CN101794887A - Vanadium battery bi-polar plate, preparation method and application thereof - Google Patents
Vanadium battery bi-polar plate, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a vanadium battery bi-polar plate, a preparation method and application thereof. The bi-polar plate uses flexible graphite as a base material and is manufactured by soaking the base material into thermosetting resin for boiling and then through the procedures of solidifying, pressing, charring, pressing, and the like. The vanadium battery bi-polar plate greatly reduces the porosity, has better sealing property, greatly reduces the charge and discharge resistance, obviously improves the charge and discharge efficiency and the anti-corrosion property, and has low production cost, simple process, easy enlargement or batch production and good application prospect in the field of vanadium battery production.
Description
Technical field
The invention belongs to the vanadium cell technical field, particularly relate to a kind of vanadium battery bi-polar plate and preparation method thereof and application.
Background technology
But vanadium cell has the big degree of depth of capacity charges and discharge, responds fast, characteristics such as addressing is flexible, cost is low, be fit to very much wind-powered electricity generation, photovoltaic etc. intermittently the energy storage of the energy and peak load regulation network, from application scenarios such as net power supplies.Bipolar plates in the vanadium cell heap mainly plays series-connected cell, conduction electron, separation both positive and negative polarity electrolyte.Because the both positive and negative polarity electrolyte of vanadium cell is the vanadium ion of high concentration and the mixed liquor of sulfuric acid, has stronger corrosivity, particularly anodal electrolyte; In addition, bipolar plate material also will guarantee not take place electrochemical reaction under the working voltage of battery, and therefore, vanadium battery bi-polar plate need possess characteristics such as resistance to chemical attack, electrochemical properties be stable.At present, be suitable for making the carbon materials that material mainly is the conductivity height, inertia is good of vanadium battery bi-polar plate most, such as high-density graphite plate, electroconductive resin plate, carbon plastic clad plate etc.
Mitsubishi oiling Co., Ltd. adopts the method that is squeezed into the type of being rolled into to make the electroconductive resin plate, and be applied in the vanadium cell system of hundred KW levels, operation result shows that the electroconductive resin plate thickness that this method is made is even, conductivity is high, mechanical strength is high, is applicable to fully to make the vanadium cell pile.Yet this method requires equipment scaleization, automation, precision height, and the preparation technique that dissolves electroconductive resin requires very highly, and technical scheme is highly confidential, and the technology of large-scale production electroconductive resin plate is still grasped in minority enterprise at present.
In addition, prices such as high-density graphite plate, electroconductive resin plate are all higher, can reach 30% in vanadium cell heap construction cost, are only second to amberplex.
Summary of the invention
The object of the present invention is to provide a kind of vanadium battery bi-polar plate and preparation method thereof and application.
The method for preparing vanadium battery bi-polar plate provided by the invention comprises the steps:
1) flexible graphite plate is placed the organic solution of thermosetting resin flood, the flexible graphite plate after obtaining flooding;
2) will be cured the flexible graphite plate after obtaining solidifying after the flexible graphite plate drying behind the described dipping;
3) flexible graphite plate after the described curing is suppressed the flexible graphite plate after obtaining suppressing;
4) flexible graphite plate after the described compacting is carried out charing, obtain the flexible graphite plate after the charing;
5) flexible graphite plate after the described charing is suppressed, obtained described vanadium battery bi-polar plate.
In above-mentioned preparation method's the step 1), described thermosetting resin is at least a in epoxy resin and the phenolic resins, the number-average molecular weight of described thermosetting resin is 200～2000g/mol, and various commercially available interior epoxy resin and the phenolic resins of above-mentioned molecular weight ranges all are applicable to this method; In the organic solution of described thermosetting resin, organic solvent is selected from least a in methyl alcohol and the ethanol; The mass percentage concentration of the organic solution of described thermosetting resin is 10～40%, preferred 30%; In the impregnation steps, temperature is the boiling point of organic solvent in the described organic solution, and the time is 1～4 hour, preferred 3 hours;
Described step 2) in the drying steps, temperature is 20～30 ℃, and the time is 12～36 hours; In the described curing schedule, temperature is 120-200 ℃, and preferred 150 ℃, the time is 0.5～2 hour, preferred 1 hour;
In the described step 3) pressing step, pressure is 30-80MPa, preferred 60MPa, and the time is 10～20 minutes, preferred 15 minutes;
Described step 4) charing step be with the flexible graphite plate after the described compacting successively through intensification A, insulation B, intensification C, insulation D, intensification E, insulation F and the H step of lowering the temperature naturally, obtain the flexible graphite plate after the described charing;
In the described intensification A step, initial temperature is 5～30 ℃, and heating rate is 1-5 ℃/min;
In the described insulation B step, temperature is 200-350 ℃, and the time is 20-90 minute;
In the described intensification C step, heating rate is 0.5-2 ℃/min;
In the described insulation D step, temperature is 400-700 ℃, and the time is 20-90 minute;
In the described intensification E step, heating rate is 1.5-4.5 ℃/min;
In the described insulation F step, temperature is 750-1000 ℃, and the time is 20-90 minute;
In the described H of the cooling naturally step, finishing temperature is 5～30 ℃.
In the described step 5) pressing step, pressure is 10-60MPa, preferred 30MPa, and the time is 10～20 minutes, preferred 15 minutes.
Above-mentioned vanadium battery bi-polar plate provided by the invention can get according to any one method preparation among the following method a-method c;
Described method a is: it is 30% that described flexible graphite plate is placed mass percentage concentration, number-average molecular weight is to boil dipping 3 hours in the methanol solution of phenolic resins of 800g/mol, drying is 24 hours under 20～30 ℃, after solidifying 1 hour under 180 ℃, compacting is 15 minutes under 50Mpa pressure, flexible graphite plate after the described compacting is carried out charing in nitrogen atmosphere, the charing program is as follows: under 5～30 ℃, be warming up to 300 ℃ with 2 ℃/min, be incubated 20 minutes, be warming up to 600 ℃ with 0.75 ℃/min, be incubated 30 minutes, be warming up to 850 ℃ with 2 ℃/min, be incubated 30 minutes, naturally cool to 5～30 ℃ after, compacting is 15 minutes under 20Mpa pressure, obtains described vanadium battery bi-polar plate;
Described method b is: it is 10% that described flexible graphite plate is placed mass percentage concentration, number-average molecular weight is to boil dipping 4 hours in the methanol solution of epoxy resin of 1000g/mol, drying is 24 hours under 20～30 ℃, after solidifying 2 hours under 120 ℃, compacting is 10 minutes under 80Mpa pressure, flexible graphite plate after the described compacting is carried out charing in nitrogen atmosphere, the charing program is as follows: under 5～30 ℃, be warming up to 200 ℃ with 1 ℃/min, be incubated 60 minutes, be warming up to 400 ℃ with 0.5 ℃/min, be incubated 90 minutes, be warming up to 1000 ℃ with 4.5 ℃/min, be incubated 90 minutes, naturally cool to 5～30 ℃ after, compacting is 10 minutes under 60Mpa pressure, obtains described vanadium battery bi-polar plate;
Described method c is: it is 40% that described flexible graphite plate is placed mass percentage concentration, number-average molecular weight is to boil dipping 1 hour in the methanol solution of phenolic resins of 800g/mol, placed 24 hours down for 20～30 ℃, after solidifying 1.5 hours under 200 ℃, compacting is 20 minutes under 30Mpa pressure, flexible graphite plate after the described compacting is carried out charing in nitrogen atmosphere, the charing program is as follows: under 5～30 ℃, be warming up to 350 ℃ with 5 ℃/min, be incubated 90 minutes, be warming up to 700 ℃ with 2 ℃/min, be incubated 20 minutes, be warming up to 750 ℃ with 1.5 ℃/min, be incubated after 20 minutes, naturally cool to 5～30 ℃ after, compacting is 20 minutes under 10Mpa pressure, obtains described vanadium battery bi-polar plate.
The application in the preparation vanadium cell of the vanadium battery bi-polar plate for preparing according to the method described above and this vanadium battery bi-polar plate also belongs to protection scope of the present invention.
Vanadium battery bi-polar plate provided by the invention is to be basic material with commercially available flexible graphite plate, boils by being impregnated in the thermosetting resin, is made through overcuring, compacting, charing, compacting supervisor again.Vanadium battery bi-polar plate provided by the invention has following advantage:
1, the porosity reduces greatly, and sealing property is better.The porosity of commercially available flexible graphite plate is generally 35-45%, and vanadium battery bi-polar plate provided by the invention, the porosity only is 7-13%.
2, charge and discharge resistance and reduce greatly, efficiency for charge-discharge obviously improves.
3, decay resistance significantly improves.Under same experiment condition, surperficial bulging can take place in flexible graphite plate after repeatedly charging and discharging circulation, be out of shape and wait the phenomenon that is corroded, and the bipolar plates of made of the present invention is improved in these areas greatly.
4, this vanadium battery bi-polar plate is material of main part with the flexible graphite plate, and cost of manufacture is low, and the price of large area flexible graphite cake is generally about 1/30 of high density glass carbon plate.
5, production cost is low, and technology is simple, easily amplifies or batch process, has good application prospects at the vanadium cell production field.
Description of drawings
Fig. 1 is the used vanadium single-cell structure schematic diagram of test bipolar plates of the present invention.
The vanadium monocell that Fig. 2 is assembled into respectively for bipolar plates, commercially available flexible graphite plate a and the glass carbon graphite plate made from embodiment 1 discharge and recharge result of the test.
The vanadium monocell that Fig. 3 is assembled into respectively for bipolar plates, commercially available flexible graphite plate a and the glass carbon graphite plate made from embodiment 1 when 90 loop tests battery discharge and recharge the impedance experiments result.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.Commercially available flexible graphite plate a described in the present invention is the flexible graphite plate as preparation vanadium battery bi-polar board raw material.The performance parameter of this commercially available flexible graphite plate is as shown in table 1:
Among table 1, the present invention as the performance parameter tabulation of the commercially available flexible graphite plate a of raw material
| Density (g/cm 3) | Ash content (%) | Surface resistivity (m Ω m) | Flexural strength (MPa) | Rebound degree (%) |
| ??1.1 | ??≤2 | ??0.8 | ??40 | ??4 |
Length, width and thickness are respectively the commercially available flexible graphite plate a of 110mm, 110mm and 2mm, and placing mass percentage concentration is the methanol solution of 30% phenolic resins (number-average molecular weight 800g/mol), boils dipping 3 hours.Room temperature (20～30 ℃) is dry down placed 24 hours, put into baking oven then, solidified 1 hour down at 180 ℃.Graphite cake after solidifying under 50Mpa pressure, was suppressed 15 minutes.Graphite cake after the compacting is placed in the atmosphere furnace of nitrogen protection; the intensification charing; heating schedule is as follows: under the room temperature (5～30 ℃); be warming up to 300 ℃ with 2 ℃/min, be incubated 20 minutes, be warming up to 600 ℃ with 0.75 ℃/min; be incubated 30 minutes; be warming up to 850 ℃ with 2 ℃/min, be incubated 30 minutes, in stove, naturally cool to room temperature afterwards.Graphite cake after the charing was suppressed 15 minutes under 20Mpa pressure, obtained vanadium battery bi-polar plate provided by the invention.
Length, width and thickness are respectively the commercially available flexible graphite plate a of 110mm, 110mm and 2mm, placing mass percentage concentration is that 10% 6101 epoxy resin are (available from the prosperous gluing Science and Technology Ltd. of Shanghai Road, product type is E-44, number-average molecular weight is 1000g/mol) methanol solution in, boil the dipping 4 hours.Room temperature (20～30 ℃) is dry down placed 24 hours, put into baking oven then, solidified 2 hours down at 120 ℃.Graphite cake after solidifying under 80Mpa pressure, was suppressed 10 minutes.Graphite cake after the compacting is placed in the atmosphere furnace of nitrogen protection; the intensification charing; heating schedule is as follows: under the room temperature (5～30 ℃); be warming up to 200 ℃ with 1 ℃/min, be incubated 60 minutes, be warming up to 400 ℃ with 0.5 ℃/min; be incubated 90 minutes; be warming up to 1000 ℃ with 4.5 ℃/min, be incubated 90 minutes, in stove, naturally cool to room temperature afterwards.Graphite cake after the charing was suppressed 10 minutes under 60Mpa pressure, obtained vanadium battery bi-polar plate provided by the invention.
Embodiment 3
Length, width and thickness are respectively the commercially available flexible graphite plate a of 110mm, 110mm and 2mm, and placing mass percentage concentration is the methanol solution of 40% phenolic resins (number-average molecular weight 800g/mol), boils dipping 1 hour.Room temperature (20～30 ℃) is dry down placed 24 hours, put into baking oven then, solidified 1.5 hours down at 200 ℃.Graphite cake after solidifying under 30Mpa pressure, was suppressed 20 minutes.Graphite cake after the compacting is placed in the atmosphere furnace of nitrogen protection; the intensification charing; heating schedule is as follows: under the room temperature (5～30 ℃); be warming up to 350 ℃ with 5 ℃/min, be incubated 90 minutes, be warming up to 700 ℃ with 2 ℃/min; be incubated 20 minutes; be warming up to 750 ℃ with 1.5 ℃/min, be incubated 20 minutes, in stove, naturally cool to room temperature afterwards.Graphite cake after the charing was suppressed 20 minutes under 10Mpa pressure, obtained vanadium battery bi-polar plate provided by the invention.
Table 2, be 60mA/cm with each embodiment bipolar plates and commercially available flexible graphite plate a, glass carbon graphite monocell that plate is adorned in current density respectively
2The determination data of the 30th charge and discharge cycles efficient tabulation down
| The bipolar plates porosity/% | Current efficiency/% | Voltage efficiency/% | Electrical efficiency/% | Average charging tension/V | Average discharge volt/V | Average impedance/Ω cm -2 | |
| Embodiment 1 | ??7 | ??94.6 | ??82.3 | ??78.2 | ??1.479 | ??1.217 | ??2.2 |
| |
??9 | ??94.1 | ??81.6 | ??76.8 | ??1.477 | ??1.213 | ??2.2 |
| Embodiment 3 | ??10 | ??94.3 | ??81.9 | ??77.2 | ??1.476 | ??1.211 | ??2.2 |
| Graphite cake is untreated | ??39 | ??94.2 | ??78.5 | ??73.9 | ??1.499 | ??1.177 | ??2.7 |
| Glass carbon graphite plate | ??0 | ??93.8 | ??82.2 | ??77.1 | ??1.473 | ??1.211 | ??2.2 |
The listed porosity is to measure according to the assay method of GB JB/T 8133.1-1999 in the table 2, as shown in Table 2, the porosity that embodiment 1-3 prepares the gained vanadium battery bi-polar plate is respectively 7%, 9% and 10%, far below the porosity of commercially available flexible graphite plate 35-45%.
Fig. 1 is the used vanadium single-cell structure schematic diagram of test vanadium battery bi-polar plate of the present invention, and wherein, 1 is proton exchange membrane, and 2 is the separatory frame, and 3 is the charcoal felt, and 4 is vanadium battery bi-polar plate, and 5 is copper coin, and 6 is end plate.
Fig. 2 is the 30th the loop test result of vanadium monocell who utilizes embodiment 1 preparation gained vanadium battery bi-polar plate, commercially available flexible graphite plate a and glass carbon graphite plate to be assembled into respectively, and charging or discharging current density is 60mA/cm
2
Fig. 3 be utilize vanadium monocell that embodiment 1 preparation gained vanadium battery bi-polar plate, commercially available flexible graphite plate a and glass carbon graphite plate be assembled into respectively when 90 loop tests battery discharge and recharge the impedance experiments result, wherein, current density is 60mA/cm
2
Among above-mentioned Fig. 2 and Fig. 3, the computing formula that discharges and recharges impedance R is:
R=(average charging tension-average discharge volt)/(current density * 2)
By Fig. 2 and Fig. 3 as can be known, its charging voltage of flexible graphite plate provided by the invention is lower, and discharge voltage is higher, and voltage efficiency obviously will be higher than the flexible graphite plate that is untreated; Its average impedance of flexible graphite plate provided by the invention is starkly lower than the flexible graphite plate that is untreated in 100 loop tests, and performance and glass carbon graphite plate are approaching.
Claims (10)
1. a method for preparing vanadium battery bi-polar plate comprises the steps:
1) flexible graphite plate is placed the organic solution of thermosetting resin flood, the flexible graphite plate after obtaining flooding;
2) will be cured the flexible graphite plate after obtaining solidifying after the flexible graphite plate drying behind the described dipping;
3) flexible graphite plate after the described curing is suppressed the flexible graphite plate after obtaining suppressing;
4) flexible graphite plate after the described compacting is carried out charing, obtain the flexible graphite plate after the charing;
5) flexible graphite plate after the described charing is suppressed, obtained described vanadium battery bi-polar plate.
2. method according to claim 1 is characterized in that: in the described step 1), described thermosetting resin is at least a in epoxy resin and the phenolic resins; In the organic solution of described thermosetting resin, organic solvent is selected from least a in methyl alcohol and the ethanol.
3. method according to claim 1 and 2 is characterized in that: in the described step 1), the mass percentage concentration of the organic solution of described thermosetting resin is 10-40%, and the number-average molecular weight of described thermosetting resin is 200～2000g/mol.
4. method according to claim 3 is characterized in that: in the described step 1), the mass percentage concentration of the organic solution of described thermosetting resin is 30%.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: in the described step 1) impregnation steps, temperature is the boiling point of organic solvent in the described organic solution, and the time is 1～4 hour;
Described step 2) in the drying steps, temperature is 20～30 ℃, and the time is 12～36 hours; In the described curing schedule, temperature is 120-200 ℃, and the time is 0.5～2 hour;
In the described step 3) pressing step, pressure is 30-80MPa, and the time is 10～20 minutes;
In the described step 5) pressing step, pressure is 10-60MPa, and the time is 10～20 minutes.
6. method according to claim 5 is characterized in that: in the described step 1) impregnation steps, temperature is the boiling point of organic solvent in the described organic solution, and the time is 3 hours;
Described step 2) in the drying steps, temperature is 25 ℃, and the time is 24 hours; In the described curing schedule, temperature is 150 ℃, and the time is 1 hour;
In the described step 3) pressing step, pressure is 60MPa, and the time is 15 minutes;
In the described step 5) pressing step, pressure is 30MPa, and the time is 15 minutes.
7. according to the arbitrary described method of claim 1-6, it is characterized in that: described step 4) charing step be with the flexible graphite plate after the described compacting successively through intensification A, insulation B, intensification C, insulation D, intensification E, insulation F and the H step of lowering the temperature naturally, obtain the flexible graphite plate after the described charing;
In the described intensification A step, initial temperature is 5～30 ℃, and heating rate is 1-5 ℃/min;
In the described insulation B step, temperature is 200-350 ℃, and the time is 20-90 minute;
In the described intensification C step, heating rate is 0.5-2 ℃/min;
In the described insulation D step, temperature is 400-700 ℃, and the time is 20-90 minute;
In the described intensification E step, heating rate is 1.5-4.5 ℃/min;
In the described insulation F step, temperature is 750-1000 ℃, and the time is 20-90 minute;
In the described H of the cooling naturally step, finishing temperature is 5～30 ℃.
8. according to the arbitrary described method of claim 1-7, it is characterized in that: described vanadium battery bi-polar plate is to get according to any one method preparation among the following method a-method c;
Described method a is: it is that the methanol solution of 30% phenolic resins boiled dipping 3 hours that described flexible graphite plate is placed mass percentage concentration, drying is 24 hours under 20～30 ℃, after solidifying 1 hour under 180 ℃, compacting is 15 minutes under 50Mpa pressure, flexible graphite plate after the described compacting is carried out charing in nitrogen atmosphere, the charing program is as follows: under 5～30 ℃, be warming up to 300 ℃ with 2 ℃/min, be incubated 20 minutes, be warming up to 600 ℃ with 0.75 ℃/min, be incubated 30 minutes, be warming up to 850 ℃ with 2 ℃/min, be incubated 30 minutes, naturally cool to 5～30 ℃ after, compacting is 15 minutes under 20Mpa pressure, obtains described vanadium battery bi-polar plate; The number-average molecular weight of described phenolic resins is 800g/mol;
Described method b is: it is that the methanol solution of 10% epoxy resin boiled dipping 4 hours that described flexible graphite plate is placed mass percentage concentration, drying is 24 hours under 20～30 ℃, after solidifying 2 hours under 120 ℃, compacting is 10 minutes under 80Mpa pressure, flexible graphite plate after the described compacting is carried out charing in nitrogen atmosphere, the charing program is as follows: under 5～30 ℃, be warming up to 200 ℃ with 1 ℃/min, be incubated 60 minutes, be warming up to 400 ℃ with 0.5 ℃/min, be incubated 90 minutes, be warming up to 1000 ℃ with 4.5 ℃/min, be incubated 90 minutes, naturally cool to 5～30 ℃ after, compacting is 10 minutes under 60Mpa pressure, obtains described vanadium battery bi-polar plate; Described epoxy resin is that the product type that the prosperous gluing Science and Technology Ltd. of Shanghai Road sells is that E-44, number-average molecular weight are 6101 epoxy resin of 1000g/mol;
Described method c is: it is that the methanol solution of 40% phenolic resins boiled dipping 1 hour that described flexible graphite plate is placed mass percentage concentration, placed 24 hours down for 20～30 ℃, after solidifying 1.5 hours under 200 ℃, compacting is 20 minutes under 30Mpa pressure, flexible graphite plate after the described compacting is carried out charing in nitrogen atmosphere, the charing program is as follows: under 5～30 ℃, be warming up to 350 ℃ with 5 ℃/min, be incubated 90 minutes, be warming up to 700 ℃ with 2 ℃/min, be incubated 20 minutes, be warming up to 750 ℃ with 1.5 ℃/min, be incubated after 20 minutes, naturally cool to 5～30 ℃ after, compacting is 20 minutes under 10Mpa pressure, obtains described vanadium battery bi-polar plate; The number-average molecular weight of described phenolic resins is 800g/mol.
9. the vanadium battery bi-polar plate for preparing of the arbitrary described method of claim 1-8.
10. the application of the described vanadium battery bi-polar plate of claim 9 in the preparation vanadium cell.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456977A (en) * | 2013-08-28 | 2013-12-18 | 广东电网公司电力科学研究院 | Method for improving operation efficiency of all-vanadium redox flow battery |
| CN106299389A (en) * | 2016-11-11 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Bipolar plate of all-vanadium redox flow battery and preparation method thereof |
| CN108598519A (en) * | 2018-05-18 | 2018-09-28 | 深圳市晶特智造科技有限公司 | A kind of bipolar plates and preparation method thereof |
| CN109411779A (en) * | 2017-08-17 | 2019-03-01 | 中国科学院金属研究所 | A kind of preparation method of vanadium cell soft graphite bipolar plates |
| CN110993981A (en) * | 2019-12-17 | 2020-04-10 | 上海大学 | Method for preparing ultrathin carbon/carbon composite bipolar plate |
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| CN1731610A (en) * | 2005-08-01 | 2006-02-08 | 南通大学 | Method for manufacturing proton exchange membrane fuel cell double plates |
| CN101290993A (en) * | 2007-04-18 | 2008-10-22 | 新源动力股份有限公司 | Flexible polar plate of mineral carbon with grooves on both sides |
| 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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| JPH02184510A (en) * | 1989-01-10 | 1990-07-19 | Showa Denko Kk | Production of carbon plate |
| CN1731610A (en) * | 2005-08-01 | 2006-02-08 | 南通大学 | Method for manufacturing proton exchange membrane fuel cell double plates |
| CN101290993A (en) * | 2007-04-18 | 2008-10-22 | 新源动力股份有限公司 | Flexible polar plate of mineral carbon with grooves on both sides |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456977A (en) * | 2013-08-28 | 2013-12-18 | 广东电网公司电力科学研究院 | Method for improving operation efficiency of all-vanadium redox flow battery |
| CN103456977B (en) * | 2013-08-28 | 2016-06-08 | 广东电网公司电力科学研究院 | Improve the method for operation efficiency of all-vanadium redox flow battery |
| CN106299389A (en) * | 2016-11-11 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Bipolar plate of all-vanadium redox flow battery and preparation method thereof |
| CN109411779A (en) * | 2017-08-17 | 2019-03-01 | 中国科学院金属研究所 | A kind of preparation method of vanadium cell soft graphite bipolar plates |
| CN108598519A (en) * | 2018-05-18 | 2018-09-28 | 深圳市晶特智造科技有限公司 | A kind of bipolar plates and preparation method thereof |
| CN110993981A (en) * | 2019-12-17 | 2020-04-10 | 上海大学 | Method for preparing ultrathin carbon/carbon composite bipolar plate |
| CN110993981B (en) * | 2019-12-17 | 2022-01-28 | 上海大学 | Method for preparing ultrathin carbon/carbon composite bipolar plate |
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Application publication date: 20100804 |