CN103682386A - Battery structure for flow energy storage batteries and all-vanadium flow energy storage battery - Google Patents
Battery structure for flow energy storage batteries and all-vanadium flow energy storage battery Download PDFInfo
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- CN103682386A CN103682386A CN201210315869.6A CN201210315869A CN103682386A CN 103682386 A CN103682386 A CN 103682386A CN 201210315869 A CN201210315869 A CN 201210315869A CN 103682386 A CN103682386 A CN 103682386A
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- battery structure
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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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- 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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0276—Sealing means characterised by their form
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- 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
Abstract
The invention relates to a battery structure for flow energy storage batteries. The battery structure comprises two collector plates and a CCM (Catalyst Coated Membrane) electrode, wherein the CCM electrode is formed by coating two sides of an ion exchange membrane with catalyst layers; electrocatalysts are contained in the catalyst layers; the CCM electrode is clamped between the two collector plates. The battery structure has the advantages that thicker materials such as a carbon-felt electrode, an electrode frame and the like in a traditional flow battery structure are saved, so that the mass and the volume of the battery are greatly reduced; compared with a traditional battery structure adopting face sealing, the battery structure disclosed by the invention can adopt line sealing to seal the battery, so that an expensive sealing fluororubber material is saved and the material cost is reduced; the battery structure is simple and feasible in preparation method and easy in operation condition controlling and is capable of realizing mass production.
Description
Technical field
The present invention relates to liquid flow energy storage battery field, the all-vanadium liquid flow energy storage battery that is specifically related to a kind of flow energy storage battery pool structure and comprises it.
Background technology
The day by day in short supply and serious problem of environmental pollution of fossil energy, impels the mankind hope of future source of energy to be placed on to wind energy, solar energy etc. are renewable, the development and utilization of clean energy resource.The feature of the renewable energy power generation such as wind energy, solar energy is unstable, discontinuous, these inferior electric currents to be connected to the grid or realize large-scale application, need to be by extensive energy-storage battery, by these inferior electric current collection get up to carry out smoothly, stable, controlled output, the demand that meets client terminal with this, realizes the application truly of regenerative resource.Flow battery is a kind of emerging secondary energy storage battery, different from other common batteries that active material is stored in to inside battery, it is stored in electrolyte the storage tank of outside batteries, by fluid pump and transfer pipeline, realize electrolysis circulating in battery cavity, and complete the charge and discharge process of battery.Such battery has system flexibly (power/capacity can independent design), the advantage such as capacitance of storage is large, addressing is free, easily realizes scale amplification.Compare other energy storage technology, it also have energy conversion efficiency high, can deep discharge, the feature such as safety and environmental protection, maintenance cost be low.This type of battery can be widely used in the renewable energy power generation energy storage such as wind energy, solar energy, and the electric power of its generation can be exported continuously and stably; Also can be used for electrical network to carry out " peak load shifting ", the night electricity of low power consumption is stored, peak of power consumption output by day, carrys out balancing electric power supply and demand with this; In addition this battery also can be used as emergency power system and stand-by station etc.All-vanadium liquid flow energy storage battery (Vanadium Flow Battery, VFB) is one of the most promising liquid flow energy storage battery in liquid flow energy storage battery.It adopts the ion V of vanadium different valence state
2+/ V
3+, VO
2 +/ VO
2+as positive and negative electrode active material, avoided to a great extent the cross pollution of both positive and negative polarity electrolyte solution respectively.In addition, its security and stability is good, energy conversion efficiency is high, long service life (life-span >15), low cost of manufacture, has started to enter commercialization and has promoted the stage.
Electrode material is one of critical material in liquid flow energy storage battery, and the main electrode material that VFB uses is at present carbon fiber felt or graphite felt.The main feature of kind electrode material is that porosity is high, and active area is relatively large.But it is for V
2+/ V
3+, VO
2 +/ VO
2+electrode reaction activity and the invertibity of oxidation-reduction pair are poor, have limited the further raising of battery performance.A lot of researchers have been developed the eelctro-catalyst of a series of powdery type, as carboxylated multi-walled carbon nano-tubes [CARBON49, (2011) 3463-3470], graphite and carbon nano tube compound material [Journal ofPower Sources184 (2008) 637-640], the doped meso-porous charcoal of nitrogen [Journal ofPower Sources195 (2010) 4375-4379] etc., these highly active powdery type eelctro-catalysts to be supported on carbon felt electrode to difficulty relatively, and in the middle of charge and discharge cycles process, easily occur coming off and pollute electrolyte.Realize the practical application of these powdery type high activated catalysts, need to explore a kind of suitable electrode material or battery structure.In addition, conventional carbon felt electrode material often needs the thickness of 4 ~ 6mm when application, and needs the battery cavities of corrosion resistant electrode frame formation to carry out sealed cell, has caused electrode volume and quality larger, has limited the raising of energy content of battery density.Explore VFB battery structure and improve the important directions that battery performance is this research field all the time.
Summary of the invention
The object of the invention is to overcome the existing all-vanadium liquid flow energy storage battery high-performance powder class eelctro-catalyst application problem of difficulty relatively, has designed a kind of all-vanadium liquid flow energy storage battery battery structure.
For achieving the above object, the technical solution used in the present invention is as follows:
A flow energy storage battery pool structure, described battery structure comprises collector plate, CCM type membrane electrode, wherein CCM type membrane electrode is to form in amberplex both sides coating Catalytic Layer, includes eelctro-catalyst in Catalytic Layer; CCM type membrane electrode is clamped between two collector plate.
In described CCM type membrane electrode surface catalytic layer eelctro-catalyst mixed binding agent be one or more in Nafion, PTFE, chlorinated polypropylene; The mass ratio of binding agent and eelctro-catalyst is 0.05: 1 ~ 0.5: 1.
Surface etch near CCM type membrane electrode one side in described collector plate has flow field structure.
Described collector plate material is metallic plate, graphite cake or carbon element composite plate.
Flow field in collector plate is single channel snake type flow field, multichannel snake type flow field, dot matrix type flow field, straight channel type flow field.
Described eelctro-catalyst is one or two or more kinds the powder in material with carbon element or the metal being supported by material with carbon element or metal oxide;
Material with carbon element is one or two or more kinds in activated carbon powder, graphite powder, carbon nano-tube, carbon fiber, Graphene, charcoal gel or Carbon foam.、
The metal that described material with carbon element supports is Pt, Ir, Ru or Bi; Metal oxide is RuO
2, WO
3, MoO
3or Mn
3o
4, their total loading is 5-60wt.%.
In described Catalytic Layer, eelctro-catalyst loading is 0.5 ~ 20mg/cm
2.
Between described collector plate and CCM type membrane electrode and between collector plate, pass through seal linear sealing.
Above-mentioned battery structure adopts following steps preparation:
1. wet film spraying process is prepared CCM type membrane electrode
(1) at room temperature, amberplex is fully soaked in deionized water, make it saturated swelling in deionized water;
(2) by eelctro-catalyst ultrasonic dispersion in alcoholic solution, alcoholic solution can adopt one or more in ethanol, propyl alcohol, isopropyl alcohol, and the ultrasonic wave time is controlled at 10 ~ 60Min.The ratio of eelctro-catalyst and alcoholic solution is: every 10mg eelctro-catalyst is dispersed in the middle of 0.5 ~ 3ml alcoholic solution;
(3) in the homodisperse system of above-mentioned eelctro-catalyst, add one or more in bonding agent and carry out ultrasonic dispersion, the mass ratio of binding agent and eelctro-catalyst is controlled at 0.05: 1 ~ and 0.5: 1.Ultrasonication 10 ~ 120Min.
(4) by the fully amberplex of swelling taking-up in deionized water, be laid on clean glass plate, its edge is fixed, adopt filter paper to suck gently the moisture on film surface.
(5) the scattered solution of step (3) is proceeded to the Sheng sap cavity of spray gun, with a kind of gas in nitrogen, argon gas, make carrier fluid gas, eelctro-catalyst is coated in to the surface of film lentamente, equably, CCM type membrane electrode surface electrical catalyst load amount is 0.5 ~ 20mg/cm
2.
(6) after completing one side spraying, again film is inserted to 5 ~ 30Min in deionized water, after taking out, repeat (4) and (5) step, carry out the spraying of an other side.Finally the CCM type membrane electrode of finished product is inserted in deionized water again, preserve stand-by.
2. flow field collector plate preparation
Engraving method: the whole collector plate of making even, thickness is 2 ~ 5mm, with digital engraving machine, by default flow field patterns, carves;
Die methods: first prepare mould by default flow field patterns, produce flow field collector plate in batches by compression moulding
3. battery assembling
The flow field collector plate of preparation and CCM are assembled according to mode described in accompanying drawing 2, and collector plate and CCM type membrane electrode carry out sealed cell with rubber ring.
Useful result of the present invention is:
(1) this battery structure has saved the materials such as thicker carbon felt electrode in traditional flow battery structure and electrode frame, has greatly reduced quality and the volume of battery, has improved mass energy density and the volume energy density of liquid flow energy storage battery.
(2) adopt linear sealing to carry out sealed cell, compare the face sealing of conventional batteries structure, saved comparatively expensive sealing fluorubber material, reduced material cost.
(3) this structure makes the application that the good powdery type electrode catalyst of catalytic performance is succeeded, solved carbon felt fiber surface support electrode catalyst more difficult, hold caducous problem.
(4) electrolyte flow resistance in flow field is less, has reduced the energy consumption of fluid pump.
(5) battery structure preparation method is simple, is easy to realize produce in enormous quantities.
(6) this kind of structure battery, has very large flexibility in design, has shown energy battery efficiency under different charging and discharging currents density, and stable cycle performance, has realized the controllability to all-vanadium liquid flow energy storage battery efficiency.
Accompanying drawing explanation
Fig. 1 is all-vanadium liquid flow energy storage battery conventional batteries structural representation;
1-collector plate wherein, 2-electrode frame, 3-electrode, 4-amberplex
Fig. 2 is all-vanadium liquid flow energy storage battery novel battery structural representation;
1-collector plate wherein, 2-CCM type membrane electrode
Fig. 3 is embodiment 1 after adopting VFB battery structure, in charging and discharging currents density, is 30mA/cm
2under charging and discharging curve;
Fig. 4 is embodiment 2 after adopting VFB battery structure, in charging and discharging currents density, is 40mA/cm
2under charging and discharging curve.
Embodiment
The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
At room temperature, Nafion115 type cation-exchange membrane is soaked in deionized water, make it saturated swelling in deionized water solution, choosing activated carbon powder is eelctro-catalyst, active carbon powder is carried out in aqueous isopropanol to ultrasonic dispersion 30Min, the ratio of eelctro-catalyst and alcoholic solution is: every 10mg eelctro-catalyst is dispersed in the middle of 2ml isopropyl alcohol; Getting Nafion solution is binding agent, and the mass ratio of binding agent and eelctro-catalyst is 0.2: 1, Nafion solution binding agent is added in the middle of the aqueous isopropanol of above-mentioned eelctro-catalyst to ultrasonic 30Min.Nafion115 type cation-exchange membrane is taken out from deionized water, be laid on clean glass plate, adopt adhesive tape that its edge is fixed, adopt filter paper to suck gently the moisture on film surface.Scattered eelctro-catalyst alcoholic solution is proceeded to the Sheng sap cavity of spray gun, with nitrogen carrier fluid gas, eelctro-catalyst is coated in to the surface of film lentamente, equably, CCM type membrane electrode surface activity powdered carbon eelctro-catalyst load amount is 5mg/cm
2, the bilateral of film sprays identical eelctro-catalyst.Collector plate is selected carbon element composite plate, and thickness is 3mm, and electrolyte solution runner is selected binary channels snake type flow field, and the flow field degree of depth is 1mm.Effective work area of amberplex and flow field collector plate is 9cm
2.
The CCM type membrane electrode that utilization prepares and flow field collector plate are carried out battery assembling by accompanying drawing 2, and used in battery initial electrolysis liquid is 0.75mol L
-1v
3++ 0.75mol L
-1vO
2 ++ 3mol L
-1h
2sO
4.At 30mAcm
-2current density carry out charge-discharge test.The all-vanadium liquid flow energy storage battery current efficiency of assembling is 92.3%, and voltage efficiency is 81.4%, and energy efficiency is 75.2%.
At room temperature, Porous-Organic type cation-exchange membrane is soaked in deionized water, make it saturated swelling in deionized water solution, choose the WO of loading 43wt.%
3/ C powder is eelctro-catalyst, by WO
3/ C powder carries out ultrasonic dispersion 30Min in aqueous isopropanol, and the ratio of eelctro-catalyst and alcoholic solution is: every 10mg eelctro-catalyst is dispersed in the middle of 3ml isopropyl alcohol; Getting PTFE solution is binding agent, and the mass ratio of binding agent and eelctro-catalyst is 0.3: 1, Nafion solution binding agent is added in the middle of the aqueous isopropanol of above-mentioned eelctro-catalyst to ultrasonic 50Min.Nafion115 type cation-exchange membrane is taken out from deionized water, be laid on clean glass plate, adopt adhesive tape that its edge is fixed, adopt filter paper to suck gently the moisture on film surface.Scattered eelctro-catalyst alcoholic solution is proceeded to the Sheng sap cavity of spray gun, with nitrogen carrier fluid gas, eelctro-catalyst is coated in to the surface of film lentamente, equably, CCM type membrane electrode surface activity powdered carbon eelctro-catalyst load amount is 3mg/cm
2, the bilateral of film sprays identical eelctro-catalyst.Collector plate is selected graphite cake, and thickness is 2mm, and electrolyte solution runner is selected point-like type flow field, and the flow field degree of depth is 1mm.Effective work area of amberplex and flow field collector plate is 9cm
2.
The CCM type membrane electrode that utilization prepares and flow field collector plate are carried out battery assembling by accompanying drawing 2, and used in battery initial electrolysis liquid is 0.75mol L
-1v
3++ 0.75mol L
-1vO
2 ++ 3mol L
-1h
2sO
4.At 40mAcm
-2current density carry out charge-discharge test.The all-vanadium liquid flow energy storage battery current efficiency of assembling is 95.2%, and voltage efficiency is 75.3%, and energy efficiency is 71.7%.
Claims (10)
1. a flow energy storage battery pool structure, is characterized in that, described battery structure comprises collector plate, CCM type membrane electrode, and wherein CCM type membrane electrode is to form in amberplex both sides coating Catalytic Layer, includes eelctro-catalyst in Catalytic Layer; CCM type membrane electrode is clamped between two collector plate.
2. battery structure according to claim 1, is characterized in that: in described CCM type membrane electrode surface catalytic layer eelctro-catalyst mixed binding agent be one or more in Nafion, PTFE, chlorinated polypropylene; The mass ratio of binding agent and eelctro-catalyst is 0.05: 1 ~ 0.5: 1.
3. battery structure according to claim 1, is characterized in that: the surface etch near CCM type membrane electrode one side in described collector plate has flow field structure.
4. according to the battery structure described in claim 1 or 3, it is characterized in that: described collector plate material is metallic plate, graphite cake or carbon element composite plate.
5. battery structure according to claim 3, is characterized in that: the flow field in collector plate is one or more in single channel snake type flow field, multichannel snake type flow field, dot matrix type flow field or straight channel type flow field.
6. battery structure according to claim 1 and 2, is characterized in that: described eelctro-catalyst is one or two or more kinds the powder in material with carbon element or the metal being supported by material with carbon element or metal oxide;
Material with carbon element is one or two or more kinds in activated carbon powder, graphite powder, carbon nano-tube, carbon fiber, Graphene, charcoal gel or Carbon foam.
7. battery structure according to claim 6, is characterized in that: the metal that described material with carbon element supports is Pt, Ir, Ru or Bi; Metal oxide is RuO
2, WO
3, MoO
3or Mn
3o
4, the total loading of metal and metal oxide is 5-60wt.%.
8. battery structure according to claim 1 and 2, is characterized in that: in described Catalytic Layer, eelctro-catalyst loading is 0.5 ~ 20mg/cm
2.
9. battery structure according to claim 1, is characterized in that: between described collector plate and CCM type membrane electrode and between collector plate, pass through seal linear sealing.
10. an all-vanadium liquid flow energy storage battery, is characterized in that: this battery is the all-vanadium liquid flow energy storage battery that adopts the arbitrary described battery structure of claim 1-9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106450351A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Combined electrode for all-vanadium redox flow battery and preparation method thereof |
| CN106972186A (en) * | 2016-01-14 | 2017-07-21 | 中国科学院金属研究所 | It is used for all-vanadium redox flow battery that there is catalysis to be combined membrane preparation method to positive and negative electrode |
| CN108461787A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院金属研究所 | A kind of preparation method of integrated composite membrane used for all-vanadium redox flow battery |
| CN111540914A (en) * | 2020-05-11 | 2020-08-14 | 辽宁大学 | Preparation method of functional porous graphene integrated electrode material and application of functional porous graphene integrated electrode material in vanadium battery |
| CN114665135A (en) * | 2022-01-30 | 2022-06-24 | 电子科技大学 | High-voltage-efficiency flow battery system |
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| CN102652374A (en) * | 2009-12-18 | 2012-08-29 | 联合工艺公司 | Flow battery with interdigitated flow field |
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| CN101179135A (en) * | 2006-09-25 | 2008-05-14 | 株式会社东芝 | Direct methanol fuel cell and production method thereof |
| CN102652374A (en) * | 2009-12-18 | 2012-08-29 | 联合工艺公司 | Flow battery with interdigitated flow field |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106972186A (en) * | 2016-01-14 | 2017-07-21 | 中国科学院金属研究所 | It is used for all-vanadium redox flow battery that there is catalysis to be combined membrane preparation method to positive and negative electrode |
| CN106450351A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Combined electrode for all-vanadium redox flow battery and preparation method thereof |
| CN106450351B (en) * | 2016-11-11 | 2019-07-26 | 攀钢集团攀枝花钢铁研究院有限公司 | All-vanadium flow battery combination electrode and preparation method thereof |
| CN108461787A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院金属研究所 | A kind of preparation method of integrated composite membrane used for all-vanadium redox flow battery |
| CN108461787B (en) * | 2017-02-17 | 2020-01-03 | 中国科学院金属研究所 | Preparation method of integrated composite membrane for all-vanadium redox flow battery |
| CN111540914A (en) * | 2020-05-11 | 2020-08-14 | 辽宁大学 | Preparation method of functional porous graphene integrated electrode material and application of functional porous graphene integrated electrode material in vanadium battery |
| CN111540914B (en) * | 2020-05-11 | 2022-06-14 | 辽宁大学 | Preparation method of functional porous graphene integrated electrode material and application of functional porous graphene integrated electrode material in vanadium battery |
| CN114665135A (en) * | 2022-01-30 | 2022-06-24 | 电子科技大学 | High-voltage-efficiency flow battery system |
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Application publication date: 20140326 |