CN108376788A - A kind of zinc-bromine flow battery pole plate - Google Patents
A kind of zinc-bromine flow battery pole plate Download PDFInfo
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- CN108376788A CN108376788A CN201810165266.XA CN201810165266A CN108376788A CN 108376788 A CN108376788 A CN 108376788A CN 201810165266 A CN201810165266 A CN 201810165266A CN 108376788 A CN108376788 A CN 108376788A
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- zinc
- plate
- zeolite imidazole
- carbon
- imidazole ester
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of zinc-bromine flow battery pole plates.The novel graphite resistor rod plate for having excellent conductive capability is prepared by the way that novel material zeolite imidazole ester skeleton structure nanometer carbon plate to be added in the pole plate in traditional petroleum coke, pitch.Meanwhile the present invention also added the enhancing particle for improving the anti-deformation nature of graphite electrode so that the zinc-bromine flow battery pole plate that the present invention is prepared has excellent electric conductivity and ability of anti-deformation.
Description
Technical field
The present invention relates to a kind of battery pole plates more particularly to a kind of zinc-bromine flow battery pole plates.
Background technology
Currently, be typically lead-acid battery in independent energy resource system accumulator as used in distributed energy resource system, and
Lead-acid battery whether self performance or for environment all there is fatal defect, for example lead-acid battery is in hot gas
The usually service life is very short in time environment, especially more serious in deep discharge；Meanwhile lead-acid battery is also harmful to environment, because
Its main component is lead, and serious environmental problem may be led to when producing and throwing aside.
Zinc liquid flow battery is a kind of liquid flow energy storage battery.Diaphragm in battery can influence the service efficiency of battery.Battery
In electrolyte cost can almost account for flow battery totle drilling cost 30%, so the entirety of the price decision of electrolyte battery is made
Valence.Zinc liquid flow battery because the high-energy density of zinc, low price and be easy it is a large amount of obtain, the system containing zinc can charge and discharge
Battery has very strong competitiveness in large-scale energy storage system.This electrolyte characteristic determines zinc liquid flow battery in cost
Aspect has prodigious advantage.Zinc-bromine flow battery electric discharge inch, the metallic zinc of surface deposition can be completely dissolved in the electrolytic solution,
To continually carry out depth charge and discharge, without causing battery loss.
For practicability, carbon material is most attraction in current ultracapacitor various types of electrodes material, it is almost
It is the selection that all capacitor products are common on the market；And conducting polymer, metal oxide etc. as electrode material also in
Among exploration, although having begun to be applied to commercial field, there is a certain distance apart from large-scale develop and use.From now on
The research emphasis of electrode material for super capacitor will focus on preparation process and the structure optimization of existing material, have both faraday's standard
The exploitation of capacitance and electric double layer capacitance new material and the large-scale production of high performance material, to adapt to market to high-performance, low
Cost, performance stablize the demand of mobile power technology.
Zinc-bromine flow battery electrolyte has certain corrosivity, and the long-term circulation immersion of electrolyte is for inside battery knot
Structure has certain corrosion swelling action, this effect to there is the change for inevitably causing both inner pad and diaphragm for a long time
Shape, deformed pole plate and diaphragm can form inhibition to inside battery liquid stream, to seriously affect battery utilization rate；With
The operation of battery, deformation run down, and battery efficiency is also gradually reduced.
Therefore, the present invention provides a kind of zinc-bromine flow battery pole plate, has excellent conductivity and anti-deformation nature.
Invention content
In view of the drawbacks described above of the prior art, the present invention develops a kind of zinc-bromine flow battery pole plate, it is characterised in that：
The pole plate includes positive plate and negative plate.
Preferably, the positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The negative plate is graphite
One kind in plate, carbon felt, graphite felt or carbon cloth.
Preferably, the carbon felt is commercially available carbon felt or is prepared using following methods：By the short carbon fiber that length is 2~5mm
Dimension, water soluble phenol resin, polyethylene glycol 200, water in mass ratio 1：(3~5)：(0.3~0.8)：(10~16) it mixes,
It is dispersed with stirring 30~50min under conditions of 200~500 revs/min；It pours into mold after pressurizeing exclusion moisture in 120~200 DEG C of perseverances
1~3h of temperature carries out solidification drying, forms carbon felt biscuit；After carbon felt biscuit is demoulded carbon is carried out in 700~1000 DEG C of 1~3h of constant temperature
Change is handled, and then in nitrogen atmosphere, 1700~2000 DEG C of 1~2h of constant temperature, is cooled to room temperature, is obtained carbon felt.
Preferably, the preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
Petroleum coke, pitch kneading are formed into core slurry；At 10~35 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to 10~30min of dispersant for ultrasonic dispersion, is configured to the zeolite imidazole ester skeleton structure of a concentration of 20~50mg/mL
Nanometer carbon plate dispersion liquid；By zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, enhancing particle kneading shape
At starch adhesive material；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 105~125 DEG C, squeeze pressure controls
10~18MPa controls 5~10min of dwell time,
S3 graphitization processings：
Then the compound green compact that step S2 is obtained is cut out by conventional roasting, graphitizable high temperature processing according to production requirement
To required shape to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；Calcination temperature control 1000~
1250 DEG C, roasting time is 10~30 days, and graphitizable high temperature processing control is at 2700~3400 DEG C, graphitizable high temperature processing time
For 15~50h.
Preferably, the mass ratio of the core slurry petrochina coke and pitch is (3~6):(1~3).
Preferably, zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, enhancing in the starch adhesive material
The mass ratio of particle is 1:(10~15):(3~5):(1~2).
A kind of graphene oxide graphite electrode is disclosed in CN106588016A in the prior art, by by graphene oxide
It is added in conventional graphite electrode thickener and a kind of graphene oxide electrode is prepared.Because graphene intensity is high, electron transfer
Graphene electrodes are applied to that in graphite electrode the flexural strength of graphite electrode articles can be improved while can also dropped by function admirable
Grade resistivity.But application of the graphene in graphite electrode has certain defect：The building-up process of graphene first is complicated, yield
Relatively low, industrialization cost is higher；Secondly, a large amount of acid solution has been used in the preparation process of graphene, be easy to cause dirt to environment
Dye；Finally, the coagulation under stronger Van der Waals'attractive force is easy between graphene sheet layer becomes graphite, thus loses the property of graphene
Energy.
The zeolite imidazole ester skeleton structure nanometer carbon plate that the present invention adds belongs to the metal-organic framework material of ordered structure
(MOFs).Zeolite imidazole ester skeleton structure nanometer carbon plate has high-specific surface area, abundant pore structure.
Preferably, the enhancing particle be tungsten oxide carbon nanotube, boron carbide micro powder, one kind in silicon carbide micro-powder or
A variety of mixing.
Preferably, the mass ratio of the core slurry and starch adhesive material is 10:(2~5).
Preferably, the preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.9~1.1g zinc acetates are dissolved in 250~300mL water and obtain aqueous zinc acetate solution by A；By 2.8~3.2g 2-
Methylimidazole, which is dissolved in 250~300mL water, obtains 2-methylimidazole aqueous solution；In 10~35 DEG C, the item of 200~500r/min
2-methylimidazole aqueous solution is added dropwise to the speed of 0.02~0.05g/s in aqueous zinc acetate solution under part, is added dropwise subsequent
Continue 20~36h of stirring under conditions of 10~35 DEG C, 200~500r/min, is filtered, washed, dry 24 at 40~60 DEG C~
48h obtains zeolite imidazole ester frame structure material；
B by zeolite imidazole ester frame structure material in nitrogen atmosphere with the heating rate of 3~5 DEG C/min from 10~35 DEG C
Be warming up to 800~1000 DEG C, and keep the temperature 1~3h at 800~1000 DEG C, then in carbon dioxide atmosphere with 5~10 DEG C/
The heating rate of min is warming up to 1200~1400 DEG C from 800~1000 DEG C, and 1.5~3h is kept the temperature at 1200~1400 DEG C, natural
It is cooled to room temperature to obtain zeolite imidazole ester skeleton structure nanometer carbon plate.
Preferably, the dispersant is a kind of or more in absolute ethyl alcohol, n,N-Dimethylformamide, tetrahydrofuran
Kind.
Preferably, the power of the ultrasonic disperse in the step S1 is 150~300W, and frequency is 24~40KHz.
Beneficial effects of the present invention：
Zinc-bromine flow battery pole plate prepared by the present invention has good electric conductivity, and resistivity is less than 6.3 μ Ω cm,
It is also equipped with excellent ability of anti-deformation simultaneously.Pole plate can keep initial shape for a long time in the long-term circulation immersion of electrolyte
Looks, to extend the service life of battery.
Specific implementation mode
Embodiment 1
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester frame structure material graphite cake.
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The preparation method of the zeolite imidazole ester frame structure material graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, zeolite imidazole ester frame structure material is added
Enter to be configured to the zeolite imidazole ester frame structure material dispersion liquid of a concentration of 40mg/mL to dispersant for ultrasonic dispersion 30min；
By zeolite imidazole ester frame structure material dispersion liquid, petroleum coke, pitch in mass ratio 1：10：3 are uniformly mixed, and are mediated in ZNH-5L
Machine (Laizhou new hongda chemical machinery Co., Ltd) is with kneading 30min forming face slurries under 200r/min；The dispersant is N,
Dinethylformamide；The power of the ultrasonic disperse is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester frame structure material graphite cake；The calcination temperature is controlled at 1200 DEG C,
Roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester frame structure material graphite cake is obtained, section is " returning " font；
Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester frame structure material is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution；2.9g2- methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 87%.
Embodiment 2
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；By zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch in mass ratio 1：10：3 are uniformly mixed,
In ZNH-5L kneaders (Laizhou new hongda chemical machinery Co., Ltd) with kneading 30min forming face slurries under 200r/min；Institute
It is N,N-dimethylformamide to state dispersant；The power of the ultrasonic disperse is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 89%.
Embodiment 3
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；Zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, tungsten oxide carbon nanotube, boron carbide is micro-
Powder in mass ratio 1：10：3：0.75：0.75 is uniformly mixed, in ZNH-5L kneaders (Laizhou new hongda chemical machinery Co., Ltd)
With kneading 30min forming face slurries under 200r/min；The dispersant is N,N-dimethylformamide；The work(of the ultrasonic disperse
Rate is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 92%.
Embodiment 4
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；Zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, tungsten oxide carbon nanotube, silicon carbide is micro-
Powder in mass ratio 1：10：3：0.75：0.75 is uniformly mixed, in ZNH-5L kneaders (Laizhou new hongda chemical machinery Co., Ltd)
With kneading 30min forming face slurries under 200r/min；The dispersant is N,N-dimethylformamide；The work(of the ultrasonic disperse
Rate is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 90%.
Embodiment 5
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；Zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, boron carbide micro powder, silicon carbide micro-powder are pressed
Mass ratio 1：10：3：0.75：0.75 be uniformly mixed, ZNH-5L kneaders (Laizhou new hongda chemical machinery Co., Ltd) with
Kneading 30min forming face slurries under 200r/min；The dispersant is N,N-dimethylformamide；The power of the ultrasonic disperse
For 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 89%.
Embodiment 6
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate be graphite cake (be purchased from Zibo Ou Zheng carbons Co., Ltd, length × width x thickness for 6cm × 6cm ×
0.5cm)。
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；Zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, tungsten oxide carbon nanotube, boron carbide is micro-
Powder, silicon carbide micro-powder in mass ratio 1：10：3：0.5：0.5：0.5 is uniformly mixed, in ZNH-5L kneaders (the new hongda chemical industry in Laizhou
Machinery Co., Ltd.) with kneading 30min forming face slurries under 200r/min；The dispersant is N,N-dimethylformamide；Institute
The power for stating ultrasonic disperse is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 95%.
Embodiment 7
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate is that (length × width is 6cm × 6cm, proportion 20g/m to carbon felt2).It is prepared using following methods：
By short carbon fiber, water soluble phenol resin, polyethylene glycol 200, the water in mass ratio 1 that length is 4mm：4：0.5：14 mixing,
It is dispersed with stirring 40min under conditions of 300 revs/min；It pours into 160 DEG C of constant temperature 2h cure after pressurization exclusion moisture in mold and do
It is dry, form carbon felt biscuit；Carbonization treatment is carried out in 800 DEG C of constant temperature 2h after carbon felt biscuit is demoulded, then in nitrogen atmosphere, 1800
DEG C constant temperature 2h, is cooled to room temperature, obtains carbon felt, cuts.
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；Zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, tungsten oxide carbon nanotube, boron carbide is micro-
Powder, silicon carbide micro-powder in mass ratio 1：10：3：0.5：0.5：0.5 is uniformly mixed, in ZNH-5L kneaders (the new hongda chemical industry in Laizhou
Machinery Co., Ltd.) with kneading 30min forming face slurries under 200r/min；The dispersant is N,N-dimethylformamide；Institute
The power for stating ultrasonic disperse is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.Assembling electrolysis
Pond：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type battery diaphragms of U.S. celgard；Positive and negative anodes electrolyte
It is the mixed liquor that water forms by the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus.Specific assembling steps refer to grandson
In 2015 professional degree of Dalian University of Technology master thesis of treasure " preparation of zinc-bromine flow battery diaphragm and performance study "
2.4.5 the assembling of monocell.Charge and discharge cycles test is carried out with 1C between 3.0~4.2V at normal temperatures.Test result：By
500 cycles, battery capacity 96%.
Embodiment 8
A kind of zinc-bromine flow battery pole plate, the pole plate include positive plate and negative plate.
The positive plate is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake.
The negative plate be carbon cloth (be purchased from Shanghai Li Shuo composite materials Science and Technology Ltd., length × width be 6cm × 6cm, than
Weight is 220g/m2)。
The preparation method of the zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is as follows：
S1 dispensings：
By petroleum coke, pitch in mass ratio 3:1 mixing, then in ZNH-5L kneaders, (the new hongda chemical machinery in Laizhou has
Limit company) with kneading 30min under 200r/min, form core slurry；At 25 DEG C, by zeolite imidazole ester skeleton structure nano-sized carbon
Piece is added to dispersant for ultrasonic dispersion 30min, is configured to the zeolite imidazole ester skeleton structure nanometer carbon plate of a concentration of 40mg/mL
Dispersion liquid；Zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, tungsten oxide carbon nanotube, boron carbide is micro-
Powder, silicon carbide micro-powder in mass ratio 1：10：3：0.5：0.5：0.5 is uniformly mixed, in ZNH-5L kneaders (the new hongda chemical industry in Laizhou
Machinery Co., Ltd.) with kneading 30min forming face slurries under 200r/min；The dispersant is N,N-dimethylformamide；Institute
The power for stating ultrasonic disperse is 300W, frequency 40KHz；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common pressurization
Dryness finalization becomes compound green compact；Temperature control is squeezed in the high-pressure drying sizing at 110 DEG C, squeeze pressure controls
15MPa controls dwell time 10min；
S3 graphitization processings：
Compound green compact that step S2 is obtained by conventional roasting, graphitizable high temperature processing, then cut out to 6cm × 6cm ×
0.5cm (length × width x thickness) is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature control is 1200
DEG C, roasting time is 22 days, and at 2700 DEG C, graphitizable high temperature processing time is 18h for graphitizable high temperature processing control.
Finally, the positive plate that material is zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake is obtained, section is " returning "
Font；Outer layer is starch adhesive material, and inside is core slurry.The mass ratio of the core slurry and starch adhesive material is 10：3.
The preparation method of the zeolite imidazole ester skeleton structure nanometer carbon plate is as follows：
0.95g zinc acetates are dissolved in 260mL water and obtain aqueous zinc acetate solution by A；2.9g 2-methylimidazoles are dissolved in
2-methylimidazole aqueous solution is obtained in 260mL water；Under conditions of 25 DEG C, 300r/min by 2-methylimidazole aqueous solution with
The speed of 0.05g/s is added dropwise in aqueous zinc acetate solution, continues to stir under conditions of 25 DEG C, 300r/min after being added dropwise
For 24 hours, 500 mesh grenadines filter, and obtained solid passes through absolute ethyl alcohol respectively, deionized water is respectively washed 3 times, washs anhydrous second every time
The volume of alcohol or deionized water is 50mL, and dry 48h, obtains zeolite imidazole ester frame structure material at 40 DEG C；
Zeolite imidazole ester frame structure material is warming up to the heating rate of 5 DEG C/min from 25 DEG C by B in nitrogen atmosphere
900 DEG C, and 2h is kept the temperature at 900 DEG C, then it is warming up to from 900 DEG C with the heating rate of 10 DEG C/min in carbon dioxide atmosphere
1200 DEG C, and 2h is kept the temperature at 1200 DEG C, cooled to room temperature obtains zeolite imidazole ester skeleton structure nanometer carbon plate.
Assemble electrolytic cell：Positive/negative plate is the positive/negative plate of the present embodiment；Diaphragm is 2400 type batteries of U.S. celgard
Diaphragm；Positive and negative anodes electrolyte is by the mixed liquor that the zinc bromide of 2.5mol/L, the sodium chloride of 2.5mol/L, surplus are that water forms.Tool
The assembling steps of body are with reference to Sun Yu " preparation of zinc-bromine flow battery diaphragm and performance study " 2015 Dalian University of Technology profession
The assembling of 2.4.5 monocells in degree master thesis.Charge and discharge cycles are carried out with 1C between 3.0~4.2V at normal temperatures
Test.Test result：It is recycled by 500 times, battery capacity 93%.
Each section raw material sources are as follows in embodiment：
Petroleum coke：Low-sulfur is burnt, and≤2.0%, 100 mesh of granularity, Shandong Chen Xuan novel charcoal materials Co., Ltd.
Pitch：Model NORMIC/ promise Micks, 85 DEG C of softening point, 101 Chemical Co., Ltd. of Jining.
The preparation of tungsten oxide carbon nanotube：By 1.0g carbon nanotubes 40mL concentrated nitric acids and the concentrated sulfuric acid mixed liquor (30mL
The concentrated sulfuric acid that concentrated nitric acid that mass fraction is 65% is 98% with 10mL mass fractions mixes) in ultrasonic disperse 30min, obtain
To dispersion liquid；The ultrasonic power is 350W, frequency 40KHz；Dispersion liquid is flowed back 3h under 140 DEG C of oil baths, 10000
It is centrifuged under conditions of rev/min, obtained precipitation is washed with deionized 3 times, and the dosage of each deionized water is 30mL, is obtained
To be deposited under 60 DEG C of normal vacuums it is dry for 24 hours up to the carbon nanotube after being acidified；Carbon nanometer after 5.0g is acidified
Pipe is added in the ammonium metatungstate aqueous solution that mass fraction is 15%, under conditions of 500 revs/min in 60 DEG C of stirred in water bath
4h, filtered solid dry 6h at 80 DEG C；Obtained solid is placed in tube furnace, with the heating rate of 5 DEG C/min from
25 DEG C are warming up to 550 DEG C, and keep the temperature 4h at 550 DEG C, up to tungsten oxide carbon nanotube after cooled to room temperature.
Boron carbide micro powder：250 mesh of granularity, boron content >=80%, Nangong City Jing Ding alloy materials Co., Ltd.
Silicon carbide micro-powder：320 mesh of granularity, big two factory of ridge grinding wheel of Yancheng City.
Zinc acetate：No. CAS：557-34-6.
2-methylimidazole：No. CAS：693-98-1.
Test case 1
Performance test methods：
(1) resistivity measurement：With reference to GB6717-86《Carbon material determination of resistivity method》Specified in DC probe pressure
Drop method carries out resistivity measurement to the positive plate obtained in Examples 1 to 6.
(2) leaching bromine deflection test：
A, 6cm × 6cm that Examples 1 to 6 is obtained × 0.5cm (length × width x thickness) zeolite imidazole ester skeleton structure nanometer
Carbon plate graphite cake, is fixed with frame, the surface requirements of graphite cake are smooth, cleaning, flawless, bubble-free and the defects of impurity, no
It must stretch or be bent, surface must not polish or polish；
B is put into the mixed aqueous solution of the zinc bromide of 2.5mol/L and the bromine of 2.5mol/L, and temperature maintains 50 DEG C, leaching
Bubble one week；
Sample after immersion is taken out, is rinsed well with clear water, dried to be measured by c；
D, with high metric, the deflection of sample in a thickness direction after being impregnated by finishing impression machine tool measuring obtains maximum change
Shape magnitude (mm).
It compares graphite electrode and buys (Zibo Ou Zheng carbons Co., Ltd) from market, 6cm × 6cm is cut to by test request
× 0.5cm (length × width x thickness).
1 resistivity of table and leaching bromine maximum deformation quantity
| Embodiment | Resistivity/μ Ω cm | Soak bromine maximum deformation quantity/mm |
| Compare graphite electrode | 8.5 | 4.7 |
| Embodiment 1 | 6.3 | 4.2 |
| Embodiment 2 | 4.7 | 3.6 |
| Embodiment 3 | 3.8 | 2.6 |
| Embodiment 4 | 4.0 | 2.7 |
| Embodiment 5 | 4.4 | 3.2 |
| Embodiment 6 | 3.0 | 2.2 |
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be in the protection domain being defined in the patent claims.
Claims (9)
1. a kind of zinc-bromine flow battery pole plate, including positive plate and negative plate, which is characterized in that the positive plate is zeolite imidazole
Ester skeleton structure nano-sized carbon piece graphite cake；The negative plate is one kind in graphite cake, carbon felt, graphite felt or carbon cloth；
Preferably, the negative plate is carbon felt；
Optimal, the carbon felt is commercially available carbon felt or is prepared using following methods：By short carbon fiber, the water that length is 2~5mm
Dissolubility phenolic resin, polyethylene glycol 200, water in mass ratio 1：(3~5)：(0.3~0.8)：(10~16) it mixes, 200~
It is dispersed with stirring 30~50min under conditions of 500 revs/min；Pour into mold pressurization exclude after moisture 120~200 DEG C of constant temperature 1~
3h carries out solidification drying, forms carbon felt biscuit；It is carried out at carbonization in 700~1000 DEG C of 1~3h of constant temperature after carbon felt biscuit is demoulded
Reason, then in nitrogen atmosphere, 1700~2000 DEG C of 1~2h of constant temperature, is cooled to room temperature, obtains carbon felt.
2. zinc-bromine flow battery pole plate as described in claim 1, it is characterised in that：The zeolite imidazole ester skeleton structure nanometer
The preparation method of carbon plate graphite cake is as follows：
S1 dispensings：
Petroleum coke, pitch kneading are formed into core slurry；At 10~35 DEG C, zeolite imidazole ester skeleton structure nanometer carbon plate is added
Enter to be configured to the zeolite imidazole ester skeleton structure nanometer of a concentration of 20~50mg/mL to 10~30min of dispersant for ultrasonic dispersion
Carbon plate dispersion liquid；By zeolite imidazole ester skeleton structure nanometer carbon plate dispersion liquid, petroleum coke, pitch, enhancing particle kneading forming face
Slurry；
S2 is at embryo forming：
Die orifice is gone out using coextrusion machinery support double-layer coextrusion so that starch adhesive material wraps up core slurry；Then common high-pressure drying
Sizing, becomes compound green compact；Temperature control is squeezed in high-pressure drying sizing at 105~125 DEG C, squeeze pressure control 10~
18MPa controls 5~10min of dwell time；
S3 graphitization processings：
Then the compound green compact that step S2 is obtained is cut out according to production requirement to institute by conventional roasting, graphitizable high temperature processing
The shape needed is to get zeolite imidazole ester skeleton structure nano-sized carbon piece graphite cake；The calcination temperature is controlled at 1000~1250 DEG C,
Roasting time is 10~30 days, graphitizable high temperature processing control at 2700~3400 DEG C, graphitizable high temperature processing time is 15~
50h。
3. zinc-bromine flow battery pole plate as claimed in claim 2, it is characterised in that：The core slurry petrochina coke and pitch
Mass ratio be (3~6):(1~3).
4. zinc-bromine flow battery pole plate as claimed in claim 2, it is characterised in that：Zeolite imidazole ester skeleton in the starch adhesive material
Structure nano carbon plate dispersion liquid, petroleum coke, pitch, enhance particle mass ratio be 1:(10~15):(3~5):(1~2).
5. zinc-bromine flow battery pole plate as claimed in claim 4, it is characterised in that：The enhancing particle is tungsten oxide carbon nanometer
The mixing of one or more of pipe, boron carbide micro powder, silicon carbide micro-powder.
6. zinc-bromine flow battery pole plate as claimed in claim 2, it is characterised in that：The quality of the core slurry and starch adhesive material
Than being 10:(2~5).
7. zinc-bromine flow battery pole plate as claimed in claim 2, it is characterised in that：The zeolite imidazole ester skeleton structure nanometer
The preparation method of carbon plate is as follows：
0.9~1.1g zinc acetates are dissolved in 250~300mL water and obtain aqueous zinc acetate solution by A；By 2.8~3.2g 2- methyl
Imidazoles, which is dissolved in 250~300mL water, obtains 2-methylimidazole aqueous solution；Under conditions of 10~35 DEG C, 200~500r/min
2-methylimidazole aqueous solution is added dropwise to the speed of 0.02~0.05g/s in aqueous zinc acetate solution, is continued after being added dropwise
10~35 DEG C, 20~36h is stirred under conditions of 200~500r/min, be filtered, washed, dry 24~48h at 40~60 DEG C,
Obtain zeolite imidazole ester frame structure material；
B heats up zeolite imidazole ester frame structure material in nitrogen atmosphere with the heating rate of 3~5 DEG C/min from 10~35 DEG C
To 800~1000 DEG C, and 1~3h is kept the temperature at 800~1000 DEG C, then with 5~10 DEG C/min's in carbon dioxide atmosphere
Heating rate is warming up to 1200~1400 DEG C from 800~1000 DEG C, and 1.5~3h, natural cooling are kept the temperature at 1200~1400 DEG C
Zeolite imidazole ester skeleton structure nanometer carbon plate is obtained to room temperature.
8. zinc-bromine flow battery pole plate as claimed in claim 2, it is characterised in that：The dispersant is absolute ethyl alcohol, N, N-
One or more of dimethylformamide, tetrahydrofuran.
9. zinc-bromine flow battery pole plate as claimed in claim 2, it is characterised in that：The work(of ultrasonic disperse in the step S1
Rate is 150~300W, and frequency is 24~40KHz.
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| CN108376788B (en) | 2020-12-08 |
| CN108376787B (en) | 2020-12-25 |
| CN108376787A (en) | 2018-08-07 |
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