CN105957985B - A kind of accumulator with corrosion resistance - Google Patents

A kind of accumulator with corrosion resistance Download PDF

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Publication number
CN105957985B
CN105957985B CN201610571585.1A CN201610571585A CN105957985B CN 105957985 B CN105957985 B CN 105957985B CN 201610571585 A CN201610571585 A CN 201610571585A CN 105957985 B CN105957985 B CN 105957985B
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parts
polyaniline
corrosion
solution
composite coating
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CN105957985A (en
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韦醒妃
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Jiangsu Huiyucheng Intelligent Equipment Research Institute Co ltd
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Nanjing Chuqing Electronic Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1245Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

This application involves a kind of accumulators with corrosion resistance, including battery jar, it is provided with electrolytic cell in the battery jar, it is equipped with upper cover on the electrolytic cell, it is characterized in that, the electrolytic cell is integral type welding structure, and electrode is provided in the electrolytic cell, and the battery jar outer surface is equipped with corrosion-resistant coating.

Description

A kind of accumulator with corrosion resistance
Technical field
This application involves battery field more particularly to a kind of accumulators with corrosion resistance.
Background technology
In daily life, the use of accumulator is very extensive, such as applied to automobile, illumination, emergency power supply etc., while by Complex in the use environment of accumulator, shell is easy in use by corrosion such as gas, liquid, to influence it Service life.
However, cladding process is usually used in existing anticorrosion technique, one layer of anticorrosive coating is coated in target object surface, Still suffer from the problems such as anticorrosive coating protection effect is bad.
Invention content
The present invention is intended to provide a kind of accumulator with corrosion resistance, set forth above to solve the problems, such as.
A kind of accumulator with corrosion resistance is provided in the embodiment of the present invention,
A kind of accumulator with corrosion resistance, including battery jar are provided with electrolytic cell in the battery jar, institute It states and is equipped with upper cover on electrolytic cell, the electrolytic cell is integral type welding structure, and electrode is provided in the electrolytic cell.
The technical solution that the embodiment of the present invention provides can include the following benefits:
Corrosion-resistant coating is arranged in the outer surface of battery jar in the present invention, which has preferable anticorrosion ability, Can with effective protection accumulator not in by environment gas, liquid etc. corrosion, or corrosion it is influenced it is smaller, to solve Problem set forth above.
The additional aspect of the application and advantage will be set forth in part in the description, and will partly become from the following description It obtains obviously, or recognized by the practice of the application.It should be understood that above general description and following detailed description are only It is exemplary and explanatory, the application can not be limited.
Description of the drawings
Using attached drawing, the invention will be further described, but the embodiment in attached drawing does not constitute any limit to the present invention System, for those of ordinary skill in the art, without creative efforts, can also obtain according to the following drawings Other attached drawings.
Fig. 1 is the structural schematic diagram of accumulator of the present invention.
Fig. 2 is the production flow diagram of anticorrosion composite coating of the present invention.
Specific implementation mode
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment Described in embodiment do not represent and the consistent all embodiments of the present invention.On the contrary, they be only with it is such as appended The example of the consistent device and method of some aspects being described in detail in claims, of the invention.
Metal is under the action of surrounding medium, since corruption can occur for chemical reaction, electrochemical reaction or physical dissolution etc. Erosion.Corrosion of metal problem spread economic every field, in life, day commonly used home appliance surface can occur corrosion and The reduction service life equally faces the various problems that metal erosion is brought, the anticorrosion to metal in fields such as traffic, machinery, chemical industry Technology has become the very important problem of Material Field.
Currently, mainly metal material and corrosive environment are kept apart, and then avoid metal using the method for surface covering Be corroded.According to the difference of covering material, surface covering is divided into metal covering and nonmetallic covering.It is to work as using anticorrosive paint One of preceding most widely used, most effective anticorrosion technique.The chief component of coating has film forming matter, solvent, color stuffing And auxiliary agent.
Polyaniline has many advantages, such as synthesis material at low cost, scratch resistance, anticorrosive, is a kind of commonly used anticorrosive to have Machine conducting polymer, studies have shown that polyaniline, which is added in epoxy resin, can be obviously improved its mechanical performance and antiseptic property, However, polyaniline compound anticorrosive paint still has the problems such as indissoluble, anticorrosion ability is poor at present, therefore develop and expand polyaniline Application in corrosion-resistant field has very important significance.
Application scenarios one:
Fig. 1 shows a kind of accumulator with corrosion resistance that embodiments herein is related to, including battery jar 1, electrolytic cell is provided in the battery jar, upper cover 2 is equipped on the electrolytic cell, and the electrolytic cell is integral type weldering Binding structure is provided with electrode in the electrolytic cell;
Preferably, 1 outer surface of the battery jar is equipped with corrosion-resistant coating 3, and 3 thickness of the corrosion-resistant coating is 400~600 μ M, the corrosion-resistant coating 3 are that anticorrosion composite coating cures 15h shapes coated in 1 outer surface of the battery jar after drying At.
Corrosion-resistant coating is arranged in the outer surface of battery jar in the present invention, which has suitable thickness, have Preferable anticorrosion ability, can with effective protection accumulator not in by environment gas, liquid etc. corrosion, to extend accumulator Service life.
Preferably, using epoxy resin as film forming matter, polyaniline/Al nano-particles are used as and fill out the anticorrosion composite coating The composite fibre of material, copper carbon fiber and polyaniline fiber composition is as network layer.
In the anticorrosion composite coating of the application, using the composite fibre that copper carbon fiber and polyaniline fiber form as net Network layers, on the one hand, copper carbon fiber has excellent flexibility and electric conductivity, is conducive to the transmission of conductive ion;Coppered carbon simultaneously Fiber is used in mixed way with polyaniline fiber, and the two interacts to form network structure so that the application composite coating is in mechanical performance side Face enhances suppleness, the impact resistance of coating, while the composite network structure enhances the wear-resisting of composite coating composite coating Property, increase service life;In terms of electrochemistry, corynebacterium copper carbon fiber mutually splices, and forms conductive network, for corrosion electricity Conductive ion has electric screening action in solution solution, enhances the corrosion resistance of coating;On the other hand, the application anticorrosion is compound In coating network layer be effectively isolated matrix and corrode electrolyte contact, have physical shielding effect, obstruction corrosive ion to The diffusion of matrix improves matrix corrosion resistance.
Preferably, the anticorrosion composite coating is using normal propyl alcohol as antifreeze.
In the application anticorrosion composite coating, normal propyl alcohol is added as antifreeze so that at low temperature, the anticorrosion is compound Paint film still has comparable corrosion resistance, meanwhile, frost resistance and composite fibre synergistic effect, anticorrosion is compound at low temperature The mechanical performance decline of paint film is relatively low, produces good effect.
It is further preferred that by Fig. 2, the preparation process of the anticorrosion composite coating is as follows:
Step 1 prepares copper carbon fiber:
Carbon fiber is taken, a diameter of 20~50 μm, carbon fiber plates one layer of copper as electrode, using electrochemical method on its surface Film, copper film thickness are 5 μm, are then cut to 2~3mm length;
Step 2 prepares polyaniline fiber:
It is 1 to take volume ratio:Aniline, is dissolved in distilled water by 60 aniline and distilled water under the action of inorganic acid, surpasses It under sound, is uniformly mixed, forms solution A, it is 1 then to take mass ratio:50 FeCl36H2O and distilled water, by FeCl36H2O It is dissolved in distilled water, forms solution B, be then uniformly mixed A, B, wherein A, B volume ratio are 2:3, A, B mixed solution are existed Reaction 10h is stood under the conditions of ice-water bath, obtains bottle green product, and reaction acquired solution filtering is first washed with deionized water into Property, then with ethyl alcohol to be washed till filtrate colourless, and product is dried to 30h in drying box, obtains polyaniline fiber;
Then, copper carbon fiber and polyaniline fiber, mass ratio 3 are taken:2, it puts it into dilute hydrochloric acid solution, constantly stirs It mixes, while acidification 2h, is then washed with deionized water to neutrality, 5h is dried in drying box, obtain composite fibre;
Step 3 prepares polyaniline/Al nano-particles:
It takes the neopelex of 3g to be dissolved into 200ml deionized waters first, the aniline of 3ml is added, in water 78 DEG C of processing 30min, are then added 0.5g Al nano-particles in bath, and magnetic agitation 1h obtains the uniform suspension of Al particles; The ammonium persulfate of 10g is dissolved in 100ml hydrochloric acid solutions, magnetic agitation 1h, then utilizes separatory funnel by ammonium persulfate solution It is added drop-wise in aniline solution, being stirred continuously makes it react 4h, is then allowed to stand filtering, will pulverize after filtrate washing drying End is to get polyaniline/Al nano-particle powders;
Step 4 prepares anticorrosion composite coating:
The application anticorrosion composite coating is using epoxy resin as film forming matter, and polyaniline/Al nano-particles are as filler, phosphorus Sour zinc, aluminium triphosphate, talcum powder and barium sulfate are as color stuffing, the composite fibre of copper carbon fiber and polyaniline fiber composition As network layer, as mixed solvent, silane coupling agent is made as auxiliary agent, polyamide 6 50 for n-butanol and N-Methyl pyrrolidone For curing agent, normal propyl alcohol is as antifreeze;
It takes 5 parts of polyanilines/Al nano-particles and 7 parts of composite fibre to be placed in beaker, 60 parts of N-Methyl pyrrolidones is added, Magnetic agitation 30min, is then sonicated 2h;
Then 10 parts of epoxy resin and 6 parts of n-butanols are put into another beaker, magnetic agitation 1h, by solution in two beakers Mixing stirs 2h, sequentially adds 3 parts of 4 parts of normal propyl alcohol, 1 part of trbasic zinc phosphate, 2 parts of aluminium triphosphate, 1 part of talcum powder and barium sulfate, then 2 parts of 50 curing agent of polyamide 6 are added after stirring 1h, the anticorrosion composite coating of the application is obtained after mechanical agitation 2h;
The anticorrosion composite coating is coated in target object surface, cures 15h after dry, after solidification, coating layer thickness is 400~600 μm.
Preferably, in terms of the experiment effect of the application anticorrosion composite coating, the anti-corruption of the application anticorrosion composite coating Corrosion energy:Corrosion resistance is evaluated by electrochemical means, and the matrix for coating different-thickness composite coating of the present invention is placed on In the Na2S solution of 4wt%, 300h, test resistance change rate are stood, it is found that the corrosion of the application composite coating is smaller from electric current, It can be effectively prevent corrosion of the corrosion electrolyte to matrix, and the anti-freezing property of the anticorrosion composite coating is good.
Application scenarios two:
Fig. 1 shows a kind of accumulator with corrosion resistance that embodiments herein is related to, including battery jar 1, electrolytic cell is provided in the battery jar, upper cover 2 is equipped on the electrolytic cell, and the electrolytic cell is integral type weldering Binding structure is provided with electrode in the electrolytic cell;
Preferably, 1 outer surface of the battery jar is equipped with corrosion-resistant coating 3, and 3 thickness of the corrosion-resistant coating is 400~600 μ M, the corrosion-resistant coating 3 are that anticorrosion composite coating cures 15h shapes coated in 1 outer surface of the battery jar after drying At.
Corrosion-resistant coating is arranged in the outer surface of battery jar in the present invention, which has suitable thickness, have Preferable anticorrosion ability, can with effective protection accumulator not in by environment gas, liquid etc. corrosion, to extend accumulator Service life.
Preferably, using epoxy resin as film forming matter, polyaniline/Al nano-particles are used as and fill out the anticorrosion composite coating The composite fibre of material, copper carbon fiber and polyaniline fiber composition is as network layer.
In the anticorrosion composite coating of the application, using the composite fibre that copper carbon fiber and polyaniline fiber form as net Network layers, on the one hand, copper carbon fiber has excellent flexibility and electric conductivity, is conducive to the transmission of conductive ion;Coppered carbon simultaneously Fiber is used in mixed way with polyaniline fiber, and the two interacts to form network structure so that the application composite coating is in mechanical performance side Face enhances suppleness, the impact resistance of coating, while the composite network structure enhances the wear-resisting of composite coating composite coating Property, increase service life;In terms of electrochemistry, corynebacterium copper carbon fiber mutually splices, and forms conductive network, for corrosion electricity Conductive ion has electric screening action in solution solution, enhances the corrosion resistance of coating;On the other hand, the application anticorrosion is compound In coating network layer be effectively isolated matrix and corrode electrolyte contact, have physical shielding effect, obstruction corrosive ion to The diffusion of matrix improves matrix corrosion resistance.
It is further preferred that by Fig. 2, the preparation process of the anticorrosion composite coating is as follows:
Step 1 prepares copper carbon fiber:
Carbon fiber is taken, a diameter of 20~50 μm, carbon fiber plates one layer of copper as electrode, using electrochemical method on its surface Film, copper film thickness are 5 μm, are then cut to 2~3mm length;
Step 2 prepares polyaniline fiber:
It is 1 to take volume ratio:Aniline, is dissolved in distilled water by 60 aniline and distilled water under the action of inorganic acid, surpasses It under sound, is uniformly mixed, forms solution A, it is 1 then to take mass ratio:50 FeCl36H2O and distilled water, by FeCl36H2O It is dissolved in distilled water, forms solution B, be then uniformly mixed A, B, wherein A, B volume ratio are 2:3, A, B mixed solution are existed Reaction 10h is stood under the conditions of ice-water bath, obtains bottle green product, and reaction acquired solution filtering is first washed with deionized water into Property, then with ethyl alcohol to be washed till filtrate colourless, and product is dried to 30h in drying box, obtains polyaniline fiber;
Then, copper carbon fiber and polyaniline fiber, mass ratio 3 are taken:2, it puts it into dilute hydrochloric acid solution, constantly stirs It mixes, while acidification 2h, is then washed with deionized water to neutrality, 5h is dried in drying box, obtain composite fibre;
Step 3 prepares polyaniline/Al nano-particles:
It takes the neopelex of 3g to be dissolved into 200ml deionized waters first, the aniline of 3ml is added, in water 78 DEG C of processing 30min, are then added 0.5g Al nano-particles in bath, and magnetic agitation 1h obtains the uniform suspension of Al particles; The ammonium persulfate of 10g is dissolved in 100ml hydrochloric acid solutions, magnetic agitation 1h, then utilizes separatory funnel by ammonium persulfate solution It is added drop-wise in aniline solution, being stirred continuously makes it react 4h, is then allowed to stand filtering, will pulverize after filtrate washing drying End is to get polyaniline/Al nano-particle powders;
Step 4 prepares anticorrosion composite coating:
The application anticorrosion composite coating is using epoxy resin as film forming matter, and polyaniline/Al nano-particles are as filler, phosphorus Sour zinc, aluminium triphosphate, talcum powder and barium sulfate are as color stuffing, the composite fibre of copper carbon fiber and polyaniline fiber composition As network layer, as mixed solvent, silane coupling agent is made as auxiliary agent, polyamide 6 50 for n-butanol and N-Methyl pyrrolidone For curing agent;
It takes 5 parts of polyanilines/Al nano-particles and 7 parts of composite fibre to be placed in beaker, 60 parts of N-Methyl pyrrolidones is added, Magnetic agitation 30min, is then sonicated 2h;
Then 10 parts of epoxy resin and 6 parts of n-butanols are put into another beaker, magnetic agitation 1h, by solution in two beakers Mixing stirs 2h, sequentially adds 3 parts of 1 part of trbasic zinc phosphate, 2 parts of aluminium triphosphate, 1 part of talcum powder and barium sulfate, adds after being stirred for 1h Enter 2 parts of 50 curing agent of polyamide 6, the anticorrosion composite coating of the application is obtained after mechanical agitation 2h;
The anticorrosion composite coating is coated in target object surface, cures 15h after dry, after solidification, coating layer thickness is 400~600 μm.
Preferably, in terms of the experiment effect of the application anticorrosion composite coating, the anti-corruption of the application anticorrosion composite coating Corrosion energy:Corrosion resistance is evaluated by electrochemical means, and the matrix for coating different-thickness composite coating of the present invention is placed on In the Na2S solution of 4wt%, 300h, test resistance change rate are stood, it is found that the corrosion of the application composite coating is smaller from electric current, It can effectively prevent corrosion of the corrosion electrolyte to matrix.
Application scenarios three:
Fig. 1 shows a kind of accumulator with corrosion resistance that embodiments herein is related to, including battery jar 1, electrolytic cell is provided in the battery jar, upper cover 2 is equipped on the electrolytic cell, and the electrolytic cell is integral type weldering Binding structure is provided with electrode in the electrolytic cell;
Preferably, 1 outer surface of the battery jar is equipped with corrosion-resistant coating 3, and 3 thickness of the corrosion-resistant coating is 0~200 μm, The corrosion-resistant coating 3 cures 15h coated in 1 outer surface of the battery jar for anticorrosion composite coating after drying and is formed.
Corrosion-resistant coating is arranged in the outer surface of battery jar in the present invention, which has suitable thickness, have Preferable anticorrosion ability, can with effective protection accumulator not in by environment gas, liquid etc. corrosion, to extend accumulator Service life.
Preferably, using epoxy resin as film forming matter, polyaniline/Al nano-particles are used as and fill out the anticorrosion composite coating The composite fibre of material, copper carbon fiber and polyaniline fiber composition is as network layer.
In the anticorrosion composite coating of the application, using the composite fibre that copper carbon fiber and polyaniline fiber form as net Network layers, on the one hand, copper carbon fiber has excellent flexibility and electric conductivity, is conducive to the transmission of conductive ion;Coppered carbon simultaneously Fiber is used in mixed way with polyaniline fiber, and the two interacts to form network structure so that the application composite coating is in mechanical performance side Face enhances suppleness, the impact resistance of coating, while the composite network structure enhances the wear-resisting of composite coating composite coating Property, increase service life;In terms of electrochemistry, corynebacterium copper carbon fiber mutually splices, and forms conductive network, for corrosion electricity Conductive ion has electric screening action in solution solution, enhances the corrosion resistance of coating;On the other hand, the application anticorrosion is compound In coating network layer be effectively isolated matrix and corrode electrolyte contact, have physical shielding effect, obstruction corrosive ion to The diffusion of matrix improves matrix corrosion resistance.
Preferably, the anticorrosion composite coating is using normal propyl alcohol as antifreeze.
In the application anticorrosion composite coating, normal propyl alcohol is added as antifreeze so that at low temperature, the anticorrosion is compound Paint film still has comparable corrosion resistance, meanwhile, frost resistance and composite fibre synergistic effect, anticorrosion is compound at low temperature The mechanical performance decline of paint film is relatively low, produces good effect.
It is further preferred that by Fig. 2, the preparation process of the anticorrosion composite coating is as follows:
Step 1 prepares copper carbon fiber:
Carbon fiber is taken, a diameter of 20~50 μm, carbon fiber plates one layer of copper as electrode, using electrochemical method on its surface Film, copper film thickness are 5 μm, are then cut to 2~3mm length;
Step 2 prepares polyaniline fiber:
It is 1 to take volume ratio:Aniline, is dissolved in distilled water by 60 aniline and distilled water under the action of inorganic acid, surpasses It under sound, is uniformly mixed, forms solution A, it is 1 then to take mass ratio:50 FeCl36H2O and distilled water, by FeCl36H2O It is dissolved in distilled water, forms solution B, be then uniformly mixed A, B, wherein A, B volume ratio are 2:3, A, B mixed solution are existed Reaction 10h is stood under the conditions of ice-water bath, obtains bottle green product, and reaction acquired solution filtering is first washed with deionized water into Property, then with ethyl alcohol to be washed till filtrate colourless, and product is dried to 30h in drying box, obtains polyaniline fiber;
Then, copper carbon fiber and polyaniline fiber, mass ratio 3 are taken:2, it puts it into dilute hydrochloric acid solution, constantly stirs It mixes, while acidification 2h, is then washed with deionized water to neutrality, 5h is dried in drying box, obtain composite fibre;
Step 3 prepares polyaniline/Al nano-particles:
It takes the neopelex of 3g to be dissolved into 200ml deionized waters first, the aniline of 3ml is added, in water 78 DEG C of processing 30min, are then added 0.5g Al nano-particles in bath, and magnetic agitation 1h obtains the uniform suspension of Al particles; The ammonium persulfate of 10g is dissolved in 100ml hydrochloric acid solutions, magnetic agitation 1h, then utilizes separatory funnel by ammonium persulfate solution It is added drop-wise in aniline solution, being stirred continuously makes it react 4h, is then allowed to stand filtering, will pulverize after filtrate washing drying End is to get polyaniline/Al nano-particle powders;
Step 4 prepares anticorrosion composite coating:
The application anticorrosion composite coating is using epoxy resin as film forming matter, and polyaniline/Al nano-particles are as filler, phosphorus Sour zinc, aluminium triphosphate, talcum powder and barium sulfate are as color stuffing, the composite fibre of copper carbon fiber and polyaniline fiber composition As network layer, as mixed solvent, silane coupling agent is made as auxiliary agent, polyamide 6 50 for n-butanol and N-Methyl pyrrolidone For curing agent, normal propyl alcohol is as antifreeze;
It takes 5 parts of polyanilines/Al nano-particles and 7 parts of composite fibre to be placed in beaker, 60 parts of N-Methyl pyrrolidones is added, Magnetic agitation 30min, is then sonicated 2h;
Then 10 parts of epoxy resin and 6 parts of n-butanols are put into another beaker, magnetic agitation 1h, by solution in two beakers Mixing stirs 2h, sequentially adds 3 parts of 4 parts of normal propyl alcohol, 1 part of trbasic zinc phosphate, 2 parts of aluminium triphosphate, 1 part of talcum powder and barium sulfate, then 2 parts of 50 curing agent of polyamide 6 are added after stirring 1h, the anticorrosion composite coating of the application is obtained after mechanical agitation 2h;
The anticorrosion composite coating is coated in target object surface, cures 15h after dry, after solidification, coating layer thickness 0 ~200 μm.
Preferably, in terms of the experiment effect of the application anticorrosion composite coating, the anti-corruption of the application anticorrosion composite coating Corrosion energy:Corrosion resistance is evaluated by electrochemical means, and the matrix for coating different-thickness composite coating of the present invention is placed on In the Na2S solution of 4wt%, 300h, test resistance change rate are stood, it is found that the corrosion of the application composite coating is smaller from electric current, It can be effectively prevent corrosion of the corrosion electrolyte to matrix, and the anti-freezing property of the anticorrosion composite coating is good.
Application scenarios four:
Fig. 1 shows a kind of accumulator with corrosion resistance that embodiments herein is related to, including battery jar 1, electrolytic cell is provided in the battery jar, upper cover 2 is equipped on the electrolytic cell, and the electrolytic cell is integral type weldering Binding structure is provided with electrode in the electrolytic cell;
Preferably, 1 outer surface of the battery jar is equipped with corrosion-resistant coating 3, and 3 thickness of the corrosion-resistant coating is 200~400 μ M, the corrosion-resistant coating 3 are that anticorrosion composite coating cures 15h shapes coated in 1 outer surface of the battery jar after drying At.
Corrosion-resistant coating is arranged in the outer surface of battery jar in the present invention, which has suitable thickness, have Preferable anticorrosion ability, can with effective protection accumulator not in by environment gas, liquid etc. corrosion, to extend accumulator Service life.
Preferably, using epoxy resin as film forming matter, polyaniline/Al nano-particles are used as and fill out the anticorrosion composite coating The composite fibre of material, copper carbon fiber and polyaniline fiber composition is as network layer.
In the anticorrosion composite coating of the application, using the composite fibre that copper carbon fiber and polyaniline fiber form as net Network layers, on the one hand, copper carbon fiber has excellent flexibility and electric conductivity, is conducive to the transmission of conductive ion;Coppered carbon simultaneously Fiber is used in mixed way with polyaniline fiber, and the two interacts to form network structure so that the application composite coating is in mechanical performance side Face enhances suppleness, the impact resistance of coating, while the composite network structure enhances the wear-resisting of composite coating composite coating Property, increase service life;In terms of electrochemistry, corynebacterium copper carbon fiber mutually splices, and forms conductive network, for corrosion electricity Conductive ion has electric screening action in solution solution, enhances the corrosion resistance of coating;On the other hand, the application anticorrosion is compound In coating network layer be effectively isolated matrix and corrode electrolyte contact, have physical shielding effect, obstruction corrosive ion to The diffusion of matrix improves matrix corrosion resistance.
Preferably, the anticorrosion composite coating is using normal propyl alcohol as antifreeze.
In the application anticorrosion composite coating, normal propyl alcohol is added as antifreeze so that at low temperature, the anticorrosion is compound Paint film still has comparable corrosion resistance, meanwhile, frost resistance and composite fibre synergistic effect, anticorrosion is compound at low temperature The mechanical performance decline of paint film is relatively low, produces good effect.
It is further preferred that by Fig. 2, the preparation process of the anticorrosion composite coating is as follows:
Step 1 prepares copper carbon fiber:
Carbon fiber is taken, a diameter of 20~50 μm, carbon fiber plates one layer of copper as electrode, using electrochemical method on its surface Film, copper film thickness are 5 μm, are then cut to 2~3mm length;
Step 2 prepares polyaniline fiber:
It is 1 to take volume ratio:Aniline, is dissolved in distilled water by 60 aniline and distilled water under the action of inorganic acid, surpasses It under sound, is uniformly mixed, forms solution A, it is 1 then to take mass ratio:50 FeCl36H2O and distilled water, by FeCl36H2O It is dissolved in distilled water, forms solution B, be then uniformly mixed A, B, wherein A, B volume ratio are 2:3, A, B mixed solution are existed Reaction 10h is stood under the conditions of ice-water bath, obtains bottle green product, and reaction acquired solution filtering is first washed with deionized water into Property, then with ethyl alcohol to be washed till filtrate colourless, and product is dried to 30h in drying box, obtains polyaniline fiber;
Then, copper carbon fiber and polyaniline fiber, mass ratio 3 are taken:2, it puts it into dilute hydrochloric acid solution, constantly stirs It mixes, while acidification 2h, is then washed with deionized water to neutrality, 5h is dried in drying box, obtain composite fibre;
Step 3 prepares polyaniline/Al nano-particles:
It takes the neopelex of 3g to be dissolved into 200ml deionized waters first, the aniline of 3ml is added, in water 78 DEG C of processing 30min, are then added 0.5g Al nano-particles in bath, and magnetic agitation 1h obtains the uniform suspension of Al particles; The ammonium persulfate of 10g is dissolved in 100ml hydrochloric acid solutions, magnetic agitation 1h, then utilizes separatory funnel by ammonium persulfate solution It is added drop-wise in aniline solution, being stirred continuously makes it react 4h, is then allowed to stand filtering, will pulverize after filtrate washing drying End is to get polyaniline/Al nano-particle powders;
Step 4 prepares anticorrosion composite coating:
The application anticorrosion composite coating is using epoxy resin as film forming matter, and polyaniline/Al nano-particles are as filler, phosphorus Sour zinc, aluminium triphosphate, talcum powder and barium sulfate are as color stuffing, the composite fibre of copper carbon fiber and polyaniline fiber composition As network layer, as mixed solvent, silane coupling agent is made as auxiliary agent, polyamide 6 50 for n-butanol and N-Methyl pyrrolidone For curing agent, normal propyl alcohol is as antifreeze;
It takes 5 parts of polyanilines/Al nano-particles and 7 parts of composite fibre to be placed in beaker, 60 parts of N-Methyl pyrrolidones is added, Magnetic agitation 30min, is then sonicated 2h;
Then 10 parts of epoxy resin and 6 parts of n-butanols are put into another beaker, magnetic agitation 1h, by solution in two beakers Mixing stirs 2h, sequentially adds 3 parts of 4 parts of normal propyl alcohol, 1 part of trbasic zinc phosphate, 2 parts of aluminium triphosphate, 1 part of talcum powder and barium sulfate, then 2 parts of 50 curing agent of polyamide 6 are added after stirring 1h, the anticorrosion composite coating of the application is obtained after mechanical agitation 2h;
The anticorrosion composite coating is coated in target object surface, cures 15h after dry, after solidification, coating layer thickness is 200~400 μm.
Preferably, in terms of the experiment effect of the application anticorrosion composite coating, the anti-corruption of the application anticorrosion composite coating Corrosion energy:Corrosion resistance is evaluated by electrochemical means, and the matrix for coating different-thickness composite coating of the present invention is placed on In the Na2S solution of 4wt%, 300h, test resistance change rate are stood, it is found that the corrosion of the application composite coating is smaller from electric current, It can be effectively prevent corrosion of the corrosion electrolyte to matrix, and the anti-freezing property of the anticorrosion composite coating is good.
Application scenarios five:
Fig. 1 shows a kind of accumulator with corrosion resistance that embodiments herein is related to, including battery jar 1, electrolytic cell is provided in the battery jar, upper cover 2 is equipped on the electrolytic cell, and the electrolytic cell is integral type weldering Binding structure is provided with electrode in the electrolytic cell;
Preferably, 1 outer surface of the battery jar is equipped with corrosion-resistant coating 3, and 3 thickness of the corrosion-resistant coating is 600~800 μ M, the corrosion-resistant coating 3 are that anticorrosion composite coating cures 15h shapes coated in 1 outer surface of the battery jar after drying At.
Corrosion-resistant coating is arranged in the outer surface of battery jar in the present invention, which has suitable thickness, have Preferable anticorrosion ability, can with effective protection accumulator not in by environment gas, liquid etc. corrosion, to extend accumulator Service life.
Preferably, using epoxy resin as film forming matter, polyaniline/Al nano-particles are used as and fill out the anticorrosion composite coating The composite fibre of material, copper carbon fiber and polyaniline fiber composition is as network layer.
In the anticorrosion composite coating of the application, using the composite fibre that copper carbon fiber and polyaniline fiber form as net Network layers, on the one hand, copper carbon fiber has excellent flexibility and electric conductivity, is conducive to the transmission of conductive ion;Coppered carbon simultaneously Fiber is used in mixed way with polyaniline fiber, and the two interacts to form network structure so that the application composite coating is in mechanical performance side Face enhances suppleness, the impact resistance of coating, while the composite network structure enhances the wear-resisting of composite coating composite coating Property, increase service life;In terms of electrochemistry, corynebacterium copper carbon fiber mutually splices, and forms conductive network, for corrosion electricity Conductive ion has electric screening action in solution solution, enhances the corrosion resistance of coating;On the other hand, the application anticorrosion is compound In coating network layer be effectively isolated matrix and corrode electrolyte contact, have physical shielding effect, obstruction corrosive ion to The diffusion of matrix improves matrix corrosion resistance.
Preferably, the anticorrosion composite coating is using normal propyl alcohol as antifreeze.
In the application anticorrosion composite coating, normal propyl alcohol is added as antifreeze so that at low temperature, the anticorrosion is compound Paint film still has comparable corrosion resistance, meanwhile, frost resistance and composite fibre synergistic effect, anticorrosion is compound at low temperature The mechanical performance decline of paint film is relatively low, produces good effect.
It is further preferred that by Fig. 2, the preparation process of the anticorrosion composite coating is as follows:
Step 1 prepares copper carbon fiber:
Carbon fiber is taken, a diameter of 20~50 μm, carbon fiber plates one layer of copper as electrode, using electrochemical method on its surface Film, copper film thickness are 5 μm, are then cut to 2~3mm length;
Step 2 prepares polyaniline fiber:
It is 1 to take volume ratio:Aniline, is dissolved in distilled water by 60 aniline and distilled water under the action of inorganic acid, surpasses It under sound, is uniformly mixed, forms solution A, it is 1 then to take mass ratio:50 FeCl36H2O and distilled water, by FeCl36H2O It is dissolved in distilled water, forms solution B, be then uniformly mixed A, B, wherein A, B volume ratio are 2:3, A, B mixed solution are existed Reaction 10h is stood under the conditions of ice-water bath, obtains bottle green product, and reaction acquired solution filtering is first washed with deionized water into Property, then with ethyl alcohol to be washed till filtrate colourless, and product is dried to 30h in drying box, obtains polyaniline fiber;
Then, copper carbon fiber and polyaniline fiber, mass ratio 3 are taken:2, it puts it into dilute hydrochloric acid solution, constantly stirs It mixes, while acidification 2h, is then washed with deionized water to neutrality, 5h is dried in drying box, obtain composite fibre;
Step 3 prepares polyaniline/Al nano-particles:
It takes the neopelex of 3g to be dissolved into 200ml deionized waters first, the aniline of 3ml is added, in water 78 DEG C of processing 30min, are then added 0.5g Al nano-particles in bath, and magnetic agitation 1h obtains the uniform suspension of Al particles; The ammonium persulfate of 10g is dissolved in 100ml hydrochloric acid solutions, magnetic agitation 1h, then utilizes separatory funnel by ammonium persulfate solution It is added drop-wise in aniline solution, being stirred continuously makes it react 4h, is then allowed to stand filtering, will pulverize after filtrate washing drying End is to get polyaniline/Al nano-particle powders;
Step 4 prepares anticorrosion composite coating:
The application anticorrosion composite coating is using epoxy resin as film forming matter, and polyaniline/Al nano-particles are as filler, phosphorus Sour zinc, aluminium triphosphate, talcum powder and barium sulfate are as color stuffing, the composite fibre of copper carbon fiber and polyaniline fiber composition As network layer, as mixed solvent, silane coupling agent is made as auxiliary agent, polyamide 6 50 for n-butanol and N-Methyl pyrrolidone For curing agent, normal propyl alcohol is as antifreeze;
It takes 5 parts of polyanilines/Al nano-particles and 7 parts of composite fibre to be placed in beaker, 60 parts of N-Methyl pyrrolidones is added, Magnetic agitation 30min, is then sonicated 2h;
Then 10 parts of epoxy resin and 6 parts of n-butanols are put into another beaker, magnetic agitation 1h, by solution in two beakers Mixing stirs 2h, sequentially adds 3 parts of 4 parts of normal propyl alcohol, 1 part of trbasic zinc phosphate, 2 parts of aluminium triphosphate, 1 part of talcum powder and barium sulfate, then 2 parts of 50 curing agent of polyamide 6 are added after stirring 1h, the anticorrosion composite coating of the application is obtained after mechanical agitation 2h;
The anticorrosion composite coating is coated in target object surface, cures 15h after dry, after solidification, coating layer thickness is 600~800 μm.
Preferably, in terms of the experiment effect of the application anticorrosion composite coating, the anti-corruption of the application anticorrosion composite coating Corrosion energy:Corrosion resistance is evaluated by electrochemical means, and the matrix for coating different-thickness composite coating of the present invention is placed on In the Na2S solution of 4wt%, 300h, test resistance change rate are stood, it is found that the corrosion of the application composite coating is smaller from electric current, It can be effectively prevent corrosion of the corrosion electrolyte to matrix, and the anti-freezing property of the anticorrosion composite coating is good.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to its of the present invention Its embodiment.This application is intended to cover the present invention any variations, uses, or adaptations, these modifications, purposes or Person's adaptive change follows the general principle of the present invention and includes the undocumented common knowledge in the art of the application Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following Claim is pointed out.
It should be understood that the invention is not limited in the precision architectures for being described above and being shown in the accompanying drawings, and And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is limited only by the attached claims.

Claims (2)

1. a kind of accumulator with corrosion resistance, including battery jar, it is provided with electrolytic cell in the battery jar, it is described Upper cover is equipped on electrolytic cell, which is characterized in that the electrolytic cell is integral type welding structure, is arranged in the electrolytic cell There is electrode;
The battery jar outer surface is equipped with corrosion-resistant coating, and the corrosion-resistant coating is that anticorrosion composite coating is coated in the electric power storage Pond shell outer surface cures 15h after drying and is formed;
The anticorrosion composite coating using epoxy resin as film forming matter, polyaniline/Al nano-particles as filler, trbasic zinc phosphate, Aluminium triphosphate, talcum powder and barium sulfate are as color stuffing, the composite fibre conduct of copper carbon fiber and polyaniline fiber composition Network layer, n-butanol and N-Methyl pyrrolidone are used as curing agent as mixed solvent, polyamide 6 50, and normal propyl alcohol is as freeze proof Agent;Above-mentioned substance mass fraction is followed successively by:10 parts of epoxy resin, polyaniline/5 parts of Al nano-particles, 1 part of trbasic zinc phosphate, trimerization phosphorus 2 parts of sour aluminium, 1 part of talcum powder, 3 parts of barium sulfate, 7 parts of composite fibre, 6 parts of n-butanol, 60 parts of N-Methyl pyrrolidone, polyamide 650 2 parts, 4 parts of normal propyl alcohol;
The preparation process of the anticorrosion composite coating is as follows:
Step 1 prepares copper carbon fiber:
Carbon fiber is taken, a diameter of 20~50 μm, carbon fiber plates one layer of copper film as electrode, using electrochemical method on its surface, Copper film thickness is 5 μm, is then cut to 2~3mm length;
Step 2 prepares polyaniline fiber:
It is 1 to take volume ratio:Aniline, is dissolved in distilled water by 60 aniline and distilled water under the action of inorganic acid, under ultrasound, It is uniformly mixed, forms solution A, it is 1 then to take mass ratio:50 FeCl36H2O and distilled water, FeCl36H2O is dissolved In distilled water, solution B is formed, is then uniformly mixed A, B, wherein A, B volume ratio are 2:3, by A, B mixed solution in ice water Reaction 10h is stood under the conditions of bath, obtains bottle green product, and reaction acquired solution filtering is first washed with deionized water to neutrality, then It is colourless it to be washed till filtrate with ethyl alcohol, product is dried 30h in drying box, obtains polyaniline fiber;
Then, copper carbon fiber and polyaniline fiber, mass ratio 3 are taken:2, it puts it into dilute hydrochloric acid solution, is stirred continuously, together When acidification 2h, be then washed with deionized water to neutrality, 5h be dried in drying box, obtain composite fibre;
Step 3 prepares polyaniline/Al nano-particles:
It takes the neopelex of 3g to be dissolved into 200ml deionized waters first, the aniline of 3ml is added, in a water bath 78 DEG C of processing 30min, are then added 0.5g Al nano-particles, magnetic agitation 1h obtains the uniform suspension of Al particles;By 10g Ammonium persulfate be dissolved in 100ml hydrochloric acid solutions, then ammonium persulfate solution is added drop-wise to by magnetic agitation 1h using separatory funnel In aniline solution, be stirred continuously make its react 4h, be then allowed to stand filtering, by filtrate washing dry after grind into powder to get Polyaniline/Al nano-particle powders;
Step 4 prepares anticorrosion composite coating:
It takes 5 parts of polyanilines/Al nano-particles and 7 parts of composite fibre to be placed in beaker, 60 parts of N-Methyl pyrrolidones, magnetic force is added 30min is stirred, 2h is then sonicated;
Then 10 parts of epoxy resin and 6 parts of n-butanols are put into another beaker, magnetic agitation 1h, solution in two beakers is mixed It closes, stirs 2h, sequentially add 3 parts of 4 parts of normal propyl alcohol, 1 part of trbasic zinc phosphate, 2 parts of aluminium triphosphate, 1 part of talcum powder and barium sulfate, then stir 2 parts of 50 curing agent of polyamide 6 are added after mixing 1h, the anticorrosion composite coating is obtained after mechanical agitation 2h.
2. accumulator according to claim 1, which is characterized in that the corrosion-resistant coating thickness is 400~600 μm.
CN201610571585.1A 2016-07-18 2016-07-18 A kind of accumulator with corrosion resistance Expired - Fee Related CN105957985B (en)

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CN203398218U (en) * 2013-07-09 2014-01-15 马鞍山市海鹰蓄电池配件厂 High-capacity traction lead-acid storage battery
CN203536542U (en) * 2013-10-22 2014-04-09 大连爱镁瑞电池有限公司 Empty battery of magnesium
CN204315633U (en) * 2014-08-28 2015-05-06 安徽龙钢金属制品有限公司 Battery cell case
CN105531841A (en) * 2013-06-04 2016-04-27 通用汽车环球科技运作有限责任公司 Plasma coating for corrosion protection of light-metal components in battery fabrication

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US6887613B2 (en) * 2002-12-04 2005-05-03 General Motors Corporation Corrosion resistant PEM fuel cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105531841A (en) * 2013-06-04 2016-04-27 通用汽车环球科技运作有限责任公司 Plasma coating for corrosion protection of light-metal components in battery fabrication
CN203398218U (en) * 2013-07-09 2014-01-15 马鞍山市海鹰蓄电池配件厂 High-capacity traction lead-acid storage battery
CN203536542U (en) * 2013-10-22 2014-04-09 大连爱镁瑞电池有限公司 Empty battery of magnesium
CN204315633U (en) * 2014-08-28 2015-05-06 安徽龙钢金属制品有限公司 Battery cell case

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