battery.
After the conductive plastic is pressed into the bipolar plate, the resistivity of the bipolar plate is 108m omega cm, the bending strength is 39MPa, and the tensile strength is 27 MPa.
FIG. 1 is an electron micrograph of the sample prepared in example 3. From the figure it can be seen that the two phases are tightly bound with no significant agglomeration.
Example 4
9 parts of maleic anhydride-grafted polyethylene and 25 parts of expanded graphite were mixed with a high-speed mixer at 600rpm for 10 minutes. And then, uniformly melting and blending the mixture with 66 parts of polypropylene at 260 ℃ by using a machine, and then pelletizing to obtain the conductive plastic for the all-vanadium redox flow battery.
After the conductive plastic is pressed into the bipolar plate, the resistivity of the bipolar plate is 314m omega cm, the bending strength is 38MPa, and the tensile strength is 31 MPa.
Comparative example 1
And taking 60 parts of polypropylene and 40 parts of expanded graphite, mechanically stirring and uniformly mixing, melting and uniformly blending at 180 ℃ by using a machine, and granulating to obtain the conductive plastic for the all-vanadium redox flow battery.
After the conductive plastic is pressed into the bipolar plate, the resistivity of the bipolar plate is 532m omega cm, the bending strength is 35MPa, and the tensile strength is 24 MPa.
Claims (6)
1. Conductive plastic for all-vanadium flow batteries, characterized in that: the material comprises the following raw materials in percentage by mass: 50-80 parts of polyolefin, 6-10 parts of maleic anhydride grafted polyolefin and 20-40 parts of expanded graphite.
2. The conductive plastic for the all-vanadium flow battery according to claim 1, wherein: the polyolefin is at least one of polyethylene, polypropylene or ethylene-propylene copolymer.
3. The preparation method of the conductive plastic for the all-vanadium flow battery, according to claim 1 or 2, is characterized in that: the method comprises the following steps:
mixing 20-40 parts of expanded graphite and 6-10 parts of maleic anhydride grafted polyolefin, then melting and blending with 50-80 parts of polyolefin at the temperature of 140 ℃ and 260 ℃, and extruding and granulating to obtain the composite material.
4. The preparation method of the conductive plastic for the all-vanadium flow battery according to claim 3, characterized by comprising the following steps: the mixing time of the expanded graphite and the maleic anhydride grafted polyolefin is 5-10 minutes.
5. The preparation method of the conductive plastic for the all-vanadium flow battery according to claim 3 or 4, characterized by comprising the following steps of: the mixing speed of the expanded graphite and the maleic anhydride grafted polyolefin is not lower than 500 rpm.
6. The method for preparing the conductive plastic for the all-vanadium flow battery according to any one of claims 3 to 5, wherein: the melt blending mode is banburying mixing and single screw extrusion granulation or double screw mixing and single screw extrusion granulation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111345315.6A CN113980377A (en) | 2021-11-15 | 2021-11-15 | Conductive plastic for all-vanadium redox flow battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111345315.6A CN113980377A (en) | 2021-11-15 | 2021-11-15 | Conductive plastic for all-vanadium redox flow battery and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110073799A1 (en) * | 2009-09-30 | 2011-03-31 | Eric Magni | Thermally conductive polymer compositions |
| CN106099121A (en) * | 2016-07-21 | 2016-11-09 | 中国科学院上海高等研究院 | Bipolar plates and its preparation method and application |
| CN111534012A (en) * | 2020-06-15 | 2020-08-14 | 广东电网有限责任公司电力科学研究院 | Polypropylene/graphite conductive composite material and preparation method and application thereof |
-
2021
- 2021-11-15 CN CN202111345315.6A patent/CN113980377A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110073799A1 (en) * | 2009-09-30 | 2011-03-31 | Eric Magni | Thermally conductive polymer compositions |
| CN106099121A (en) * | 2016-07-21 | 2016-11-09 | 中国科学院上海高等研究院 | Bipolar plates and its preparation method and application |
| CN111534012A (en) * | 2020-06-15 | 2020-08-14 | 广东电网有限责任公司电力科学研究院 | Polypropylene/graphite conductive composite material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 何小芳等: "聚丙烯基石墨导电复合材料研究进展", 《中国塑料》 * |
| 侯静等: "溶液插层法制备MHA-g-EG导电纳米复合材料", 《塑料工业》 * |
| 卞军 等: "《聚合物共混改性基础》", 31 January 2018, 西南交通大学出版社 * |
| 李军桦 等: "《塑料配方设计》", 30 September 2019, 中国轻工业出版社 * |
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