CN110277560A - Collector and preparation method thereof, electrode slice and preparation method thereof and lead-acid battery - Google Patents
Collector and preparation method thereof, electrode slice and preparation method thereof and lead-acid battery Download PDFInfo
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- CN110277560A CN110277560A CN201910578866.3A CN201910578866A CN110277560A CN 110277560 A CN110277560 A CN 110277560A CN 201910578866 A CN201910578866 A CN 201910578866A CN 110277560 A CN110277560 A CN 110277560A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- Y02E60/10—Energy storage using 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
A kind of collector, the collector are made of fiber reinforcement type carbon aerogel composite material；The fiber reinforcement type carbon aerogel composite material is highly conductive porous carbon material, and the fiber reinforcement type carbon aerogel composite material includes charcoal-aero gel and fiber, and the fiber is filled in the charcoal-aero gel.The invention further relates to the preparation method of collector, electrode slice, the preparation method of electrode slice and lead-acid batteries.
Description
Technical field
The present invention relates to collector and lead storage battery field more particularly to a kind of collectors, the preparation method of collector, electricity
Pole piece, the preparation method of electrode slice and lead-acid battery.
Background technique
Lead-acid battery occupies great market share in secondary cell market, is one of major impetus power supply of electric vehicle, tool
Have the advantages that using temperature range is big, highly-safe, cost performance is high.Because the atomic number of lead is high, density is big, in specific energy side
There is obvious disadvantage in face compared with emerging lithium ion battery.Therefore, occupation rate of market of the lead-acid battery in mobile application be gradually
It is nibbled by lithium ion battery.And in existing lead-acid battery technology, highdensity metal is often used as grid, and in electrification
It learns in charge and discharge process, positive and negative anodes active material cannot react completely, so that the specific energy of lead-acid battery is low, cycle life
It is short.
Summary of the invention
In view of this, the present invention provides the preparation of collector, collector that a kind of specific energy density is high and has extended cycle life
Method, electrode slice, the preparation method of electrode slice and lead-acid battery.
A kind of collector, the collector are made of fiber reinforcement type carbon aerogel composite material；The fiber reinforcement type
Carbon aerogel composite material is highly conductive porous carbon material, and the fiber reinforcement type carbon aerogel composite material includes charcoal airsetting
Glue and fiber, the fiber are filled in the charcoal-aero gel.
Further, the fiber is chopped carbon fiber.
Further, the fiber reinforcement type carbon aerogel composite material further includes artificial foramen template, the artificial casement
Plate is filled in the charcoal-aero gel.
Further, the artificial foramen template is foamed plastics and/or hollow membrane.
Further, in the fiber reinforcement type carbon aerogel composite material, the volume basis of the charcoal-aero gel contains
Amount is 80%~85%, and the volumn concentration of the fiber is 10%, and the volumn concentration of the artificial foramen template is 5%
~10%.
A kind of preparation method of collector as described above, comprising steps of configuration precursor solution, the precursor solution
For polymerizable water system high-molecular precursor solution；Fiber is added into the precursor solution and divides the fiber uniformly
It is dispersed in the precursor solution；It heats the precursor solution to be allowed to that home position polymerization reaction occurs, obtains a hydrogel；It is described
Fiber is filled in the hydrogel；The dry hydrogel, obtains the organogel with ideal network structure；And in anaerobic
Heating carbonizes the organogel under environment, obtains fiber reinforcement type carbon aerogel composite material.
Further, in the step of " heating the precursor solution to be allowed to that home position polymerization reaction occurs, obtain a hydrogel "
Before rapid, further comprise the steps of: and artificial foramen template is added in the precursor solution and keeps the artificial foramen template evenly dispersed
In the precursor solution, the artificial foramen template is filled in the hydrogel.
Further, it before " fiber is added into the precursor solution " the step of, further comprises the steps of: to described
Fiber is chopped and is surface-treated.
Further, the surface treatment is using in plasma discharge, surface coupling, surface grafting, process for surface oxidation
At least one.
Further, the charcoal-aero gel is that home position polymerization reaction occurs by resorcinol and formaldehyde to be prepared, in original
In the polymerization process of position, reaction temperature is 70~90 degrees Celsius, and the reaction time is between 48~78 hours.
Further, " heating carbonize the organogel " the step of before or step after, further comprise the steps of: to institute
It states organogel or the fiber reinforcement type carbon aerogel composite material carries out sharp processing.
A kind of electrode slice, the electrode slice include a collector as described above and are supported in the hole of the collector
Electrode active material.
Further, the electrode active material is nanoscale electrodes active material；When the electrode slice is negative electrode plate
When, the electrode active material is negative electrode active material, and the negative electrode active material is elementary lead；When the electrode slice is
When electrode film, the electrode active material is active positive electrode material, and the active positive electrode material is brown lead oxide.
Further, the electrode slice further includes insulating passivation layer, to reduce the reaction speed of the side reaction of electrode slice；Institute
Insulating passivation layer is stated to be formed on the position of the unsupported electrode active material of the electrode slice.
A kind of production method of electrode slice, comprising steps of using collector as described above as grid carrier, the grid
Carrier is highly conductive porous material；And the load electrode active material in the hole of the grid carrier.
It further, later further include step in the step of " the load electrode active material in the hole of the grid carrier "
Rapid: insulation is passivated the electrode slice, forms insulation passivation on the surface of the unsupported electrode active material of the electrode slice
Layer.
Further, the electrode active material is nanoscale electrodes active material, by dipping-curing process described
Nanoscale electrodes active material is loaded in the hole of grid carrier.
A kind of lead-acid battery, the lead-acid battery include isolation film and electrolyte, and the lead-acid battery further includes institute as above
The electrode film and negative electrode plate stated, the electrode film, negative electrode plate, isolation film are respectively positioned in the electrolyte, it is described just
Electrode slice and negative electrode plate are spaced apart by the isolation film, and the electrode film and negative electrode plate pass through metal and/or conduction
Material connection, with built-up circuit.
Further, the electrode film and the negative electrode plate further include insulating passivation layer, to reduce electrode slice
The reaction speed of side reaction；The insulating passivation layer be formed in the electrode film and the negative electrode plate it is unsupported it is described just
On the position of electrode active material or negative electrode active material.
Charcoal-aero gel is combined production by the present invention with fiber, and to form mushy fiber reinforcement type charcoal-aero gel compound
Material, and mushy fiber reinforcement type carbon aerogel composite material production collector is used, 1) fiber reinforcement type charcoal gas
The density of grid collector can be greatly lowered in the porous rate of gel complex material, to improve specific energy density；2) exist
In charge and discharge process, there is electrochemical reaction in the intracorporal pore surface of afflux, to participate in the reaction of battery；In addition, adopting
Use nanoscale electrodes active material as electrode active material, the nano level active material granule degree in hole is small, surface area is big,
Bigger high rate performance and utilization efficiency can be brought, so as to promote the cycle life of the lead-acid battery；3) fibre
Tieing up further includes artificial foramen template in enhanced carbon aerogel composite material, and the artificial foramen template is filled in the charcoal-aero gel
It is interior, the macroscopic pores of some large apertures can be manufactured, in the charcoal-aero gel so as to further enrich the hole of charcoal-aero gel
Gap rate, so that the density of grid collector is further decreased, to improve specific energy density and cycle life.
Specific embodiment
For can the present invention is further explained reaches the technical means and efficacy that predetermined goal of the invention taken, below in conjunction with compared with
Good embodiment, to the preparation method of collector provided by the invention, collector, electrode slice, the preparation method of electrode slice and lead
Specific embodiment, structure, feature and its effect of battery are made as described in detail below.
Better embodiment of the present invention provides a kind of electrode slice, and the electrode slice includes collector and is supported on the afflux
Electrode active material on body.
Wherein, the collector is made of fiber reinforcement type carbon aerogel composite material, the fiber reinforcement type charcoal airsetting
Glue composite material is mushy material, and the electrode active material is supported on the fiber reinforcement type carbon aerogel composite material
In hole.
The fiber reinforcement type carbon aerogel composite material includes charcoal-aero gel and fiber, is formed in the charcoal-aero gel
A large amount of hole, the fiber are filled in the charcoal-aero gel.
In the present embodiment, the charcoal-aero gel occurs what home position polymerization reaction was prepared by resorcinol and formaldehyde
Highly conductive mushy material.
Wherein, the fiber is used to increase the flexibility and machinability of the fiber reinforcement type carbon aerogel composite material.
Wherein, the fiber can be but be not limited to the inorfils such as carbon fiber, ceramic fibre, glass fibre, polyester
The synthetic fibers such as fiber, Fypro, vinal, polyacrylonitrile fibre, regenerated fiber, macromolecular fibre, mixing
The mineral fibres such as fiber and chrysotile, crocidolite.
Preferably, the fiber is carbon fiber.
Preferably, the carbon fiber is chopped carbon fiber.In the present embodiment, the length of the chopped carbon fiber is 3
Millimeter is between 4 centimetres.
Wherein, both the carbon fiber and the charcoal-aero gel combine, not only can be in the fiber reinforcement type charcoal airsetting
Good conductive network structure is established in glue composite material, additionally it is possible to limit the fiber reinforcement type carbon aerogel composite material
The volume contraction in drying carbonization process in preparation method, to enhance the fiber reinforcement type carbon aerogel composite material
Structural strength.
Wherein, the fiber reinforcement type carbon aerogel composite material further includes artificial foramen template, and the artificial foramen template is filled out
It fills in the charcoal-aero gel.Wherein, the artificial foramen template in the charcoal-aero gel for forming the macro of some large apertures
View hole, to further increase the porosity of the charcoal-aero gel.
In the fiber reinforcement type carbon aerogel composite material, the volumn concentration of the charcoal-aero gel is 80%~
85%, the volumn concentration of the fiber is 10%, and the volumn concentration of the artificial foramen template is 5%~10%.
Wherein, the artificial foramen template can be but be not limited to foamed plastics and/or hollow membrane.
Preferably, the artificial foramen template is bead foamed plastics.
Preferably, the electrode active material is nanoscale electrodes active material.
Wherein, when the electrode slice is negative electrode plate, the electrode active material is negative electrode active material, the negative electricity
Pole active material is elementary lead.
Wherein, when the electrode slice is electrode film, the electrode active material is active positive electrode material, the positive electricity
Pole active material is brown lead oxide.
The electrode slice further includes insulating passivation layer, to reduce the reaction speed of the side reaction of electrode slice.It is described exhausted
Edge passivation layer formation is on the position of the unsupported electrode active material of the electrode slice.
The present invention also provides the preparation methods of a collector, include the following steps:
The first step, configures precursor solution, and the precursor solution is polymerizable water system high-molecular precursor solution.
Second step, fiber is added into the precursor solution and so that the fiber is dispersed in the presoma molten
In liquid.
Third step heats the precursor solution and is allowed to that home position polymerization reaction occurs, obtains a hydrogel.The fiber is filled out
It fills in the hydrogel.
4th step, the dry hydrogel, obtains the organogel with ideal network structure.
5th step, heating carbonizes the organogel under oxygen-free environment, obtains fiber reinforcement type charcoal-aero gel composite wood
Material.
Wherein, the fiber is used to increase the flexibility and machinability of the fiber reinforcement type carbon aerogel composite material.
Wherein, it before the second step the step of, further comprises the steps of: and the fiber is chopped and is surface-treated.
Wherein, carrying out chopped purpose to the fiber is: dispersing in the precursor solution convenient for the fiber.?
In present embodiment, the carbon fiber is chopped carbon fiber.Preferably, the length of the chopped carbon fiber is at 3 millimeters to 4 centimetres
Between.
Wherein, the surface treatment generally using physical methods such as plasma discharges or uses water solution system and chemistry side
Method processing.Wherein, the processing time of plasma discharge is preferably 0.1 second to 5 seconds.Carrying out surface treatment using chemical method includes
But it is not limited to the methods of surface coupling, surface grafting, surface oxidation.
Wherein, it before the third step the step of, further comprises the steps of: and artificial foramen template is added in the precursor solution simultaneously
It is dispersed in the artificial foramen template in the precursor solution, the artificial foramen template is filled in the hydrogel.
Wherein, the artificial foramen template is used to be formed the macroscopic pores of some large apertures in the charcoal-aero gel, thus into
One step improves the porosity of the charcoal-aero gel.
Wherein, it before four steps the step of, further comprises the steps of: and the hydrogel is immersed in organic solution (for example, third
Ketone) in, so that acetone all replaces the moisture in the hydrogel, to obtain organogel.Wherein, described in being replaced using acetone
Moisture in hydrogel can reduce hydrogel and the risk that capillary is shunk occurs in the drying hydrogel, described to prevent
Hydrogel shape changes, or even cracking.
Wherein, it before or after the step of five steps, further comprises the steps of: to the aeroge or the fiber reinforcement type
Carbon aerogel composite material carries out sharp processing.
Wherein, the charcoal-aero gel is that home position polymerization reaction occurs by resorcinol and formaldehyde to be prepared.Gather in situ
It closes in reaction process, reaction temperature is 70~90 degrees Celsius, and the reaction time is between 48~78 hours.By more fully polymerizeing
Reaction, enhances the intensity and conductive intensities of charcoal-aero gel.In other words, the precursor solution include resorcinol, formaldehyde,
Solvent and catalyst.In the present embodiment, the solvent is deionized water, and the catalyst is a small amount of sodium carbonate.
Wherein, the density of the fiber reinforcement type charcoal-aero gel is 0.5g/cm3~1.0g/cm3, average pore size be 1~
3nm, specific surface area 500m2/ g~1500m2/g。
The present invention also provides the preparation methods of an electrode slice, include the following steps:
The first step, using collector as described above as grid carrier, the grid carrier is highly conductive porous material.
Second step, the load electrode active material in the hole of the grid carrier.
After the fiber reinforcement type carbon aerogel composite material (carbon material) is added into lead-acid battery, in anode and cathode
Certain side reaction can occur.The oxidation of oxygen evolution reaction or carbon is shown as in anode, cathode shows as evolving hydrogen reaction.Two pairs are anti-
It should be all on the proportional influence of the coulombic efficiency of battery, need exist to reducing the degree of side reaction.Therefore, " in the grid
Insulation, which is further comprised the steps of:, after the step of load nanoscale electrodes active material in the hole of carrier " is passivated the electrode slice,
The surface of the unsupported nanoscale electrodes active material of the electrode slice forms insulating passivation layer, to reduce the journey of side reaction
Degree.
Preferably, the electrode active material is nanoscale electrodes active material.
Wherein, when the electrode slice is negative electrode plate, the electrode active material is elementary lead, and the electrode slice is positive electricity
When pole piece, the electrode active material is brown lead oxide.
Preferably, by loading nanoscale electrodes active material in the hole of grid carrier described in dipping-curing process.
Wherein, when the electrode slice is electrode film, " dipping-curing process " includes the following steps:
Grid carrier is immersed in lead salt solution by the first step.
Second step solidifies lead, thus in grid supported on carriers nanoscale solids by chemistry or electrochemical process
Lead.
Third step takes out the grid carrier, dry, and in the position coating insulation passivation for not covering the solid lead
Layer.
4th step makes the lead monoxide in the solid lead be oxidized to brown lead oxide by formation process.
Wherein, in dipping-curing process of electrode film, the solid sheath include lead monoxide, basic lead sulphate, lead and
Brown lead oxide etc..
Wherein, when the electrode slice is negative electrode plate, " dipping-curing process " includes the following steps:
Grid carrier is immersed in lead salt solution by the first step；
Second step solidifies lead by chemistry or electrochemical process, to form nanoscale solid on grid carrier
Lead；
Third step takes out the grid carrier, dry, and in the position coating insulation passivation for not covering the solid lead
Layer；And
4th step makes the lead monoxide in solid lead be reduced into elementary lead by formation process.
Wherein, in dipping-curing process of negative electrode plate, the solid sheath includes lead monoxide, lead sulfate, lead, nothing
Machine swelling agent, organic expander and antioxidant etc..
The present invention also provides a kind of lead-acid battery, the lead-acid battery includes electrode film, negative electrode plate, isolation film and electricity
Liquid is solved, the electrode film, negative electrode plate, isolation film are respectively positioned in the electrolyte, and the electrode film and negative electrode plate are logical
It crosses the isolation film to be spaced apart, the electrode film and negative electrode plate are connected by metal and/or conductive material, to form
Circuit.
Wherein, the electrode film includes collector and the active positive electrode material that is supported on the collector.It is described
Negative electrode plate includes collector and the negative electrode active material that is supported on the collector.
Wherein, the collector is made of fiber reinforcement type carbon aerogel composite material, the fiber reinforcement type charcoal airsetting
Glue composite material is mushy material, and the electrode active material loads the hole of the fiber reinforcement type carbon aerogel composite material
In gap.
Wherein, the fiber reinforcement type carbon aerogel composite material includes charcoal-aero gel and fiber, in the charcoal-aero gel
It is formed with a large amount of hole, the fiber is filled in the charcoal-aero gel.
Wherein, the fiber reinforcement type carbon aerogel composite material further includes artificial foramen template, and the artificial foramen template is filled out
It fills in the charcoal-aero gel.
Preferably, the negative electrode active material is nanoscale negative electrode active material, and the active positive electrode material is
Nanoscale negative electrode active material.The negative electrode active material is elementary lead, and the active positive electrode material is brown lead oxide.
The electrode film and the negative electrode plate further include insulating passivation layer, to reduce the side reaction of electrode slice
Reaction speed.The insulating passivation layer is formed in the unsupported positive electrode active material of the electrode film or negative electrode plate
On the position of material or negative electrode active material.
The present invention is specifically described below by Examples and Comparative Examples.
The preparation of 1 fiber reinforcement type charcoal-aero gel of embodiment
In 3 liters of cuboid container, the resorcinol and formaldehyde being dissolved in water are with molar ratio 1:2 mixing, phenol
The ratio of aldehyde and water is 1:8, and addition accounts for the sodium carbonate liquor of resorcinol 1/1000.Stirring is allowed to uniformly mixed in 30 minutes.Add
Enter the carbon fiber that 30 grams of length are 5 millimeters makes carbon fiber be uniformly dispersed by stirring and ultrasonic disperse.Container is sealed, is placed in
85 DEG C of environment are kept for 4 days, obtain hydrogel.60 DEG C of dryings obtain organogel in 24 hours under normal pressure.Machining, cutting
At grid shape.It handles 2 hours and carbonizes in 800 DEG C under oxygen-free environment.The carbon aerogels of fiber reinforcement type can be obtained.
The preparation of 2 fiber reinforcement type charcoal-aero gel of embodiment
In 3 liters of cuboid container, the resorcinol and formaldehyde being dissolved in water are with molar ratio 1:2 mixing, phenol
The ratio of aldehyde and water is 1:9, and addition accounts for the sodium carbonate liquor of resorcinol 1/800.Stirring is allowed to uniformly mixed in 30 minutes.It is added
The polyacrylonitrile fibre that 40 grams of length is 4 millimeters, 1 gram of benzene sulfonic acid sodium salt make polyacrylonitrile fibre point by stirring and ultrasonic disperse
It dissipates uniform.Container is sealed, 85 DEG C of environment are placed in, is kept for 3 days, obtains hydrogel.60 DEG C of dryings obtain for 24 hours under normal pressure
Organogel.Machining, is cut into grid shape.It handles 2 hours and carbonizes in 800 DEG C under oxygen-free environment.Carbon can be obtained
Fibre-reinforced carbon aerogels.
Preparation of the embodiment 3 with eurypyloue fiber reinforcement type charcoal-aero gel
In 2 liters of cuboid container, the resorcinol and formaldehyde being dissolved in water are with molar ratio 1:2 mixing, phenol
The ratio of aldehyde and water is 1:9, and addition accounts for the sodium carbonate liquor of resorcinol 1/800.Stirring is allowed to uniformly mixed in 30 minutes.It is added
The polyacrylonitrile fibre that 30 grams of length is 4 millimeters makes polyacrylonitrile fibre be uniformly dispersed by stirring and ultrasonic disperse.It is added
Volume is about 1 liter, and the foamed plastics bead that granularity is 1 millimeter seals container, and bead should be full of container, to avoid buoyancy
Influence causes system uniformity to decline.85 DEG C of environment are placed in, is kept for 3.5 days, obtains hydrogel.60 DEG C of dryings 24 are small under normal pressure
When obtain organogel.Machining, is cut into grid shape.It handles 2 hours and carbonizes in 800 DEG C under oxygen-free environment.?
It obtains with eurypyloue fiber reinforcement type carbon aerogels.
Embodiment 4 with eurypyloue fiber reinforcement type carbon aerogels as the electrode slice of collector to prepare
Using embodiment 3 obtain with eurypyloue fiber reinforcement type carbon aerogels as grid (collector), directly cathode
Cream (negative electrode active material) is coated on grid, uses metallic lead as the lead of grid, prepares negative electricity with conventional lead acid battery method
Pole piece, and be melted into.The electrode slice can be used as electrode film or negative electrode plate, be controlled by chemical conversion.
Embodiment 5 is prepared by the electrode of collector of fiber reinforcement type charcoal-aero gel
Using fiber reinforcement type charcoal-aero gel described in embodiment 2 as grid, the saturation that grid carrier is immersed in lead acetate is molten
30 minutes in liquid, vacuumized therebetween to exclude bubble.Grid is taken out, is dried 10 hours at 60 DEG C.It impregnates again, drying is primary.
It is heat-treated 30 minutes as 400 DEG C under nitrogen protection later, obtains leaded oxide carried aeroge, and be melted into.The electricity
Pole piece can be used as electrode film or negative electrode plate, be controlled by chemical conversion.
Embodiment 6 carries out the preparation of the lead-acid battery of circuit connection using conductive polymer material
With dispenser made of embodiment 5 or 6 after the bi-component epoxide-resin for being filled with conductive material is mixed
Electrode slice (electrode film and negative electrode plate) connects, built-up circuit, and electrode slice and isolation film are placed in electrolyte, from
And obtain lead-acid battery that can be practical.
Charcoal-aero gel is combined production by the present invention with fiber, and to form mushy fiber reinforcement type charcoal-aero gel compound
Material, and mushy fiber reinforcement type carbon aerogel composite material production collector is used, 1) fiber reinforcement type charcoal gas
The density of grid collector can be greatly lowered in the porous rate of gel complex material, to improve specific energy density；2) exist
In charge and discharge process, there is electrochemical reaction in the intracorporal pore surface of afflux, to participate in the reaction of battery；In addition, adopting
Use nanoscale electrodes active material as electrode active material, the nano level active material granule degree in hole is small, surface area is big,
Bigger high rate performance and utilization efficiency can be brought, so as to promote the cycle life of the lead-acid battery；3) directly sharp
It uses fiber reinforcement type carbon aerogel composite material as collector, can be crushed to avoid to carbon, to ensure that the fibre
Enhanced carbon aerogel composite material and its excellent electric conductivity are tieed up, it is high after the active material in electrode slice is consumed
Conductive fiber reinforcement type carbon aerogel composite material can be used as current path, to further promote the lead-acid battery
Cycle life；4) fiber can not only be established in conjunction with charcoal-aero gel in the fiber reinforcement type carbon aerogel composite material
Good conductive network structure, additionally it is possible to limit the fiber reinforcement type carbon aerogel composite material in dry carbonization process
Volume contraction, so as to enhance the structural strength of the fiber reinforcement type carbon aerogel composite material；5) fiber reinforcement
It further include artificial foramen template in type carbon aerogel composite material, the artificial foramen template is filled in the charcoal-aero gel, can
The macroscopic pores of some large apertures are manufactured, in the charcoal-aero gel so as to further enrich the pore-size distribution of charcoal-aero gel.
The above is only better embodiment of the invention, not the limitation to the present invention in any form, though
The right present invention has been that better embodiment is disclosed above, is not intended to limit the invention, any person skilled in the art,
Without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified to
With the equivalent implementations of variation, but without departing from the technical solutions of the present invention, according to the technical essence of the invention to
Any simple modification, equivalent change and modification that upper embodiment is done, all of which are still within the scope of the technical scheme of the invention.
Claims (19)
1. a kind of collector, which is characterized in that the collector is made of fiber reinforcement type carbon aerogel composite material；The fibre
Tieing up enhanced carbon aerogel composite material is highly conductive porous carbon material, the fiber reinforcement type carbon aerogel composite material packet
Charcoal-aero gel and fiber are included, the fiber is filled in the charcoal-aero gel.
2. collector as described in claim 1, which is characterized in that the fiber is chopped carbon fiber.
3. collector as described in claim 1, which is characterized in that the fiber reinforcement type carbon aerogel composite material further includes
Artificial foramen template, the artificial foramen template are filled in the charcoal-aero gel.
4. collector as claimed in claim 3, which is characterized in that the artificial foramen template is foamed plastics and/or hollow thin
Film.
5. collector as claimed in claim 3, which is characterized in that in the fiber reinforcement type carbon aerogel composite material,
The volumn concentration of the charcoal-aero gel is 80%~85%, and the volumn concentration of the fiber is 10%, described artificial
The volumn concentration of hole template is 5%~10%.
6. a kind of preparation method of collector as described in any one in claim 1-5, comprising steps of
Precursor solution is configured, the precursor solution is polymerizable water system high-molecular precursor solution；
Fiber is added into the precursor solution and is dispersed in the fiber in the precursor solution；
It heats the precursor solution to be allowed to that home position polymerization reaction occurs, obtains a hydrogel；The fiber is filled in the water
In gel；
The dry hydrogel, obtains the organogel with ideal network structure；And
Heating carbonizes the organogel under oxygen-free environment, obtains fiber reinforcement type carbon aerogel composite material.
7. the preparation method of collector as claimed in claim 6, which is characterized in that " heating the precursor solution to be allowed to
Occur home position polymerization reaction, obtain a hydrogel " the step of before, further comprise the steps of:
Artificial foramen template is added in the precursor solution and so that the artificial foramen template is dispersed in the presoma molten
In liquid, the artificial foramen template is filled in the hydrogel.
8. the preparation method of collector as claimed in claim 6, which is characterized in that " fiber is being added into the presoma
In solution " the step of before, further comprise the steps of:
The fiber is chopped and is surface-treated.
9. the preparation method of collector as claimed in claim 8, which is characterized in that the surface treatment is put using plasma
At least one of electricity, surface coupling, surface grafting, process for surface oxidation.
10. the preparation method of collector as claimed in claim 6, which is characterized in that the charcoal-aero gel is by resorcinol
Home position polymerization reaction occurs with formaldehyde to be prepared, in situ in polymerization process, reaction temperature is 70~90 degrees Celsius, instead
Between seasonable between 48~78 hours.
11. the preparation method of collector as claimed in claim 6, which is characterized in that " heating carbonizes the organogel "
The step of before or step after, further comprise the steps of:
Sharp processing is carried out to the organogel or the fiber reinforcement type carbon aerogel composite material.
12. a kind of electrode slice, which is characterized in that the electrode slice includes a collector as described in any one in claim 1-5
And it is supported on the electrode active material in the hole of the collector.
13. electrode slice as claimed in claim 12, which is characterized in that the electrode active material is nanoscale electrodes activity material
Material；When the electrode slice is negative electrode plate, the electrode active material is negative electrode active material, the negative electrode active material
Material is elementary lead；When the electrode slice is electrode film, the electrode active material is active positive electrode material, the positive electricity
Pole active material is brown lead oxide.
14. electrode slice as claimed in claim 12, which is characterized in that the electrode slice further includes insulating passivation layer, to reduce
The reaction speed of the side reaction of electrode slice；The insulating passivation layer is formed in the unsupported nanoscale electrodes of the electrode slice
On the position of active material.
15. a kind of production method of electrode slice, comprising steps of
Using collector as described in any one in claim 1-5 as grid carrier, the grid carrier is highly conductive porous material
Material；And
The load electrode active material in the hole of the grid carrier.
16. the production method of electrode slice as claimed in claim 15, which is characterized in that " in the hole of the grid carrier
Insulation is further comprised the steps of: after the step of middle load nanoscale electrodes active material " and is passivated the electrode slice, in the electrode slice
The unsupported electrode active material surface formed insulating passivation layer.
17. the production method of electrode slice as claimed in claim 15, which is characterized in that by dipping-curing process described
Nanoscale electrodes active material is loaded in the hole of grid carrier.
18. a kind of lead-acid battery, the lead-acid battery includes isolation film and electrolyte, which is characterized in that the lead-acid battery is also
Including electrode film as claimed in claim 13 and negative electrode plate, the electrode film, negative electrode plate, isolation film are respectively positioned on institute
It states in electrolyte, the electrode film and negative electrode plate are spaced apart by the isolation film, the electrode film and negative electrode plate
It is connected by metal and/or conductive material, with built-up circuit.
19. lead-acid battery as claimed in claim 18, which is characterized in that the electrode film and the negative electrode plate also wrap
Insulating passivation layer is included, to reduce the reaction speed of the side reaction of electrode slice；The insulating passivation layer is formed in the electrode film
And the negative electrode plate the unsupported active positive electrode material or negative electrode active material position on.
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| CN111740116A (en) * | 2020-05-14 | 2020-10-02 | 超威电源集团有限公司 | Current collector of carbon-containing material felt electroplating coating and preparation method thereof |
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