CN113956498A - Polyolefin-based conductive plastic for all-vanadium redox flow battery and preparation method thereof - Google Patents
Polyolefin-based conductive plastic for all-vanadium redox flow battery and preparation method thereof Download PDFInfo
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- CN113956498A CN113956498A CN202111345312.2A CN202111345312A CN113956498A CN 113956498 A CN113956498 A CN 113956498A CN 202111345312 A CN202111345312 A CN 202111345312A CN 113956498 A CN113956498 A CN 113956498A
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- 239000004033 plastic Substances 0.000 title claims abstract description 40
- 229920003023 plastic Polymers 0.000 title claims abstract description 40
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 38
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 150000003254 radicals Chemical class 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- -1 polyethylene Polymers 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000005452 bending Methods 0.000 abstract description 11
- 238000004146 energy storage Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 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
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of bipolar plates for all-vanadium redox flow batteries, and particularly relates to polyolefin-based conductive plastic for all-vanadium redox flow batteries and a preparation method thereof. The invention aims to provide polyolefin-based conductive plastic for an all-vanadium redox flow battery and a preparation method thereof. The polyolefin-based conductive plastic for the all-vanadium redox flow battery is prepared by uniformly mixing 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator, then uniformly melting and blending the mixture with 30-50 parts of polyolefin at the temperature of 150-. When the prepared conductive plastic is manufactured into a bipolar plate, the resistivity is 5-87m omega cm, the bending strength is 40-51MPa, and the tensile strength is 29-42 MPa.
Description
Technical Field
The invention belongs to the technical field of bipolar plates for all-vanadium redox flow batteries, and particularly relates to polyolefin-based conductive plastic for all-vanadium redox flow batteries and a preparation method thereof.
Background
With the global energy revolution and the advancement of energy transformation, renewable green energy is rapidly developed. However, the power generation modes such as wind power generation, photovoltaic power generation and the like are greatly influenced by natural factors such as weather and the like, so that the power output is unstable, the operation load of a power grid is increased, and phenomena such as 'garbage electricity' and 'electricity abandon' are often caused. In order to popularize and use new energy, the aim of double carbon is fulfilled, and energy storage becomes a good solution. The peak clipping and valley filling of the power grid can be realized through energy storage, and the stable operation of the power grid is ensured. In the existing energy storage facilities, physical energy storage modes such as water pumping energy storage, compressed air energy storage, flywheel energy storage and the like are greatly limited by geographical conditions, and a plurality of places cannot be arranged. The chemical energy storage has the advantages of being rapid in arrangement, controllable in scale and the like. The all-vanadium 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 all-vanadium redox flow battery system is the core and is composed of an electrode, a liquid 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 suggests that conductive plastics based on graphite filling are the most suitable materials for all vanadium flow battery bipolar plates. Wherein the graphite filler provides a complete conductive path and the plastic serves as physical support and corrosion protection. In order to improve the electrical conductivity of the bipolar plate, a higher graphite filling amount is often required, resulting in poor mechanical properties of the whole material. How to realize the balance of conductivity and mechanical properties is a difficult problem for preparing the bipolar plate for the high-performance all-vanadium redox flow battery.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the polyolefin-based conductive plastic for the all-vanadium redox flow battery and the preparation method thereof, and the conductive plastic can simultaneously meet the requirements on conductivity and mechanical property.
The invention solves the first technical problem of providing polyolefin-based conductive plastic for all-vanadium redox flow batteries, which comprises the following raw materials in parts by mass: 30-50 parts of polyolefin, 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator.
Wherein the polyolefin is polyethylene or polypropylene.
The free radical initiator is benzoyl peroxide, dicumyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile or azobisisoheptonitrile.
Wherein the mesh number of the expanded graphite is more than 100 meshes.
The second technical problem to be solved by the invention is to provide a preparation method of the polyolefin-based conductive plastic for the all-vanadium redox flow battery, which comprises the following steps:
and (2) uniformly mixing 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator, then uniformly melting and blending with 30-50 parts of polyolefin at the temperature of 150-260 ℃, and extruding and granulating to obtain the high-performance high-temperature-resistant high-performance polyolefin.
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: according to the invention, through a free radical initiation reaction, the expanded graphite and the polyolefin substrate are subjected to a grafting reaction, so that the compatibility of two phases is promoted, a more uniform dispersion system is formed, and a better conductive system is formed. In addition, compared with graphite, the expanded graphite is softer, the damage effect on the polyolefin substrate is relatively small after the expanded graphite is added as a solid filler, the stress concentration effect brought by the solid filler can be weakened to a certain extent, and the mechanical property of the polyolefin substrate is maintained. Meanwhile, due to the action of the free radical initiator, the polyolefin has higher rigidity and mechanical stability after being converted into the micro-crosslinked polyolefin. When the conductive plastic prepared by the invention is made into a bipolar plate, the resistivity is 5-87m omega cm, the bending strength is 40-51MPa, and the tensile strength is 29-42 MPa.
Drawings
FIG. 1 is an electron micrograph of a sample prepared according to example 1 of the present invention.
Detailed Description
The expanded graphite is a loose and porous vermicular substance obtained by intercalating, washing, drying and high-temperature expanding natural graphite flakes. Compared with natural graphite, the expanded graphite is softer, has the characteristics of certain compression resilience and the like, and is favorable for improving the mechanical property of the expanded graphite when the expanded graphite is compounded with a base material. Meanwhile, the surface of the material has partial active groups, and chemical modification can be carried out.
Therefore, the invention provides polyolefin-based conductive plastic for an all-vanadium redox flow battery, which comprises the following raw materials in parts by mass: 30-50 parts of polyolefin, 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator.
When the conductive plastic prepared by the invention is made into a bipolar plate, the resistivity is 5-87m omega cm, the bending strength is 40-51MPa, and the tensile strength is 29-42 MPa.
The polyolefin referred to in the present invention means polyethylene and polypropylene.
The free radical initiator refers to one of benzoyl peroxide, dicumyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile and azobisisoheptonitrile.
According to the invention, by adding the free radical initiator and carrying out free radical initiation reaction, the expanded graphite and the polyolefin substrate are subjected to grafting reaction, so that the compatibility of two phases is promoted, a more uniform dispersion system is formed, and a better conductive system is formed. Meanwhile, due to the action of the free radical initiator, the polyolefin has higher rigidity and mechanical stability after being converted into the micro-crosslinked polyolefin.
The invention provides a preparation method of the conductive plastic, which is characterized in that 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator are uniformly mixed by a high-speed mixer, then are melted and uniformly blended with 30-50 parts of polyolefin at the temperature of 150-.
The conductive plastic is prepared by melting and blending polyolefin, expanded graphite and a free radical initiator. 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
Taking 70 parts of expanded graphite and 0.1 part of benzoyl peroxide, and uniformly mixing by using a high-speed stirrer. Then the mixture is melted and blended evenly with 30 parts of polypropylene at 260 ℃, and then 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 5m omega cm, the bending strength is 40MPa, and the tensile strength is 29 MPa.
FIG. 1 is an electron micrograph of a sample prepared according to example 1 of the present invention. From the figure, it can be seen that the two phases are tightly combined without significant agglomeration, demonstrating good dispersibility between the expanded graphite and the polyolefin.
Example 2
60 parts of expanded graphite and 0.2 part of benzoyl peroxide are uniformly mixed by using a high-speed stirrer. Then, the mixture is melted and blended evenly with 40 parts of polypropylene at 210 ℃, and then 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 28m omega cm, the bending strength is 44MPa, and the tensile strength is 36 MPa.
Example 3
50 parts of expanded graphite and 0.3 part of dicumyl peroxide are uniformly mixed by using a high-speed stirrer. Then, the mixture is melted and blended evenly with 50 parts of polypropylene at the temperature of 150 ℃, and then 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 87m omega cm, the bending strength is 51MPa, and the tensile strength is 42 MPa.
Example 4
And uniformly mixing 65 parts of expanded graphite and 0.8 part of azodiisobutyronitrile by using a high-speed stirrer. And then, uniformly melting and blending the mixture with 35 parts of polyethylene at 245 ℃, and then pelletizing 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 18m omega cm, the bending strength is 41MPa, and the tensile strength is 32 MPa.
Example 5
55 parts of expanded graphite and 1.0 part of azobisisoheptonitrile are uniformly mixed by a high-speed mixer. Then, the mixture is melted and blended with 45 parts of polyethylene at 225 ℃ uniformly, and then 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 43m omega cm, the bending strength is 43MPa, and the tensile strength is 33 MPa.
Example 6
And uniformly mixing 62 parts of expanded graphite and 0.4 part of potassium persulfate by using a high-speed stirrer. Then, the mixture is melted and blended with 38 parts of polyethylene at 240 ℃ uniformly, and then 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 29m omega cm, the bending strength is 42MPa, and the tensile strength is 32 MPa.
Example 7
And uniformly mixing 56 parts of expanded graphite and 0.6 part of ammonium persulfate by using a high-speed stirrer. Then the mixture is melted and blended evenly with 42 parts of polypropylene at 180 ℃, and then 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 36m omega cm, the bending strength is 46MPa, and the tensile strength is 37 MPa.
Comparative example 1
And (3) melting and uniformly blending 50 parts of expanded graphite and 50 parts of polypropylene at 150 ℃, and then pelletizing 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 236m omega cm, the bending strength is 43MPa, and the tensile strength is 35 MPa.
Claims (6)
1. The polyolefin-based conductive plastic for the all-vanadium redox flow battery is characterized in that: the material comprises the following raw materials in percentage by mass: 30-50 parts of polyolefin, 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator.
2. The polyolefin-based conductive plastic for all-vanadium flow batteries according to claim 1, characterized in that: the polyolefin is polyethylene or polypropylene.
3. The polyolefin-based conductive plastic for all-vanadium flow batteries according to claim 1 or 2, characterized in that: the free radical initiator is benzoyl peroxide, dicumyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile or azobisisoheptonitrile.
4. The polyolefin-based conductive plastic for all-vanadium flow batteries according to any one of claims 1 to 3, wherein: the mesh number of the expanded graphite is more than 100 meshes.
5. The method for preparing the conductive plastic for the polyolefin-based all-vanadium flow battery of any one of claims 1 to 4, wherein: the method comprises the following steps:
and (2) uniformly mixing 50-70 parts of expanded graphite and 0.1-1 part of free radical initiator, then uniformly melting and blending with 30-50 parts of polyolefin at the temperature of 150-260 ℃, and extruding and granulating to obtain the high-performance high-temperature-resistant high-performance polyolefin.
6. The preparation method of the conductive plastic for the polyolefin-based all-vanadium flow battery according to claim 5, characterized in that: 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 |
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| CN202111345312.2A CN113956498A (en) | 2021-11-15 | 2021-11-15 | Polyolefin-based 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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| CN202111345312.2A CN113956498A (en) | 2021-11-15 | 2021-11-15 | Polyolefin-based conductive plastic for all-vanadium redox flow battery and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080149363A1 (en) * | 2006-12-20 | 2008-06-26 | Suh Joon Han | Semi-Conducting Polymer Compositions for the Preparation of Wire and Cable |
| JP2010090261A (en) * | 2008-10-08 | 2010-04-22 | Tigers Polymer Corp | Rubber composition containing expansive graphite and method of peroxide-crosslinking thereof |
| CN102070830A (en) * | 2010-12-21 | 2011-05-25 | 上海林洋储能科技有限公司 | Highly conductive composite material |
| CN103627089A (en) * | 2013-12-19 | 2014-03-12 | 华东理工大学 | Method for preparing carbon nanotube/expanded graphite/polypropylene conductive composite material |
-
2021
- 2021-11-15 CN CN202111345312.2A patent/CN113956498A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080149363A1 (en) * | 2006-12-20 | 2008-06-26 | Suh Joon Han | Semi-Conducting Polymer Compositions for the Preparation of Wire and Cable |
| JP2010090261A (en) * | 2008-10-08 | 2010-04-22 | Tigers Polymer Corp | Rubber composition containing expansive graphite and method of peroxide-crosslinking thereof |
| CN102070830A (en) * | 2010-12-21 | 2011-05-25 | 上海林洋储能科技有限公司 | Highly conductive composite material |
| CN103627089A (en) * | 2013-12-19 | 2014-03-12 | 华东理工大学 | Method for preparing carbon nanotube/expanded graphite/polypropylene conductive composite material |
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Application publication date: 20220121 |