CN103811778A - Proton exchange membrane fuel cell bipolar plate with high mechanical property, electric conductivity and thermal conductivity - Google Patents
Proton exchange membrane fuel cell bipolar plate with high mechanical property, electric conductivity and thermal conductivity Download PDFInfo
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- CN103811778A CN103811778A CN201410049561.0A CN201410049561A CN103811778A CN 103811778 A CN103811778 A CN 103811778A CN 201410049561 A CN201410049561 A CN 201410049561A CN 103811778 A CN103811778 A CN 103811778A
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- graphite
- thermal conductivity
- matched moulds
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- 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
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a proton exchange membrane fuel cell composite material bipolar plate which consists of a phenolic resin, titanium carbide, graphite and a curing agent. The bipolar plate has the electric conductivity of 210S/cm, the bending strength of 36MPa, the compressive strength of 105MPa and the thermal conductivity of 40<-6> W/mK. The graphite powder, the modified phenolic resin and the titanium carbide powder are selected. The titanium carbide (TiC) is in a face-centered cubic crystal form, is high in melting point, high in thermal conductivity, high in hardness, high in chemical stability and high in high-temperature oxidation resistance, does not react with acids at normal temperature and has high corrosion resistance and extremely high electric conductivity (higher than that of pure graphite), the mechanical property, electric conductivity and thermal conductivity of the phenolic resin/graphite composite material bipolar plate can be greatly improved, and the prepared bipolar plate has high electric conductivity, high thermal conductivity, high strength and high hydrogen corrosion resistance.
Description
The application is application number: the divisional application of 201110145554.7, the applying date: 2011-06-01, title " Composite Bipolar Plates For Polymer Electrolyte Membrane Fuel Cell and production method ".
Technical field
The present invention relates to a kind of advanced composite material (ACM) bipolar plates formula and the manufacturing process of Proton Exchange Membrane Fuel Cells.
Background technology
21st century is the century of energy scarcity, and the rationally efficient utilization of the exploitation to novel energy, the existing energy has become the theme of development in this century.At present, the fossil energies such as oil, natural gas and coal that the mankind depend on for existence reduce increasingly, will be instead the renewable resources such as Hydrogen Energy, solar energy and wind energy.Meanwhile, because the inefficient combustion to existing resource (as oil, natural gas and coal) is used, both waste the energy, also environment had been caused to severe contamination, become the major issue that must solve this century.
Fuel cell (Fuel Cells) is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that a kind of electricity can directly be converted into chemical energy electric energy.Energy conversion efficiency high (40%-60%); Environmental friendliness, discharges nitrogen oxide and oxysulfide hardly; The discharge capacity of carbon dioxide also reduces more than 50% than conventional power generation usage factory.Just because of these outstanding superiority, the research and development of fuel cell technology enjoys the attention of national governments and major company of the world, is considered to the cleaning of 21 century first-selection, efficient generation technology, becomes everybody and researches and develops focus.
Hydrogen-oxygen proton exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell, PEMFC) using hydrogen fuel, air or oxygen is oxidant, except thering is the feature that fuel cell is general (as high in energy conversion efficiency, environmental friendliness etc.), also have simultaneously can start fast in room temperature (working temperature is generally at 60～100 ℃), without electrolyte loss, water easily discharge, the outstanding feature such as the life-span is long, specific power and energy height, particularly its emission is water, has realized pollution-free zero discharge.Therefore, it is acknowledged as the first-selected power supply that promises to be military affairs, space flight, navigation, electric automobile and regional power station most.
Bipolar plates is the critical piece of Proton Exchange Membrane Fuel Cells (PEMFC), and bipolar plates profile is generally plate, and single or double has the flow field (groove) of dark 1mm, wide 1mm left and right, is the passage for hydrogen and flow of oxygen.The major function of bipolar plates has: (1) distributes fuel and the oxidant in battery; (2) monocell in split cell group; (3) conduction current; (4) transmission generates water, moisture; (5) cool batteries group.The expense of bipolar plates accounts for the over half of fuel cell, seriously hinders the commercialization of Proton Exchange Membrane Fuel Cells, finds cheaply, and the life-span, long bipolar plate material became the extremely urgent problem of Proton Exchange Membrane Fuel Cells commercialization.
At present, main material and the method for manufacture bipolar plates have:
(1) pure graphite bi-polar plate
The general coke that adopts graphite powder, pulverizing mixes with graphitisable resin or pitch, strict with certain heating schedule in graphitizing furnace, be warming up to 2500～2700 ℃, preparation atresia or low porosity (being not more than 1%), only contain the graphite block of nano grade pore, through cutting and grinding, prepare the graphite cake that thickness is 2～5 mm again, machine work shares duct and paints the flow field needing with computer engraving machine at its surperficial quarter.The preparation technology of this graphite bi-polar plate not only complicated, consuming time, expense is high, and be difficult to realize batch production.Graphite material has superior electric conductivity, and thermal conductivity and anti-wear performance are a kind of low density materials, are the preferred material of bipolar plates always, and the high temperature graphitization in process for machining and the machine work of gas flow are to cause the expensive main cause of bipolar plates.
(2) metal double polar plates
Metal material bipolar plates has the advantages such as the good and gas permeation rate of high conductivity, high-termal conductivity, mechanical strength is low, but metal is under the environment of fuel cell operation, and easily corrosion can not meet the requirement of long-term use.Making the outstanding advantage of bipolar plate material with metal sheet is to be particularly suitable for batch production, as adopted stamping technology to prepare the bipolar plates of various configurations.The matter of utmost importance that adopts metal sheet to prepare bipolar plates is to solve it at PEMFC condition of work (oxidation, reducing atmosphere, certain current potential and faintly acid electrolyte) under stability (being anticorrosive problem), another problem is exactly also to need further to investigate its life-span.
(3) graphite/polymer
For reducing the preparation cost of graphite bi-polar plate, meet the requirement using in enormous quantities, prepare composite material double pole plate by graphite powder and fluoropolymer resin and other various formulas and similar approach.This method due to adopt compression molding, so runner directly one-shot forming go out, have the advantages that efficiency is high, cost is low, become current PEMFC bipolar plates and there is one of research direction of development prospect, abroad have large-scale production.But there is the deficiencies such as conductivity is low, intensity is low, thermal conductivity is low in the bipolar plates ratio that the bipolar plates that this method is produced and above-mentioned two kinds of methods are produced.
Summary of the invention
For the aspect requirement of bipolar plates mechanical property, it is mainly fitting tight and when fastening, must there be certain resistance to compression and bending strength, when work, do not have impact, alternate load complicated applied force situation, so meeting under certain mechanics performance condition, be mainly to improve its conduction, heat conductivility and corrosion resistance.The object of the present invention is to provide Composite Bipolar Plates For Polymer Electrolyte Membrane Fuel Cell and production method that a kind of mechanical property, conduction and thermal conductivity are good.
Of the present invention is exactly that solution is:
A kind of Composite Bipolar Plates For Polymer Electrolyte Membrane Fuel Cell, is characterized in that: the raw material by following percentage by weight is made:
Phenolic resins 5% ~ 20%
Titanium carbide 1% ~ 10%
Graphite 60% ~ 93%
Curing agent 1% ~ 10%.
Described curing agent is hexamethylenetetramine.
A production method for Composite Bipolar Plates For Polymer Electrolyte Membrane Fuel Cell, is characterized in that: comprise the steps:
1) graphite of the titanium carbide of the phenolic resins of 5% ~ 20% percentage by weight, 1% ~ 10% percentage by weight and 60% ~ 93% percentage by weight is mixed, then put into 60 ~ 100 ℃ of baking ovens and dry 1 ~ 5 h;
2) dried powder is taken out, add curing agent, put into mold cavity, mold cavity is processed with runner (flow field), makes by all one-shot formings of runner after mold pressing; (2) matched moulds: carry out matched moulds after reinforced, the matched moulds time is 5s ~ 30s, and the pressure of matched moulds is at 5 ~ 60 MPa, and compression molding temperature is 130 ~ 220 ℃, and temperature retention time is 1 ~ 15min.; 3) exhaust: need release exhaust after mould matched moulds, the number of times of exhaust is 1 ~ 3 time, and each time is 3s ~ 20s; (5) demoulding: after having solidified, use the push rod demoulding.
3) after compression molding, put into baking oven by clamp clamps bipolar plates, insulation is processed, and makes bipolar plates further solidify to obtain finished product.Annealing temperature is 80 ~ 130 ℃, and temperature retention time is 4 ~ 24h.
Hybrid mode described in step 1) is that ball milling is dry mixed or thinks alcohol solvent wet mixing.
The present invention selects graphite powder, phenol-formaldehyde resin modified and titanium carbide powder.Titanium carbide (TiC) belongs to face-centered cubic crystal formation, fusing point is high, good heat conductivity, hardness is large, and chemically stable is good, and high-temperature oxidation resistance is good, do not react with acid at normal temperatures, have very strong decay resistance and very high conductivity (also higher than pure graphite), can greatly improve mechanical property, conduction and the thermal conductivity of PF Resin/Graphite Composite bipolar plates, the bipolar plates making not only has higher conductivity, thermal conductivity, higher intensity and resistance to hydrogen-type corrosion.
The performance of the bipolar plates that the present invention makes can reach:
Conductivity 210S/cm, bending strength 36 MPa, compression strength 105 MPa, pyroconductivity 40
-6w/mK.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the production method flow chart of one embodiment of the invention.
Embodiment
Embodiment 1:
1) graphite of the titanium carbide of the phenolic resins of 10% percentage by weight, 10% percentage by weight and 77% percentage by weight is carried out to ball milling and be dry mixed, then put into 60 ~ 100 ℃ of baking ovens and dry 1 ~ 5 h;
2) dried powder is taken out, add the curing agent hexamethylenetetramine of 3% percentage by weight, put into mold cavity, mold cavity is processed with runner (flow field), makes by all one-shot formings of runner after mold pressing; (2) matched moulds: carry out matched moulds after reinforced, the matched moulds time is 5s ~ 30s, and the pressure of matched moulds is at 40 MPa, and compression molding temperature is 200 ℃, and temperature retention time is 5min.; 3) exhaust: need release exhaust after mould matched moulds, the number of times of exhaust is 1 ~ 3 time, and each time is 3s ~ 20s; (5) demoulding: after having solidified, use the push rod demoulding.
3) after compression molding, put into baking oven by clamp clamps bipolar plates, insulation is processed, and makes bipolar plates further solidify to obtain finished product.Annealing temperature is 80 ~ 130 ℃, and temperature retention time is 4 ~ 24h.
The performance of the bipolar plates making is as follows:
Conductivity 210S/cm, bending strength 36 Mpa, compression strength 105 Mpa, pyroconductivity 40
-6w/mK.
Embodiment 2:
1) by 5% ~ 20%(example 5%, 12%, 20%) phenolic resins, 1% ~ 10%(example 1%, 5%, 10% of percentage by weight) titanium carbide and 60% ~ 93%(example 60%, 75%, 93% of percentage by weight) graphite of percentage by weight mixes, then put into 60 ~ 100 ℃ of (60 ℃, 80 ℃, 100 ℃ of examples) baking ovens and dry 1 ~ 5 h;
2) dried powder is taken out, adds 1 ~ 10%(example 1%, 6%, 10%) curing agent of percentage by weight, put into mold cavity, mold cavity is processed with runner (flow field), makes by all one-shot formings of runner after mold pressing; (2) matched moulds: carry out matched moulds after reinforced, the matched moulds time is 5s ~ 30s, and the pressure of matched moulds is at 5 ~ 60 MPa(example 5 MPa, 30 MPa, 60 MPa), compression molding temperature is 130 ~ 220 ℃ (130 ℃, 180 ℃, 220 ℃ of examples), temperature retention time is 1 ~ 15min.; 3) exhaust: need release exhaust after mould matched moulds, the number of times of exhaust is 1 ~ 3 time, and each time is 3s ~ 20s; (5) demoulding: after having solidified, use the push rod demoulding.
3) after compression molding, put into baking oven by clamp clamps bipolar plates, insulation is processed, and makes bipolar plates further solidify to obtain finished product.Annealing temperature is 80 ~ 130 ℃ (80 ℃, 100 ℃, 130 ℃ of examples), and temperature retention time is 4 ~ 24h.
Hybrid mode described in step 1) is that ball milling is dry mixed or thinks alcohol solvent wet mixing.
Claims (1)
1. the good dual polar plates of proton exchange membrane fuel cell of mechanical property, conduction and thermal conductivity, is characterized in that: the raw material by following percentage by weight is made:
Phenolic resins 10%
Titanium carbide 10%
Graphite 77%
Curing agent 3%.
Described curing agent is hexamethylenetetramine;
Conductivity 210S/cm, bending strength 36 Mpa, compression strength 105 Mpa, pyroconductivity 40
-6w/mK;
Preparation method comprises the steps:
1) graphite of the titanium carbide of the phenolic resins of 10% percentage by weight, 10% percentage by weight and 77% percentage by weight is carried out to ball milling and be dry mixed, then put into 60 ~ 100 ℃ of baking ovens and dry 1 ~ 5 h;
2) dried powder is taken out, add the curing agent hexamethylenetetramine of 3% percentage by weight, put into mold cavity, mold cavity is processed with runner, makes by all one-shot formings of runner after mold pressing; (2) matched moulds: carry out matched moulds after reinforced, the matched moulds time is 5s ~ 30s, and the pressure of matched moulds is at 40 MPa, and compression molding temperature is 200 ℃, and temperature retention time is 5min; (3) exhaust: need release exhaust after mould matched moulds, the number of times of exhaust is 1 ~ 3 time, and each time is 3s ~ 20s; (4) demoulding: after having solidified, use the push rod demoulding;
3) after compression molding, put into baking oven by clamp clamps bipolar plates, insulation is processed, and makes bipolar plates further solidify to obtain finished product; Annealing temperature is 80 ~ 130 ℃, and temperature retention time is 4 ~ 24h.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110145554.7A CN102244271B (en) | 2011-06-01 | 2011-06-01 | Composite bipolar plate for proton exchange membrane fuel cell and production method thereof |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110145554.7A Division CN102244271B (en) | 2011-06-01 | 2011-06-01 | Composite bipolar plate for proton exchange membrane fuel cell and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103811778A true CN103811778A (en) | 2014-05-21 |
| CN103811778B CN103811778B (en) | 2016-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201110145554.7A Expired - Fee Related CN102244271B (en) | 2011-06-01 | 2011-06-01 | Composite bipolar plate for proton exchange membrane fuel cell and production method thereof |
| CN201410049561.0A Active CN103811778B (en) | 2011-06-01 | 2011-06-01 | The dual polar plates of proton exchange membrane fuel cell that mechanical property, conduction and thermal conductivity are good |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201110145554.7A Expired - Fee Related CN102244271B (en) | 2011-06-01 | 2011-06-01 | Composite bipolar plate for proton exchange membrane fuel cell and production method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336053A (en) * | 2019-07-16 | 2019-10-15 | 中南大学 | A kind of preparation method of the fuel battery double plates containing runner |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544525B (en) * | 2012-01-11 | 2013-05-15 | 南通大学 | Method for injection molding of composite bipolar plate of proton exchange membrane fuel cell |
| GB2501702B (en) * | 2012-05-01 | 2019-11-20 | Intelligent Energy Ltd | A current collector component for a fuel cell |
| CN102664272B (en) * | 2012-05-23 | 2014-04-16 | 济南鲁东耐火材料有限公司 | Hydrogen fuel cell polar plate and preparation process thereof |
| CN103633340B (en) * | 2013-12-17 | 2016-06-08 | 哈尔滨工业大学 | A kind of modified expanded graphite base composite material double pole plate and preparation method thereof |
| US10170749B2 (en) * | 2016-06-07 | 2019-01-01 | Nanotek Instruments, Inc. | Alkali metal battery having an integral 3D graphene-carbon-metal hybrid foam-based electrode |
| CN107611458B (en) * | 2017-09-06 | 2020-07-24 | 氢源科技(赣州)有限公司 | Proton exchange membrane fuel cell bipolar plate and preparation method thereof |
| CN115621483B (en) * | 2022-09-26 | 2024-02-02 | 海卓动力(北京)能源科技有限公司 | MXene composite bipolar plate and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002065568A2 (en) * | 2001-02-14 | 2002-08-22 | Mosaic Energy L.L.C. | Internal mold release agent for low cost composite bipolar plates |
| US20020127457A1 (en) * | 2001-01-10 | 2002-09-12 | Victor Trapp | Bipolar plates for fuel cell stacks |
| CN1591941A (en) * | 2003-09-05 | 2005-03-09 | 中国科学院大连化学物理研究所 | Fuel cell composite material double polar plate and its making method |
| CN1964113A (en) * | 2006-11-29 | 2007-05-16 | 武汉理工大学 | A bipolar plate for conductive ceramics/graphite proton exchange membrane fuel cell and its manufacture method |
| CN101593837A (en) * | 2009-06-30 | 2009-12-02 | 哈尔滨工业大学 | Expanded graphite/phenolic resin composite bipolar plate and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083641A (en) * | 1998-05-08 | 2000-07-04 | The United States Of America As Represented By The United States Department Of Energy | Titanium carbide bipolar plate for electrochemical devices |
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2011
- 2011-06-01 CN CN201110145554.7A patent/CN102244271B/en not_active Expired - Fee Related
- 2011-06-01 CN CN201410049561.0A patent/CN103811778B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020127457A1 (en) * | 2001-01-10 | 2002-09-12 | Victor Trapp | Bipolar plates for fuel cell stacks |
| WO2002065568A2 (en) * | 2001-02-14 | 2002-08-22 | Mosaic Energy L.L.C. | Internal mold release agent for low cost composite bipolar plates |
| CN1591941A (en) * | 2003-09-05 | 2005-03-09 | 中国科学院大连化学物理研究所 | Fuel cell composite material double polar plate and its making method |
| CN1964113A (en) * | 2006-11-29 | 2007-05-16 | 武汉理工大学 | A bipolar plate for conductive ceramics/graphite proton exchange membrane fuel cell and its manufacture method |
| CN101593837A (en) * | 2009-06-30 | 2009-12-02 | 哈尔滨工业大学 | Expanded graphite/phenolic resin composite bipolar plate and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110336053A (en) * | 2019-07-16 | 2019-10-15 | 中南大学 | A kind of preparation method of the fuel battery double plates containing runner |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103811778B (en) | 2016-03-09 |
| CN102244271B (en) | 2014-03-26 |
| CN102244271A (en) | 2011-11-16 |
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Effective date of registration: 20201216 Address after: 277000 No.31, East 2nd Lane, shanguo South Road, Longquan street, Tengzhou City, Zaozhuang City, Shandong Province Patentee after: Tengzhou Fangguan Enterprise Management Consulting Co.,Ltd. Address before: 226019 Jiangsu city of Nantong province sik Road No. 9 Patentee before: NANTONG University |