CN101853942A - Double electrode plate for all-vanadium liquid flow energy storage battery and preparation method thereof - Google Patents
Double electrode plate for all-vanadium liquid flow energy storage battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Double electrode plate for an all-vanadium liquid flow energy storage battery, which has a layer-type structure divided into five layers from top to bottom, the outermost layers of two sides are respectively a surface conducting layer (1) and a surface conducting layer (5) and are composed of polyacrylonitrile graphite felt; secondary inner layers on two sides are respectively a carbon cloth conducting layer (2) and a carbon cloth conducting layer (4) and are made of carbon fiber braided fabric; a middle layer is a master conducting layer (3) and is made of polyacrylonitrile graphite felt. Conducting material is added in vinyl resin at ratio and the mixture is evenly stirred, and initiator and accelerator are added to obtain conducting resin; the conducting resin is coated on the carbon cloth conducting layer (2), the master conducting layer (3) and the carbon cloth conducting layer (4); all conducting layers are stacked in order, and the surface conducting layer (1) is arranged on the topside, and the surface conducting layer (5) is arranged downmost; the obtained product is put into a die to pressurize for 5MPa and is solidified at normal temperature for 6 hours to obtain the double battery lead plate. The double battery lead plate has high electric conductivity, favourable mechanical strength, simple manufacturing and low production cost.
Description
Technical field
Patent of the present invention relates to a kind of double electrode plate, and it belongs to battery manufacturing technology field, and it can be applicable among the all-vanadium liquid flow energy storage battery.
Background material
All-vanadium liquid flow energy storage battery is the novel energy-storage battery that latest developments are got up, it is that vanadium ion by different valence state transforms mutually, realize the storage and the release of electric energy, avoided variety classes active material between positive and negative half-cell to interpenetrate the cross pollution of generation from principle, because it has the energy conversion efficiency height, stored energy capacitance is big, long working life, can surpass deep discharge and can not produce irreversible damage battery, system design is flexible, and the power of battery and capacity can combination in any, and battery manufacturing and offal treatment do not produce any pollution to environment, be a kind of battery of environmental type, be subjected to the favor of battery industry deeply.Can be widely used among the supporting energy storage device of solar-energy photo-voltaic cell, wind electricity generating system, emergency power system and peak-load regulation, it also is the key areas that all-vanadium liquid flow energy storage battery is used that the electric energy of following electric automobile provides.
Battery lead plate is the all-vanadium liquid flow energy storage battery important components, and it is in very rugged environment work down, and it is proposed very high requirement, require the double electrode plate chemical stability good, electro-chemical activity is good, the mechanical strength height, impermeability is good, low cost of manufacture and long working life.Be in the all-vanadium liquid flow energy storage battery in research and development or pilot scale stage at present, mostly adopt the double electrode plate that is made of graphite cake, it is the Composite Double battery lead plate of base material with the macromolecular material that employing is also arranged.
The chemical stability of graphite cake electrode is good, and the conductance height has certain mechanical strength, and graphite cake performance of watertightness after treatment improves, and can satisfy the instructions for use of all-vanadium liquid flow energy storage battery to a certain extent.But when battery lead plate is in when discharging and recharging work under the high current density for a long time, the etching phenomenon can appear in the graphite electrode plate surface.Herein, along with the power raising of all-vanadium liquid flow energy storage battery, the battery lead plate area increases, and is subjected to the restriction of graphite electrode plate manufacturing process, and the manufacture difficulty of large size electro pole plate increases thereupon, and corresponding cost sharply rises.Owing to exist above-mentioned shortcoming, affect the promotion and application of graphite electrode plate, thereby make many units turn to research and test with the macromolecular material being the combination electrode plate of base material.
With the macromolecular material is the combination electrode plate of base material, the electric conducting material that a certain amount of acid resistance of blending is good in macromolecular material (as graphite, carbon black, conductive black, conducting powder, carbon fiber, conductive fiber etc.) makes polymer modification exactly, increase conductance, formation can be applicable to the battery lead plate material that all-vanadium liquid flow energy storage battery uses.This class battery lead plate manufacturing process is simple, with low cost, can obtain the battery lead plate of arbitrary dimension, improves in battery charge and discharge process electrode plate surface etching phenomenon.Because macromolecular material belongs to the insulator category, along with the increase of electric conducting material blending amount, conductance improves, but certain limit is arranged, and too much blending descends the bond strength between macromolecular material and the blend, and blend will come off.Therefore says that this class combination electrode plate is not as good as graphite electrode plate aspect electric conductivity, cause using the energy conversion efficiency decline of the all-vanadium liquid flow energy storage battery of combination electrode.
By the battery lead plate electrical conduction mechanism as can be known, because there is resistance in battery lead plate, battery produces voltage drop in the battery lead plate both sides and forms energy loss in charge and discharge process, is to influence one of all-vanadium liquid flow energy storage battery energy conversion efficiency decrease reason.
The voltage drop of battery lead plate both sides can be calculated by following formula roughly
V is the voltage drop of battery lead plate both sides in the formula;
I is the electric current that flows through battery lead plate;
R is the resistance of battery lead plate;
ρ is the battery lead plate resistivity of material;
δ is the thickness of battery lead plate;
I is the current density that flows through the battery lead plate electric current;
S is the area of battery lead plate.
From following formula as can be known, reduce the voltage drop of battery lead plate both sides, reduce i, three parameters of ρ and δ all can be proved effective.The current density i that discharges and recharges is an operational factor, is that size along with the battery charging and discharging electric current is in continuous variation.The electricalresistivity's of main at present consideration electrode material decline and the minimizing of battery lead plate thickness δ.Reduce the thickness of battery lead plate, it is subjected to the restriction of the mechanical strength of battery lead plate, especially for high-power all-vanadium liquid flow energy storage battery.Reduce the resistivity of battery lead plate material, as macromolecular material is the combination electrode of base material, can not depend merely on the amount that improves the blending electric conducting material and reduce, the combination electrode plate voltage drop that therefore will reduce macromolecular material and be base material has become one of key technology of present double electrode plate research.Should be from electrode plate structure, aspects such as battery lead plate material and battery lead plate manufacture craft are taken all factors into consideration just and can be proved effective.
Summary of the invention
Patent of the present invention provides a kind of double electrode plate of all-vanadium liquid flow energy storage battery, and it can comprehensively improve the performance of present double electrode plate, has following characteristics:
1. chemical stability height can be competent at a job in the highly acid electrolyte of all-vanadium liquid flow energy storage battery;
2. conduct electricity very well, help the raising of all-vanadium flow accumulate energy content of battery conversion efficiency;
3. discharge and recharge work under long-term high current density, its surface does not produce etching and obscission, long working life;
4. easily manufactured, there is not the production bottleneck of making the large scale double electrode plate;
5. production cost is low.
Patent of the present invention solves its technical problem, and the technical scheme of employing is:
1. select the base material of the vinylite of acidproof excellent anti-corrosion performance as double electrode plate for use, the blending electric conducting material carries out modification to it, prepares double electrode plate.Therein ethylene base resin is that phenolic aldehyde epoxy vinyl fat, bisphenol-A epoxy vinyl esters, HET acid modified epoxy vinyl esters, brominated bisphenol epoxy vinyl refer to, the modified epoxy vinyl fat of elastomer-modified epoxy vinyl fat, isocyanates.
2. acidproof corrosion resistant electric conducting material has graphite, conducting powder, conductive black, conductive fiber, carbon fiber etc., select for use this among two or more mixture that constitutes electric conducting material add among the vinylite, constitute electroconductive resin.
3. the mixing proportion of vinylite and electric conducting material mixture by optimizing screening, under the condition of assurance to the adhesion strength of blending electric conducting material, improves the conductance of double electrode plate material as possible.
4. double electrode plate is a layered structure, and this structure can make double electrode plate improve conductance, and enhance mechanical strength reduces thickness.It is divided into five layers up and down:
Ground floor is the surface conductance layer, made by the polyacrylonitrile graphite felt, it is bonded on the second layer conductive carbon layer of cloth, makes the double electrode plate surface form porous network structure, to increase double electrode plate and the contacted surface area of electrolyte, improve the electric conductivity of double electrode plate.
The second layer is the conductive carbon layer of cloth, carbon fiber preform by the coated with conductive resin is made, the mediate both sides of layer of it and the 4th layer, say from mechanical strength, having high-intensity carbon fiber preform, be positioned at the outside of double electrode plate intensity neutral line, is to be very favourable to the mechanical strength that strengthens double electrode plate, then allow the thickness of attenuate double electrode plate, reduce the resistance value of double electrode plate.
Taking the electricity layer polyacrylonitrile graphite felt by the coated with conductive resin as the leading factor for the 3rd layer constitutes.Because graphite felt is the porous, electrically conductive network system, its resistance is very little.
The 4th layer is the conductive carbon layer of cloth, is made by the carbon fiber preform of coated with conductive resin, and it is identical with the function of the second layer.
The effect of patent of the present invention:
1. adopt layered structure can strengthen the double electrode plate mechanical strength, its thickness of attenuate improves electric conductivity.
2. the outer surface up and down of double electrode plate is the porousness network structure, and is big with the contacted surface area of electrolyte, improved electric conductivity.
3. the employing vinylite has excellent decay resistance.
4. the vinyl tree refers to and the optimization proportioning of electric conducting material, and electric conductivity improves.
5. the preparation method is simple, adopts the normal temperature cure method, the product percent of pass height, and production cost is low.
Description of drawings
Below in conjunction with drawings and Examples patent of the present invention is further specified
Fig. 1 is the structural representation of patent of the present invention
Among the figure
1. surface conductance layer;
2. conductive carbon layer of cloth;
3. main conductive layer;
4. conductive carbon layer of cloth;
5. surface conductance layer.
Embodiment
Take by weighing 100 parts of phenolic aldehyde epoxy vinyl esters, in mass ratio is that to take by weighing mass ratio be 4: 1 the conductive black and the mixture of charcoal fiber for 10: 6 ratio, mix and stirred 0.2-1 hour, electric conducting material is fully mixed with resin, add 3 parts of initator methyl ethyl ketone peroxides again, 1 part of promoter ring cobalt octoate liquid stirs and obtained electroconductive resin in 2-3 minute.Electroconductive resin is coated in conductive carbon layer of cloth (2), on main conductive layer (3) and the conductive carbon layer of cloth (4).Be stacked together in order then, and at the top and bottom lay surface conductance layer (1) and surface conductance layer (5) respectively, put into mould, pressurize 5Mpa solidified 6 hours at normal temperatures, then made double electrode plate.
Take by weighing 100 parts of bisphenol-A epoxy vinyl esters, in mass ratio is that 10: 5 ratio takes by weighing the mixture that mass ratio is 4: 3: 1 conducting powder, carbon black, conductive fiber, mix and stirred 0.2-1 hour, electric conducting material is fully mixed with resin, add 2 parts of initator methyl ethyl ketone peroxides again, 4 parts of promoter ring cobalt octoate liquid stir and obtained electroconductive resin in 2-3 minute.On electroconductive resin coated with conductive carbon cloth layer (2), main conductive layer (3) and conductive carbon layer of cloth (4).Be stacked together in order then, and, put into mould pressurize 5Mpa, solidified at normal temperatures 6 hours, then make double electrode plate at the top and bottom lay surface conductance layer (1) and surface conductance layer (5) respectively.
Take by weighing 100 parts of isocyanate-modified epoxy vinyl esters, in mass ratio is that 10: 6 ratio takes by weighing the mixture that mass ratio is 4: 3 conductive blacks, conductive fiber, mix and stirred 0.2-1.0 hour, electric conducting material is fully mixed with resin, add 3 parts of initator methyl ethyl ketone peroxides again, 3 parts of promoter ring cobalt octoate liquid stir and obtained electroconductive resin in 2-3 minute, and electroconductive resin is coated on conductive carbon layer of cloth (2), main conductive layer (3) and the conductive carbon layer of cloth (4).Be stacked together in order then, and at the top and bottom lay surface conductance layer (1) and surface conductance layer (5) respectively, put into mould, pressurize 5Mpa solidified 6 hours at normal temperatures, then made double electrode plate.
Claims (5)
1. double electrode plate for all-vanadium liquid flow energy storage battery and preparation method thereof, it is characterized in that: double electrode plate is a layered structure, is divided into five layers up and down, and ground floor is surface conductance layer (1), be made up of the polyacrylonitrile graphite felt, it is bonded on the second layer conduction charcoal layer of cloth (2); The second layer is conductive carbon layer of cloth (2), is made up of the carbon fiber preform of coated with conductive resin; Take electricity layer (3) as the leading factor, form for the 3rd layer by the polyacrylonitrile graphite felt of coated with conductive resin; The 4th layer of conductive carbon layer of cloth (4) is made up of the carbon fiber preform of coated with conductive resin; Layer 5 is surface conductance layer (5), is made up of the polyacrylonitrile graphite felt, and it is bonded on the 4th layer of conduction charcoal layer of cloth (4).
2. double electrode plate for all-vanadium liquid flow energy storage battery according to claim 1 and preparation method thereof is characterized in that: add electric conducting material in proportion and mix stirring in vinylite, add initator and promoter again, obtain electroconductive resin; Again this electroconductive resin is coated on conductive carbon layer of cloth (2) uniformly, on main conductive layer (3) and the conductive carbon layer of cloth (4), stack in order then at the top and bottom lay surface conductance layer (1) and surface conductance layer (5) respectively, put into mould, pressurize 5Mpa, solidified at normal temperatures 6 hours, and promptly made double electrode plate for all-vanadium liquid flow energy storage battery.
3. according to described double electrode plate for all-vanadium liquid flow energy storage battery of claim 1 and preparation method thereof, it is characterized in that: vinylite is phenolic aldehyde epoxy vinyl ester, bisphenol-A epoxy vinyl esters, HET acid modified epoxy vinyl esters, bromine second bisphenol-A epoxy alicyclic vinyl, elastomer-modified epoxy vinyl fat, isocyanide acetate modified epoxy vinyl fat.
4. double electrode plate for all-vanadium liquid flow energy storage battery according to claim 1 and preparation method thereof is characterized in that: electric conducting material is two or more the mixture in conductive black, conducting powder, graphite, carbon fiber, conductive fiber, the carbon black.
5. double electrode plate for all-vanadium liquid flow energy storage battery according to claim 1 and preparation method thereof, it is characterized in that: the conductive carbon layer of cloth uses carbon fiber or conductive fiber braid to make, its parameter is: Density is through being 10-12/25mm ± 1, and latitude is 10～12/25 ± 1, and grammes per square metre is 250g/m
2, thickness is 0.4mm.
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