CN114824342A - Preparation method of graphite polar plate, fuel cell and vehicle - Google Patents
Preparation method of graphite polar plate, fuel cell and vehicle Download PDFInfo
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- CN114824342A CN114824342A CN202110117848.2A CN202110117848A CN114824342A CN 114824342 A CN114824342 A CN 114824342A CN 202110117848 A CN202110117848 A CN 202110117848A CN 114824342 A CN114824342 A CN 114824342A
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- graphite
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- liquid
- graphite sheet
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 109
- 239000010439 graphite Substances 0.000 title claims abstract description 109
- 239000000446 fuel Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000007723 die pressing method Methods 0.000 claims abstract description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000004299 exfoliation Methods 0.000 claims 2
- 238000005086 pumping Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 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
- H01M8/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
-
- 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
Abstract
The invention relates to the technical field of fuel cells, in particular to a preparation method of a graphite polar plate, the graphite polar plate, a fuel cell and a vehicle, wherein the preparation method comprises the steps of extracting a liquid-phase graphene dispersion liquid through an expanded graphite plate; prepressing expanded graphite into a low-density porous graphite sheet; enabling the liquid-phase graphene dispersion liquid to enter an internal pore channel of the low-density porous graphite sheet and then drying to obtain the graphene composite low-density graphite sheet; carrying out die pressing on the graphene composite low-density graphite sheet; impregnating the pressed graphene composite low-density graphite sheet with resin, and curing and molding; the graphite polar plate obtained by the preparation method has the specific flexibility of resin, ensures excellent conductivity, has low cost and price in the whole preparation process, is simple in process, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a graphite polar plate, a preparation method of the graphite polar plate, a fuel cell and a vehicle.
Background
Energy is an important basis for human survival and development, and at present, traditional non-renewable energy sources such as coal, petroleum, natural gas and the like are still main energy sources. However, the energy sources have limited reserves, low energy conversion efficiency and more secondary pollutants, and cause great harm to the environment. Therefore, the search for new sustainable clean energy is an urgent problem to be solved.
Currently, fuel cell technology is receiving more and more attention due to its advantages of low pollution, high efficiency, wide fuel source, etc., and becomes an energy technology with great prospect in the 21 st century. The fuel cell realizes the conversion from chemical energy to electric energy by respectively carrying out redox reactions on fuel (hydrogen, methanol and the like) and oxide (oxygen) at an anode and a cathode without a heat engine process, so the fuel cell is not limited by Carnot cycle, has high energy conversion efficiency (40-60 percent), and has the characteristics of cleanness, no pollution, no noise, no infrared and the like.
The bipolar plate serves as one of the key components of a fuel cell, and has the main functions of distributing reactant gases, transporting reactant products, collecting and conducting current, supporting a membrane electrode, transferring excess heat, and the like. At present, the polar plate material of the proton exchange membrane fuel cell mainly comprises two types, namely metal and graphite. The graphite polar plate is divided into a machine-carved graphite plate and a mould-pressed graphite plate, wherein the machine-carved graphite plate firstly carbonizes graphite at high temperature, then resin is impregnated to obtain a graphite flat plate, and finally a channel is carved on the flat plate through machining to obtain the graphite plate. Although the graphite polar plate has high strength and good conductivity, the processing is time-consuming and high in cost, and the cost of the fuel cell is not reduced; the mould pressing graphite plate is firstly mould pressed by the expanded graphite through a mould pressing machine, and then resin is impregnated to obtain the mould pressing graphite polar plate. The molded graphite polar plate has simple manufacture and low cost, is suitable for large-scale industrial production, and is the main development direction of the current bipolar plate.
However, the molded graphite electrode plate has the defects that the expanded graphite forms a graphite sheet structure in the molded graphite electrode plate, and discontinuous points are formed between adjacent graphite sheets due to incomplete contact, so that the conduction of current is influenced by the presence of the discontinuous points, and the electrical conductivity is weakened.
Patent CN 109921055 a discloses an ultrathin graphene composite flexible graphite bipolar plate and a preparation method thereof. According to the method, a graphene film is firstly adhered to the outer surface of a flexible graphite polar plate, and then the flexible graphite plate is obtained through mould pressing and polar plate bonding processes. The flexible graphite polar plate prepared by the method has obviously improved gas barrier performance and contact resistance because the outer surface of the flexible graphite polar plate is provided with the ultra-thin compact graphene film. However, since the graphene film is only adhered to the surface, the bulk resistivity is still not effectively improved, and the bipolar plate is continuously subjected to gas purging in the using process, the graphene film with surface viscosity is likely to peel off from the polar plate under long-time purging, so that the problems of flow channel blockage, performance reduction and the like are caused.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the graphite polar plate, the fuel cell and the vehicle are low in price and simple in preparation process.
In order to solve the above technical problems, a first technical solution adopted by the present invention is:
a method for preparing graphite electrode plate includes
Extracting a liquid-phase graphene dispersion liquid through an expanded graphite plate;
prepressing expanded graphite into a low-density porous graphite sheet;
enabling the liquid-phase graphene dispersion liquid to enter an internal pore channel of the low-density porous graphite sheet and then drying to obtain the graphene composite low-density graphite sheet;
carrying out die pressing on the graphene composite low-density graphite sheet;
and impregnating the pressed graphene composite low-density graphite sheet with resin, and curing and molding.
Preferably, the liquid-phase graphene dispersion liquid is obtained from the expanded graphite plate by an ultrasonic stripping method.
Preferably, the step of obtaining the liquid-phase graphene dispersion liquid by the ultrasonic stripping method of the expanded graphite plate comprises
According to the mass ratio of 0.5-1.5: 1, adding expanded graphite into deionized water, and adding a dispersing agent;
carrying out ultrasonic treatment on the prepared mixture, wherein the ultrasonic temperature is 30-50 ℃, the power is 100-300W, and the time is 50-200 h;
and after the ultrasonic treatment is finished, centrifuging the sample, controlling the centrifugal rotation speed to be 5000-10000 rpm, and taking supernatant after centrifuging to obtain the liquid-phase graphene dispersion liquid.
Preferably, the dispersing agent is sodium lignosulfonate, and the concentration of the sodium lignosulfonate is 0.2-2 g/L;
preferably, the density of the low-density porous graphite sheet is 0.05-0.5 g/cm 3 。
Preferably, the low-density porous graphite sheet is immersed in the liquid-phase graphene dispersion liquid for vacuumizing and pressurizing treatment, so that the liquid-phase graphene dispersion liquid enters the inner pore channels of the low-density porous graphite sheet.
Preferably, the graphene composite low-density graphite sheet is molded by a molding press.
In order to solve the above technical problem, the second technical solution adopted by the present invention is:
a graphite polar plate is prepared by the preparation method.
In order to solve the above technical problems, the third technical solution adopted by the present invention is:
a fuel cell comprises a plurality of graphite polar plates.
In order to solve the above technical problems, a fourth technical solution adopted by the present invention is:
a vehicle comprises the graphite polar plate and/or the fuel cell.
The invention has the beneficial effects that: the graphite polar plate obtained by the preparation method has the specific flexibility of resin, ensures excellent conductivity, has low cost and price in the whole preparation process, is simple in process, and is suitable for large-scale industrial production.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Example one
(1) Taking expanded graphite and deionized water according to the mass ratio of 0.5: 1, adding expanded graphite into deionized water, and adding sodium lignosulfonate as a dispersing agent, wherein the concentration of the sodium lignosulfonate is 0.2 g/L;
(2) carrying out ultrasonic treatment on the prepared mixture, controlling the temperature to be 30 ℃, the power to be 100W and the time to be 50 h;
(3) after the ultrasonic treatment is finished, centrifuging the sample, controlling the centrifugal rotating speed to be 5000rpm, and taking supernatant after centrifuging to obtain water-phase graphene dispersion liquid;
(4) prepressing expanded graphite into a low-density graphite plate with the density of 0.05g/cm3, immersing the graphite plate in water-phase graphene dispersion liquid, vacuumizing and pressurizing to enable the graphene dispersion liquid to enter an inner pore channel of the low-density graphite plate, and drying to obtain the graphene composite low-density graphite plate;
(5) and carrying out mould pressing on the graphene composite low-density graphite flake through a mould pressing machine, then impregnating resin, curing and drying to obtain the graphene composite flexible graphite polar plate.
Example two
(1) Taking expanded graphite and deionized water according to the mass ratio of 1: 1, adding expanded graphite into deionized water, and adding sodium lignosulfonate as a dispersing agent, wherein the concentration of the sodium lignosulfonate is 1 g/L;
(2) carrying out ultrasonic treatment on the prepared mixture, controlling the temperature to be 40 ℃, the power to be 200W and the time to be 150 h;
(3) after the ultrasonic treatment is finished, centrifuging the sample, controlling the centrifugal rotating speed to be 8000rpm, and taking the supernatant after centrifugation to obtain the water-phase graphene dispersion liquid;
(4) prepressing expanded graphite into a low-density graphite plate with the density of 0.25g/cm3, immersing the graphite plate in water-phase graphene dispersion liquid, vacuumizing and pressurizing to enable the graphene dispersion liquid to enter an inner pore channel of the low-density graphite plate, and drying to obtain the graphene composite low-density graphite plate;
(5) and carrying out mould pressing on the graphene composite low-density graphite flake through a mould pressing machine, then impregnating resin, curing and drying to obtain the graphene composite flexible graphite polar plate.
EXAMPLE III
(1) Taking expanded graphite and deionized water according to the mass ratio of 1.5: 1, adding expanded graphite into deionized water, and adding sodium lignosulfonate as a dispersing agent, wherein the concentration of the sodium lignosulfonate is 2 g/L;
(2) carrying out ultrasonic treatment on the prepared mixture, controlling the temperature to be 50 ℃, the power to be 300W and the time to be 200 h;
(3) after the ultrasonic treatment is finished, centrifuging the sample, controlling the centrifugal rotation speed to be 10000rpm, and taking supernatant after centrifuging to obtain water-phase graphene dispersion liquid;
(4) prepressing expanded graphite into a low-density graphite plate with the density of 0.5g/cm3, immersing the graphite plate in water-phase graphene dispersion liquid, vacuumizing and pressurizing to enable the graphene dispersion liquid to enter an inner pore channel of the low-density graphite plate, and drying to obtain the graphene composite low-density graphite plate;
(5) and carrying out mould pressing on the graphene composite low-density graphite flake through a mould pressing machine, then impregnating resin, curing and drying to obtain the graphene composite flexible graphite polar plate.
Example four
A graphite electrode plate produced by the production method described in any one of the first to third embodiments.
EXAMPLE five
A fuel cell comprising the graphite plate of any one of the embodiments.
EXAMPLE six
A vehicle comprising the graphite electrode plate of embodiment one to embodiment three and/or the fuel cell of embodiment five.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (10)
1. The preparation method of the graphite polar plate is characterized by comprising the following steps
Extracting a liquid-phase graphene dispersion liquid through an expanded graphite plate;
prepressing expanded graphite into a low-density porous graphite sheet;
enabling the liquid-phase graphene dispersion liquid to enter an internal pore channel of the low-density porous graphite sheet and then drying to obtain the graphene composite low-density graphite sheet;
carrying out die pressing on the graphene composite low-density graphite sheet;
and impregnating the pressed graphene composite low-density graphite sheet with resin, and curing and molding.
2. The method of manufacturing a graphite plate according to claim 1, wherein the expanded graphite sheet is subjected to an ultrasonic exfoliation method to obtain a liquid-phase graphene dispersion.
3. The method for preparing the graphite electrode plate according to claim 2, wherein the step of obtaining the liquid-phase graphene dispersion liquid from the expanded graphite plate by the ultrasonic exfoliation method comprises
According to the mass ratio of 0.5-1.5: 1, adding expanded graphite into deionized water, and adding a dispersing agent;
carrying out ultrasonic treatment on the prepared mixture, wherein the ultrasonic temperature is 30-50 ℃, the power is 100-300W, and the time is 50-200 h;
and after the ultrasonic treatment is finished, centrifuging the sample, controlling the centrifugal rotation speed to be 5000-10000 rpm, and taking supernatant after centrifuging to obtain the liquid-phase graphene dispersion liquid.
4. The method for preparing the graphite electrode plate according to claim 3, wherein the dispersant is sodium lignosulfonate, and the concentration of the sodium lignosulfonate is 0.2-2 g/L.
5. The method of claim 1, wherein the low density porous graphite sheet has a density of 0.05 to 0.5g/cm 3 。
6. The method of preparing a graphite plate of claim 1, wherein the low-density porous graphite sheet is immersed in the liquid-phase graphene dispersion liquid, and the liquid-phase graphene dispersion liquid is subjected to vacuum pumping and pressurization treatment to enter the inner pore channels of the low-density porous graphite sheet.
7. The method of manufacturing a graphite electrode plate according to claim 1, wherein the graphene composite low-density graphite sheet is molded by a molding press.
8. A graphite electrode plate, characterized by being produced by the production method according to any one of claims 1 to 7.
9. A fuel cell comprising a plurality of graphite plates as claimed in claim 8.
10. A vehicle comprising the graphite electrode plate of claim 8 and/or the fuel cell of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110117848.2A CN114824342A (en) | 2021-01-28 | 2021-01-28 | Preparation method of graphite polar plate, fuel cell and vehicle |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110117848.2A CN114824342A (en) | 2021-01-28 | 2021-01-28 | Preparation method of graphite polar plate, fuel cell and vehicle |
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| CN114824342A true CN114824342A (en) | 2022-07-29 |
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| CN202110117848.2A Pending CN114824342A (en) | 2021-01-28 | 2021-01-28 | Preparation method of graphite polar plate, fuel cell and vehicle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001085032A (en) * | 1999-09-16 | 2001-03-30 | Kemitsukusu:Kk | Gas impermeable expansive graphite plate for fuel cell |
| US20070128494A1 (en) * | 2005-12-05 | 2007-06-07 | Aruna Zhamu | Integrated bipolar plate/diffuser for a proton exchange membrane fuel cell |
| CN102569834A (en) * | 2010-12-22 | 2012-07-11 | 清华大学 | High-intensity flexible graphite double-pole plate and preparation method thereof |
| CN103801274A (en) * | 2014-02-28 | 2014-05-21 | 天津工业大学 | Preparation method of oil-absorbing hollow fiber porous membrane |
| CN104876210A (en) * | 2015-04-13 | 2015-09-02 | 华南理工大学 | Method for preparing water-phase graphene dispersion liquid by employing ultrasonic stripping |
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