CN102324529B - Preparation method of conductive plastic bipolar plate of vanadium battery - Google Patents
Preparation method of conductive plastic bipolar plate of vanadium battery Download PDFInfo
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- CN102324529B CN102324529B CN201110249153.6A CN201110249153A CN102324529B CN 102324529 B CN102324529 B CN 102324529B CN 201110249153 A CN201110249153 A CN 201110249153A CN 102324529 B CN102324529 B CN 102324529B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a preparation method of a conductive plastic bipolar plate of a vanadium battery. According to the invention, high-molecular resin and conductive carbon black are adopted as raw materials for producing conductive plastic; metal powder is used for producing a metal micro-particle suspension; in a mixture of high-molecular resin and conductive carbon black, the high-molecular resin and the conductive carbon black are sufficiently mixed; an appropriate amount of the metal micro-particle suspension is doped, such that a material used for producing the conductive plastic base material is formed; and the material is pressed by using a mold, such that the conductive plastic bipolar plate is prepared. The metal micro-particle suspension is formulated according to the type and dosage of the adopted conductive plastic. Different from common conductive plastic bipolar plates of vanadium batteries, according to the invention, an appropriate amount of metal micro-particles are doped in the components used for preparing the conductive plastic, such that the content of high-molecular resin can be greatly increased, and the content of conductive carbon black is reduced. The prepared conductive plastic bipolar plate is improved both in conductivity and in strength. The method provided by the invention has advantages of simple method, reasonable technology, wide raw material source, and easy application.
Description
Technical field
The invention belongs to energy storage field, relate to the preparation method of the manufacture of battery material, particularly a kind of conductive plastic bipolar plate of vanadium battery.
Background technology
Vanadium redox battery is a kind of novel energy storage device, and it is made up of pile, positive and negative electrolyte storage tank and other sub controlling units.Its energy stores with the form of both positive and negative polarity electrolyte, in charge and discharge process, in the both sides of amberplex, oxidation reaction and reduction reaction occurs respectively:
Anodal reaction:
e
0=1.00V
Negative reaction: V
3++ e
-→ V
2+e
0=-0.26V
Vanadium redox battery has special battery structure, can realize degree of depth high current density discharge, and its energy is high, cheap.And, its manufacture, use and discarded process does not all produce harmful substance.So its application is wide, can be the place such as mansion, airport stand-by power supply is provided, can be used as the supporting energy storage device of solar energy, photovoltaic generating system, also can be used for peak load regulation network etc.
According to the knowledge of the applicant, bipolar plates is one of critical material of manufacturing vanadium redox battery, and at present, conventional bipolar plates has Metal Substrate bipolar plates, graphite-like bipolar plates and conductive plastics class bipolar plates.For example Chinese patent literature (number of patent application: 200610129486.4) disclosed " a kind of fuel battery metal double polar plate with face coat ", its structure comprises metallic matrix, is characterized in: described metal base surface is provided with chromium nitride coating; Described chromium nitride coating thickness is 0.5 μ m-10 μ m; Described chromium nitride coating is film fine and close, free of pinholes.This metal double polar plates adopts Ion Beam Surface Modification technology, forms thin film, to keep shape and the precision of matrix at matrix surface; And require adhesion between coating and matrix high, make every effort to accomplish coating even compact, thereby make this bipolar plates in operation of fuel cells potential range, there is longer stability and good mechanical property.Because this invention is for the having relatively high expectations of film, cause production technology relative complex.
Chinese patent literature (number of patent application: 200310108021.7) disclose " a kind of manufacture method of fuel cell graphite pole ", it is to adopt thermal pressure mold pressing one-shot forming, by the graphite powder of mixing thoroughly in proportion in advance and mixed with resin, put into the mould of preheating, thermal pressure compression molding, the mixed proportion of graphite powder and resin is 1: 0.15～0.4; For improving Forming Quality, also can in resin, add curing agent and diluent.This invention can increase the conductivity of pole plate, but its cost is higher.
Applicant thinks after analyzing in earnest and study the manufacture of existing bipolar plates and pole plate and using basic condition, Metal Substrate pole plate is due to corrosion resistant reason, large-scale application not yet at present, though graphite bi-polar plate is applied, also exist side of the positive electrode to have the shortcoming of etching phenomenon and bad mechanical strength.And the application of conductive plastics is quietly being risen, this is that just to have density little due to conductive plastics itself, machine-shaping is easy, cost is low, be applicable to some noticeable features such as large-scale continuous production, therefore, conductive plastic bi-polar plate is becoming the focus of research of the same trade, but himself there is the shortcoming of poorly conductive, need to take effective technical measures and process are improved in earnest and overcome.
According to interrelated data introduction, in order to improve the electric conductivity of conductive plastics pole plate, in conventional conductive plastic pad preparation process, tend to add a large amount of conductive carbon blacks, this not only damages the mechanical performance of conductive plastics pole plate, and in the situation that vanadium cell overcharges, as anodal conductive plastics polar board surface, amorphous carbon black leakage can occur, thereby cause the volume resistance of pole plate to increase.And in the time that the vanadium cell circular flow time is long, the conductive plastics pole plate of side of the positive electrode there will be the even phenomenon of layering of bulge, has a strong impact on the useful life of vanadium cell.
Summary of the invention
The object of the invention is, for the deficiencies in the prior art, study and improve, a kind of preparation method of conductive plastic bipolar plate of vanadium battery is proposed, the bipolar plates of preparing by the present invention, the deficiency of conventional conductive plastic bi-polar plate electric conductivity be can overcome, and life-span and the mechanical performance of bipolar plates improved.
Technical solution of the present invention is: adopt macromolecule resin and conductive carbon black as the raw material of making conductive plastic bi-polar plate, in macromolecule resin, add conductive carbon black, form the mixture of macromolecule resin and conductive carbon black, it is characterized in that, adopt metal dust, make metal particle suspension, in the mixture of macromolecule resin and conductive carbon black, doping is by the metal particle suspension of metal powder, form the material of making conductive plastics matrix, by the compressing conductive plastic bi-polar plate of preparing of mould, concrete steps are again:
1) add conductive carbon black at macromolecule resin, carry out by weight mixed preparing, through fully mixing, stir, form the mixture of macromolecule resin and conductive carbon black;
2) the conductive plastics type and the consumption preparing metal microparticle suspending liquid that adopt as requested: first select suitable metal particle type, take again appropriate metal dust, in metal dust, add liquid surface modifier, fully stir, form metal particle suspension;
3) mixture of macromolecule resin and conductive carbon black is fully mixed with the metal particle suspension of doping, stir, make macromolecule resin and conductive carbon black and the metal particle can be evenly indissoluble, form the material of making conductive plastics matrix;
4) again by form make conductive plastics matrix material stirring evenly after, be placed in fixed funnel and carry out suction filtration, and be placed in baking oven and dry;
5) form after the drying materials of making conductive plastics matrix, then the mould compression molding that is placed in ad hoc type, be prepared into conductive plastic bi-polar plate.
It is characterized in that, in the macromolecule resin forming and the mixture of conductive carbon black, macromolecule resin accounts for 70% of total weight---and 95%, conductive carbon black is total weight 5%---30%.
It is characterized in that, macromolecule resin adopts the one in PE, PP, PVC.
It is characterized in that, macromolecule resin adopts by any two in PE, PP, PVC to match well arbitrarily than the mixture combining.
It is characterized in that, macromolecule resin adopts by PE, PP, tri-kinds of mixtures that combine with any proportioning of PVC.
It is characterized in that, adopt metal powder metal particle, then make metal particle suspension.
It is characterized in that, metal particle can be metallic particles, metallic fiber, whisker or other metal particles.
It is characterized in that, form the metal particle of the material of making conductive plastics matrix, need to be according to prepared one-tenth conductive plastic bi-polar plate the proportioning of the requirement difference to its plastic substrate and conductive carbon black choose suitable dosage.
Advantage of the present invention is, method is simple, and technique is reasonable, and raw material sources are extensive, is convenient to implement.The conductive plastic bi-polar plate that the present invention produces is different from conventional conductive plastic bipolar plate of vanadium battery, the present invention is making the appropriate metal particle that adulterates in the component of conductive plastics, consequent good effect is can significantly improve the content of macromolecule resin and reduce the content of conductive carbon black.Can, in keeping conductive plastic bi-polar plate conductivity, reduce in a large number the consumption of conductive carbon black, and therefore can improve the mechanical performance of pole plate.
Brief description of the drawings
Fig. 1, process chart of the present invention
Embodiment
Describe with reference to the accompanying drawings embodiments of the invention in detail below.
As shown in Figure 1, embodiments of the invention 1 are by process chart of the present invention, adopting macromolecule resin, conductive carbon black is raw material, choose a certain amount of macromolecule resin by proportioning, in the macromolecule resin of choosing, add a small amount of conductive carbon black, form the mixture of macromolecule resin and conductive carbon black, in the mixture of macromolecule resin and conductive carbon black, macromolecule resin accounts for 70% of total weight---and 95%, conductive carbon black is total weight 5%---30%.Adopt metal dust, make metal particle suspension, as doping materials.The metal particle suspension that appropriate doping is made up of metal dust in the mixture of macromolecule resin and conductive carbon black, forms the material of making conductive plastics matrix, then prepares conductive plastic bi-polar plate by mould compression molding.
The typical process flow adopting: comprise the multiple concrete steps of batching, mixing, stirring, suction filtration and compression molding.
One, batching, mixing, whipping step
1) in proportion macromolecule resin raw material and a small amount of conductive carbon black adding are prepared, through fully mixing, dispersed with stirring, the mixture of formation macromolecule resin and conductive carbon black;
2) according to the conductive plastics type and the consumption preparing metal microparticle suspending liquid that adopt: first select suitable metal particle type, the consumption of the metal particle suspension of preparing on request again, take appropriate metal dust, in metal dust, add surface modifier, fully dispersed with stirring, forms needed metal particle suspension; The surface modifier adding is liquid surface modifier.
3) mixture of macromolecule resin and conductive carbon black is fully mixed with the metal particle suspension of doping, dispersed with stirring, makes macromolecule resin and conductive carbon black and the metal particle can be evenly indissoluble, thereby forms the material of making conductive plastics matrix.
Two, suction filtration step
4) again by form make conductive plastics matrix material stirring evenly after, be placed in fixed funnel and carry out suction filtration, and be placed in baking oven and dry.
Three, compression molding step
5) form after the drying materials of making conductive plastics matrix, the mould compression molding that is placed in ad hoc type, is prepared into conductive plastic bi-polar plate.
Embodiment 1, according to above-mentioned concrete steps, can prepare the conductive plastic bipolar plate of vanadium battery of electric conductivity and satisfactory mechanical property.In the concrete steps of stating on the implementation, can take as required following concrete component, proportioning and technological measure:
1, in the macromolecule resin forming and the mixture of conductive carbon black, macromolecule resin accounts for 70% of total weight---and 95%, conductive carbon black is total weight 5%---30%;
2, macromolecule resin adopts the one in PE, PP, PVC;
3, macromolecule resin adopts by any two in PE, PP, PVC to match well arbitrarily than the composition combining;
4, macromolecule resin adopts by PE, PP, tri-kinds of compositions that combine with any proportioning of PVC.
5, metal dust is first made metal particle, then the metal particle suspension of making;
6, metal particle can be metallic particles, metallic fiber, whisker or other metal particles.
7, form the metal particle of the material of making conductive plastics matrix, be prepared into the requirement difference of conductive plastic bi-polar plate to its plastic substrate and the proportioning of conductive carbon black according to required, and choose suitable dosage.
Example 2:
By PE, PP, PVC is 30: 40: 30 composition macromolecule resin mixtures in mass ratio, this macromolecule resin mixture being made up of multiple macromolecule resin is prepared with conductive carbon black again, two kinds of compositions of macromolecule resin and conductive carbon black fully mix according to mass ratio at 95: 5, stir and disperse to form the mixture of macromolecule resin and conductive carbon black, macromolecule resin is fully mixed according to mass ratio with metal particle suspension with the mixture of conductive carbon black at 90: 10, stir and form the material of making conductive plastics matrix, the material of making conductive plastics matrix is placed in to fixed funnel suction filtration 1 hour, then being placed in baking oven dries, after oven dry, put into mould compression molding, make conductive plastic bi-polar plate.Metal particle suspension is according to the conductive plastics type adopting and consumption preparation.Specifically making way is, first selects suitable metal particle type, then the consumption of the metal particle suspension of preparing on request, take appropriate metal dust, in metal dust, add surface modifier, fully dispersed with stirring, forms needed metal particle suspension; The surface modifier adding is liquid surface modifier.Wherein, the metal particle that making metal particle suspension adopts can be metallic particles, metallic fiber, whisker or other metal particles.
Embodiment 3:
By PE, PP is 40: 60 composition macromolecule resin mixtures in mass ratio, macromolecule resin and conductive carbon black fully mix according to mass ratio at 90: 10, stir and form the mixture of macromolecule resin and conductive carbon black, macromolecule resin is fully mixed according to mass ratio with conductive carbon black mixture and metal particle suspension at 95: 5, stir and make the material of conductive plastics matrix, the material of conductive plastics matrix is placed in to fixed funnel suction filtration 1 hour, then being placed in baking oven dries, after oven dry, put into the mould compression molding of ad hoc type, make conductive plastic bi-polar plate.According to the conductive plastics type and the consumption preparing metal microparticle suspending liquid that adopt.Specifically making way is, first selects suitable metal particle type, then the consumption of the metal particle suspension of preparing on request, take appropriate metal dust, in metal dust, add surface modifier, fully dispersed with stirring, forms needed metal particle suspension; The surface modifier adding is liquid surface modifier.Wherein, the metal particle that making metal particle suspension adopts can be metallic particles, metallic fiber, whisker or other metal particles.
Embodiment 4:
By PP, the PVC mixture of 50: 50 composition macromolecule resins in mass ratio.Then, the mixture of macromolecule resin and conductive carbon black carry out mixed preparing, macromolecule resin and conductive carbon black fully mix according to mass ratio at 85: 15, stir, form the mixture of macromolecule resin and conductive carbon black, macromolecule resin is fully mixed according to mass ratio with metal particle suspension with the mixture of conductive carbon black at 85: 15, stir, make the material of conductive plastics matrix, by the material of conductive plastics matrix, be placed in fixed funnel suction filtration 1 hour, then being placed in baking oven dries, after oven dry, put into the mould compression molding of ad hoc type, make conductive plastic bi-polar plate.According to the conductive plastics type and the consumption preparing metal microparticle suspending liquid that adopt.Specifically making way is, first selects suitable metal particle type, then the consumption of the metal particle suspension of preparing on request, take appropriate metal dust, in metal dust, add surface modifier, fully dispersed with stirring, forms needed metal particle suspension; The surface modifier adding is liquid surface modifier.Wherein, the metal particle that making metal particle suspension adopts can be metallic particles, metallic fiber, whisker or other metal particles.
Claims (7)
1. the preparation method of a conductive plastic bipolar plate of vanadium battery, adopt macromolecule resin and conductive carbon black as the raw material of making conductive plastic bi-polar plate, in macromolecule resin, add conductive carbon black, form the mixture of macromolecule resin and conductive carbon black, adopt metal dust, make metal particle suspension, in the mixture of the macromolecule resin forming and conductive carbon black, macromolecule resin accounts for 90% of total weight---and 95%, conductive carbon black is 5% of total weight---10%, it is characterized in that, in the mixture of macromolecule resin and conductive carbon black, doping is by the metal particle suspension of metal powder, form the material of making conductive plastics matrix, again by the compressing conductive plastic bi-polar plate of preparing of mould, concrete steps are:
1) add conductive carbon black at macromolecule resin, carry out by weight mixed preparing, through fully mixing, stir, form the mixture of macromolecule resin and conductive carbon black;
2) the conductive plastics type and the consumption preparing metal microparticle suspending liquid that adopt as requested: first select suitable metal particle type, take again appropriate metal dust, in metal dust, add liquid surface modifier, fully stir, form metal particle suspension;
3) mixture of macromolecule resin and conductive carbon black is fully mixed with the metal particle suspension of doping, stir, make macromolecule resin and conductive carbon black and the metal particle can be evenly indissoluble, form the material of making conductive plastics matrix;
4) again by form make conductive plastics matrix material stirring evenly after, be placed in fixed funnel and carry out suction filtration, and be placed in baking oven and dry;
5) form after the drying materials of making conductive plastics matrix, then the mould compression molding that is placed in ad hoc type, be prepared into conductive plastic bi-polar plate.
2. the preparation method of a kind of conductive plastic bipolar plate of vanadium battery according to claim 1, is characterized in that, macromolecule resin adopts the one in PE, PP, PVC.
3. the preparation method of a kind of conductive plastic bipolar plate of vanadium battery according to claim 1, is characterized in that, macromolecule resin adopts by any two in PE, PP, PVC to match well arbitrarily than the mixture combining.
4. the preparation method of a kind of conductive plastic bipolar plate of vanadium battery according to claim 1, is characterized in that, macromolecule resin adopts by PE, PP, tri-kinds of mixtures that combine with any proportioning of PVC.
5. the preparation method of a kind of conductive plastic bipolar plate of vanadium battery according to claim 1, is characterized in that, adopts metal powder metal particle, then makes metal particle suspension.
6. the preparation method of a kind of conductive plastic bipolar plate of vanadium battery according to claim 1, is characterized in that, metal particle can be metallic particles, metallic fiber, whisker or other metal particles.
7. the preparation method of a kind of conductive plastic bipolar plate of vanadium battery according to claim 1, it is characterized in that, form the metal particle of the material of making conductive plastics matrix, need to be according to prepared one-tenth conductive plastic bi-polar plate the proportioning of the requirement difference to its plastic substrate and conductive carbon black choose suitable dosage.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104530595A (en) * | 2014-12-24 | 2015-04-22 | 陈程 | High-strength PVC (polyvinyl chloride) conducting composite material and preparation method thereof |
| CN104530562A (en) * | 2014-12-24 | 2015-04-22 | 陈程 | High-strength PP (polypropylene) conducting composite material and preparation method thereof |
| CN104530527A (en) * | 2014-12-24 | 2015-04-22 | 陈程 | High-strength PE (polyethylene) conducting composite material and preparation method thereof |
| CN104530594A (en) * | 2014-12-24 | 2015-04-22 | 陈程 | High-strength PS (polystyrene) conducting composite material and preparation method thereof |
| CN105810955B (en) * | 2016-05-05 | 2018-05-01 | 攀钢集团研究院有限公司 | The preparation method of vanadium cell electrode |
| CN108134105A (en) * | 2017-12-06 | 2018-06-08 | 深圳市晶特智造科技有限公司 | A kind of plastic bipolar plate and preparation method thereof |
| CN110970627B (en) * | 2018-09-29 | 2022-08-16 | 中国科学院大连化学物理研究所 | Bipolar plate for flow battery and preparation and application thereof |
| CN111816886B (en) * | 2020-09-11 | 2021-01-15 | 杭州德海艾科能源科技有限公司 | Vanadium cell splicing conductive plastic bipolar plate |
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| CN101399331A (en) * | 2007-09-26 | 2009-04-01 | 中国科学院金属研究所 | Production method for high conductivity bi-polar plates for acorn cell |
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| CN1086929A (en) * | 1992-09-04 | 1994-05-18 | 单一检索有限公司 | Flexible, conducting plastic electrode and manufacture method thereof |
| CN1567618A (en) * | 2003-07-04 | 2005-01-19 | 中南大学 | Preparation method of electrode for all-vanadium ion flow battery |
| CN101009376A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Integrated pole dual-pole board for oxidation deoxidization liquid energy-storing battery and its preparation |
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Effective date of registration: 20160706 Address after: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 143 Patentee after: Wuhan Nari Limited Liability Company of State Grid Electric Power Research Institute Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 143 Patentee before: Wuhan Nari Limited Liability Company of State Grid Electric Power Research Institute Patentee before: State Grid Electric Power Research Insititute |