CN104681812B - Graphite composite carbon electrode material for lead acid battery, electrode prepared from electrode material and preparing method of electrode - Google Patents
Graphite composite carbon electrode material for lead acid battery, electrode prepared from electrode material and preparing method of electrode Download PDFInfo
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- CN104681812B CN104681812B CN201510018761.4A CN201510018761A CN104681812B CN 104681812 B CN104681812 B CN 104681812B CN 201510018761 A CN201510018761 A CN 201510018761A CN 104681812 B CN104681812 B CN 104681812B
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 78
- 239000010439 graphite Substances 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 28
- 239000007772 electrode material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 17
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 235000011149 sulphuric acid Nutrition 0.000 claims description 18
- 239000001117 sulphuric acid Substances 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
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- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
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- 239000010949 copper Substances 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- -1 is obtained Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 6
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- 230000002687 intercalation Effects 0.000 claims description 5
- 238000009830 intercalation Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- 238000005255 carburizing Methods 0.000 claims 1
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- 238000005260 corrosion Methods 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 2
- 238000009825 accumulation Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
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- 230000006835 compression Effects 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000994 depressogenic effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 239000010410 layer Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
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- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
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- 230000023556 desulfurization Effects 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
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- 239000013081 microcrystal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery preparing, and in particular relates to a graphite composite carbon electrode material for a lead acid battery, an electrode prepared from the electrode material and a preparing method of the electrode. The graphite composite carbon electrode material for the lead acid battery consists of the following components in percentage by mass: 30-98% of powdered carbon or graphite paper and the balance being a binding agent; the powdered carbon mainly contains expanded graphite sulfate powder and/or expanded graphite sulfate worms; the binding agent is composed of thermosetting resin and a resin-type additive, wherein the weight of resin-type additive accounts for 5-40% of the total weight of the binding agent; and the resin-type additive is selected from any one or any combinations of lignin, asphalt and bitumen. The carbon electrode provided by the invention has the excellent properties of low resistance, high mechanical strength, sulfuric acid corrosion resistance, light weight, long service life and the like; as the inner core of the electrode of the lead acid battery, a carbon electrode can replace part lead grids, so that the battery is quite suitable for vehicles and clean energy accumulation.
Description
Technical field
The invention belongs to cell manufacturing techniques field, and in particular to a kind of graphite composite carbon electrode material for lead-acid battery
Material, its electrode for preparing and preparation method thereof.
Background technology
Lead-acid battery is used in every field as inexpensive secondary cell, and its market scale exceedes other secondary cells
Summation, but its disadvantage is that energy density is low and cycle life is short.Colelctor electrode and electrode material are lead and Lead oxide brown,
High as the lead proportion of colelctor electrode, weight weight reduces energy density, and after its corrosion is lost in, the life-span of battery is also most.It is common
Product energy density be 30 watt-hours/kilogram, the deeper cavity life-span of 100-200 time, if the life-span will be increased, its energy density drops
To 20 watt-hours/kilogram, such as with its energy density of carbon electrode up to 120 watt-hours/kilogram.There are patent utilization Linesless charcoal and Carbon foam in the U.S.
Electrode industrialization as lead-acid battery（US6979513B2, US7033703B2, US7060391B2, US8399134B2）,
And higher its work(of reduction of electrode resistance of the patent application US20110083966A1 of high density carbon electrode, Linesless charcoal and Carbon foam
Rate density, although the complex internal resistance of graphite and graphite is low, its acid resistance is poor.
Increase the resistance to sulfuric acid and mechanical strength of graphite and its composite, it is the practical of graphite electrode to reduce internal resistance
Prerequisite.The interlayer structure of graphite is molecular separating force, is easily invaded by sulphuric acid and causes swelling and destruction, the low difficulty of its mechanical strength
To load highdensity electrode active material, the present invention is that the composite of modified graphite meets plumbic acid with as electrode material
Battery is required.Its surface hot dip or one layer of lead of plating or metal when in use strengthens the bond strength with lead plaster.
The content of the invention
The present invention provides a kind of graphite composite carbon electrode material for lead-acid battery, and which has low resistance, high machinery strong
The premium properties such as degree, sulfuric acid corrosion resistant, lightweight and long-life.
The invention provides carbon electrode made by a kind of described graphite composite carbon electrode material.
The invention provides a kind of preparation method for being adapted to a large amount of production graphite composite carbon electrodes.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of graphite composite carbon electrode material for lead-acid battery, which includes component as follows in terms of mass fraction：
Powdered carbon or graphite paper 30%-98%, balance of binding agent,
Powdered carbon main component is sulphuric acid expanded graphite powder and/or sulphuric acid expanded graphite worm, and other powdered carbons such as white carbon black is living
Also the alternative part graphite powder such as property powdered carbon, coke powder；
Binding agent is made up of thermosetting resin and resin type additive, and wherein resin type additive accounts for binding agent gross weight
5%-40%, is that reduces cost and increase manufacturability resin type additive obtain the higher lignin of charcoal rate, cypress selected from high temperature carbonization
One or more combination in oil and Colophonium, Colophonium and pitch performance and cost are close to, typically from one kind therein.
When the material is produced, although solvent and other auxiliary agents are added in the formula of electrode material, increase manufacturability, can't change multiple
The performance of composite electrode.
Preferably, the thermosetting resin is made up of epoxy resin and phenolic resin, the quality of its epoxy resin is accounted for
30%-90%.Phenolic resin 30%-90%, Colophonium 0-40% and lignin 0-40% compositions.
Preferably, described graphite powder or graphite paper are 800-1200 DEG C of expanded graphite powder of sulphuric acid intercalation high temperature or graphite
Paper.
Carbon electrode made by a kind of described graphite composite carbon electrode material.Further, the thickness of carbon electrode is 0.1 milli
Rice is to 10 millimeters.
A kind of preparation method of described carbon electrode, the binding agent are obtained resin solution, are set after being mixed with organic solvent
Lipoprotein solution obtains compound after mixing with powdered carbon, obtains solidifying composite plate after being dried hot-press solidifying；Not higher than 80 DEG C of baking temperature,
The temperature of hot pressing is 120 DEG C to 250 DEG C, and pressure is 0.3 to 20 MPa；
Solidification composite plate carbonization obtains graphite composite carbon electrode, 300 DEG C to 1400 DEG C of carbonization temperature, pressure -0.1 to 10,000,000
Handkerchief, 1 to 60 DEG C of programming rate/min, atmosphere are vacuum, nitrogen or vapor or the two gaseous mixture.Further, in compound
The embedded Copper Foil or copper cash for accounting for compound cumulative volume 5 to 40%, then carry out hot-press solidifying.
A kind of preparation method of described carbon electrode, the binding agent obtain resin solution after mixing with organic solvent, will
It is dried at a temperature of not higher than 80 DEG C after resin solution immersion graphite paper, then after double-roll rolling mill compacting, hot-press solidifying is consolidated
Change composite plate, the temperature of hot pressing is 120 DEG C to 250 DEG C, pressure is 0.3 to 20 MPa；
Solidification composite plate carbonization obtains graphite composite carbon electrode, 300 DEG C to 1400 DEG C of carbonization temperature, pressure -0.1 to 10,000,000
Handkerchief, 1 to 60 DEG C of programming rate/min, atmosphere are vacuum, nitrogen or vapor or the two gaseous mixture.Further, resin solution
In the compound that immersion graphite paper is obtained, the embedded Copper Foil or copper cash for accounting for graphite paper cumulative volume 5 to 40% forms Copper Foil or copper cash
Carry out hot-press solidifying after graphite paper sandwich structure again.
Its raw material is the low expanded graphite powder of sulphuric acid swelling effect, graphite worm or graphite paper, can also add part burnt
Charcoal, white carbon black and activated carbon powder change its acid resistance；Thermosetting resin comes selected from phenolic resin, polyester resin, epoxy resin, span
One or more in imide resin, polyimides.
The present invention adopts the sulphuric acid expanded graphite powder or graphite paper of resistance to sulphuric acid for high connductivity carrier, the heat curing-type tree of low cost
The resin type such as fat and Colophonium additive is binding agent, produces high strength graphite composite carbon electrode.The use of the electrode can subtract
The weight of low battery, the life-span for increasing battery and the performance for improving battery.
The main component of carbon electrode is the carbon and charcoal of various patterns, the conductivity highest of graphite in all of raw material of wood-charcoal, its
6 yuan of rings that chemical bond is formed for sp2 hydridization, and layered crystal structure, native graphite include defect and easily cause inserting for sulphuric acid
Layer and expansion, it is necessary to remove in advance, the present invention are sulphuric acid intercalation 800-1200 DEG C of desulfurization of high temperature using highly developed technique
Expanded graphite, expanded graphite worm can also be pressed into the graphite paper of porous, can buy similar expanded graphite powder and stone from market
Black paper；The non crystalline structure that activated carbon is mainly formed with sp3 hydridization, its conductivity is very low, but which is resistance to sulfuric acid very good,
Between graphite and activated carbon, this is due to its raw material to the property of coke --- coking coal includes substantial amounts of polycyclic aromatic hydrocarbon knot
Structure, in coking is locally easier to form mesophase and graphite microcrystal.Must be low as electrode its ash of lead-acid battery, with
Avoid the granularity of the negative effect to cell electrochemical reaction, its powder body from should be less than 30 mesh, be the good particularly pole of uniformity
Thin electrodes material its granularity should be less than 325 mesh, and the present invention is without limiting to its minimum particle size.Powdered carbon is in the formula of electrode material
Occupy less than more than 30% 98%, conductivity is too low very little, the too low acid resistance of high mechanical properties is poor, the scope being more suitable for is 70% He
Between 90%.
Binding agent in formula is used to bond structure of the various powdered carbons formation with mechanical strength and protect graphite not by sulfur
Sour swelling., compared with the binding agent for being suitable as powdered carbon and graphite paper, itself and solution viscosity are low easily and powdered carbon for thermosetting resin
Mixing and immersion graphite paper, thermoplastic plastic viscosity is high difficult with the mixing of other materials and is difficult to immerse graphite paper.It is more normal
The thermosetting resin seen has phenolic resin, polyester resin, epoxy resin, bimaleimide resin, polyimides etc., wooden
Element, Colophonium and pitch can also be added in resin to modified and reduces cost.Solvent is used for increasing manufacturability dissolving resin
With its viscosity of reduction, according to the different solvent combination of different Choice of Resin, arene and ketone and ethanol are common
Solvent, phenolic resin are adapted to use alcohol type solvent, and epoxy resin then suitable aromatic hydrocarbon and ketone and its mixed solvent, can be with
Adding some auxiliary agents increases manufacturability and other performance, and such as surfactant increases the wellability of liquid and pressed powder.Tree
Fat occupies less than more than 2% 70% in the formula of electrode material, and too high conductivity is too low, and the too low acid resistance of low mechanical strength is poor,
The scope being more suitable for is between 10% and 30%.To increase manufacturability and electric conductivity and reduces cost, present invention uses polynary
Epoxy-resin systems, phenolic aldehyde and lignin are firming agent, after the Colophonium rich in polynary benzene ring structure and pitch increase low-temperature carbonization
Electric conductivity and the acidproof protection to graphite.In the thermosetting resin, liquid epoxy ratio is from 30% to 90%, firming agent phenolic aldehyde
The summation 5% to 40% of resin 30% to 90%, resin type additive Colophonium, pitch and lignin, although solvent and other auxiliary agents plus
Enter in technical recipe, increase manufacturability, the performance of combination electrode can't be changed.
The graphite composite carbon electrode material of the present invention can be by 2 kinds of different process productions, and technique 1 is by various raw materials
Flakiness is suppressed after mixing and is heating and curing and carbonization；Technique 2 is that graphite is fabricated to flexible, porous graphite paper to be then immersed in gluing
Mixture heat drying solidification and carbonization；The low resistance and high intensity material of metal or carbon fiber can also be added in technique 1 and 2
Material.Graphite composite carbon electrode production technological process is shown in Fig. 1.
Technique 1：Formula is pressed first by resin and solvent and auxiliary agent dissolving mix homogeneously, is subsequently adding various powdered carbons high
Moment of torsion agitator mix homogeneously, weighs during required compound is put into mould and uniformly sprawls, not higher than 80 DEG C of baking temperature, low temperature
It is dried to most of solvent and volatilizees, matched moulds tool, hot-press solidifying is into carbon composite electrode plate.Thickness of slab 0.1 is to 10mm.Pressure 0.3 to 20
MPa, pressure is too low to be difficult to compacting and reaches desired density, the requirement of too high increase equipment, and the content more high pressure of powdered carbon is also more
It is high.The solidification temperature of common resin such as phenolic aldehyde, epoxy and polyester from 120 DEG C to 250 DEG C, 3 minutes hardening times to 2 hours,
The temperature higher time is shorter, and 200 DEG C of solidification temperature is needed 15 minutes or so.This technique can also increase product by automatization
Can, for example batch mixing powder is mated formation continuous drying compression elevated cure on the conveyor belt.To reduce current impedance, Copper Foil or copper cash with
And other metal materials can be embedded in solidification in compound.
Technique 2：The resin solution that porous graphite paper is immersed in high-pressure bottle, vacuum were forced into 3 to 20 after 1 to 10 minute
Air pressure 5 to 30 minutes, it is ensured that in resin solution immersion paper, be dried after then taking out removal surface resin, baking temperature is not higher than
, desired thickness is depressed into double rod milling trains, the solidification of high temperature press is shaped to battery lead plate, and thickness of slab is 0.1 to 10mm, its solidification by 80 DEG C
Condition from 120 DEG C to 250 DEG C, 3 minutes to 2 hours hardening time, 0.3 to 20 MPa of pressure.This technique may also be employed continuous work
Skill is produced, for example, solidified with the rolling of volume to volume Continuous Heat.To reduce current impedance, Copper Foil or copper cash and other metal materials can
To solidify in embedded double-layer graphite paper.
To increase acid resistance and conductivity, composite carbon electrode material can be with high in noble gases and vapor atmosphere
Warm carbonization, carbonization temperature from 300 to 1400 DEG C, 1 to 60 DEG C of programming rate/min, carbonization time 1 to 10 hour, the higher charcoal of temperature
The change time is shorter, and, to 10 MPas, the pressure of carbonization is more higher in high yield, and mechanical strength is higher, and negative pressure of vacuum is easy for pressure -0.1
Form open endoporus.Jing after high temperature carbonization, graphite composite carbon electrode is obtained, conductivity is more than 5x105S/m.Which is dense in volume
Change without thickness and mechanical strength after soaking 7 days at 50 DEG C in the sulphuric acid of degree 45%, dough-making powder external compression intensity is stretched in face and is surpassed
10 MPas are crossed, the demand of lead-acid battery electrode is met.
The carbon electrode of present invention production has low resistance, high mechanical properties, sulfuric acid corrosion resistant, lightweight and long-life etc.
Premium properties, substitutes part stereotype grid as the inner core of the electrode of lead-acid battery, makes battery be highly suitable for vehicle and cleaning
Energy energy storage.
Description of the drawings
Fig. 1 is graphite composite carbon electrode production technological process.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.It should be appreciated that this
Bright enforcement is not limited to the following examples, and any pro forma flexible and/or change made to the present invention will all fall
Enter the scope of the present invention.
In the present invention, if not refering in particular to, all of part, percentage ratio are unit of weight, the equipment for being adopted and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments, if no special instructions, is the normal of this area
Rule method.
The graphite powder adopted in embodiment or graphite paper, are sulphuric acid intercalation heating expansion process and are obtained, and swelling temperature is
800-1200 DEG C, the technique is common process, and non-invention emphasis to be studied, here do not do tired stating.
Embodiment 1：
50 grams of liquid epoxies and 50 grams of acetone are mixed, 20 grams of phenolic aldehyde is added, 15 grams of asphalt powders and 15 grams
Lignin stirring becomes homogeneous solution, adjusts viscosity with acetone obtained to the rear heating expansions with sulphuric acid intercalation of 100cP or so
The graphite powder of 900 gram of 325 mesh is mixed into wet-milling, and this wet-milling is mated formation in mould, about 1.8 kilogram/square metre of density of mating formation,
50 DEG C are dried 30min, in 220 DEG C of high temperature press interior-heat pressure 10min of preheating, 3 MPas of pressure.The thick carbon composites of 1mm are obtained,
The material rises to 500 DEG C of carbonization 2 hours in 1 MPa of vapor with 10 DEG C/min in autoclave, obtains the thick graphite of about 1mm multiple
Close carbon electrode.Jing is tested, the graphite composite carbon electrode in the sulphuric acid of volumetric concentration 45% at 50 DEG C after immersion 7 days without thickness
Change with mechanical strength, dough-making powder external compression intensity is stretched in face more than 10 MPas, the demand of lead-acid battery electrode is met.
Embodiment 2：
50 grams of liquid epoxies and 50 grams of acetone are mixed, 20 grams of phenolic aldehyde is added, 15 grams of asphalt powders and 15 grams
Lignin stirring becomes homogeneous solution, with the autoclave for pouring 500 milliliters after acetone regulation viscosity to 100cP or so into, incites somebody to action
In the solution that the graphite paper of 1.0 gram/cc of 1.3 millimeters thick of density is inserted in kettle, then vacuum 5min after lid is forced into 2
MPa keep 30min to take out, remove the solution on surface, 60 DEG C of dryings were depressed into 1 millimeter with pair rod milling trains after 2 hours, then high temperature
Press solidifies, and is shaped to sheet material, 220 DEG C of time 10min of press temperature, 3 MPas of pressure, the material in autoclave with 10 DEG C/
Min rises to 500 DEG C of carbonization 2 hours in 1 MPa of vapor, obtains about 1mm thickness composite graphite composite carbon electrodes.
Jing is tested, the graphite composite carbon electrode in the sulphuric acid of volumetric concentration 45% at 50 DEG C after immersion 7 days without thickness and
Mechanical strength changes, and stretches dough-making powder external compression intensity more than 10 MPas, meet the demand of lead-acid battery electrode in face.
Embodiment 3：
50 grams of liquid epoxies and 50 grams of acetone are mixed, 20 grams of phenolic aldehyde is added, 15 grams of asphalt powders and 15 grams
Lignin stirring becomes homogeneous solution, with the autoclave for pouring 500 milliliters after acetone regulation viscosity to 100cP or so into, incites somebody to action
In the solution that 1.0 gram/cc of 0.6 millimeters thick graphite paper of density is inserted in kettle, then vacuum 5min after lid is forced into 2,000,000
Handkerchief keeps 30min to take out, and removes the solution on surface, and 60 DEG C of dryings were depressed into 0.5 millimeter with pair rod milling trains after 2 hours, by 0.1 millimeter
Graphite paper of the thick Copper Foil with two panels slightly larger than Copper Foil same size is coated, and then the solidification of high temperature press, is shaped to graphite coat copper
The sandwich sheet material of paper tinsel, 220 DEG C of time 10min of press temperature, 3 MPas of pressure, the material is in autoclave with 10 DEG C/min liters
To 500 DEG C of carbonization 2 hours in 1 MPa of nitrogen, about 1mm thickness composite graphite composite carbon electrodes are obtained.
Jing is tested, the graphite composite carbon electrode in the sulphuric acid of volumetric concentration 45% at 50 DEG C after immersion 7 days without thickness and
Mechanical strength changes and embeds the corrosion of Copper Foil, stretches dough-making powder external compression intensity more than 10 MPas in face, meets plumbic acid electricity
The demand of pond electrode.
Embodiment described above is one kind preferably scheme of the present invention, not the present invention is made any pro forma
Limit, also have other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (6)
1. a kind of carbon electrode made by graphite composite carbon electrode material for lead-acid battery, it is characterised in that the carbon electrode
It is obtained by the following method：By carbon dust or graphite paper 30%-98%, the mass percentage of balance of binding agent, first by binding agent
Resin solution is obtained after mixing with organic solvent, resin solution obtains compound after mixing with carbon dust, after dry, hot-press solidifying
To solidification composite plate, or resin solution after first mixed binding agent with organic solvent, is obtained, resin solution immersion graphite paper is done
After dry, Jing after double-roll rolling mill compacting, hot-press solidifying obtains solidifying composite plate；The solidification composite plate for obtaining carbonization is obtained final product into carbon electricity again
Not higher than 80 DEG C of pole, wherein baking temperature, the temperature of hot pressing is 120 DEG C to 250 DEG C, and pressure is 0.3 to 20 MPa；Carburizing temperature
300 DEG C to 1400 DEG C, pressure -0.1 to 10 MPas, 1 to 60 DEG C of programming rate/min, atmosphere be vacuum, nitrogen or vapor or
The two gaseous mixture；Wherein, carbon dust main component is sulphuric acid expanded graphite powder and/or sulphuric acid expanded graphite worm, the binding agent
It is made up of thermosetting resin and resin type additive, wherein resin type additive accounts for the 5%-40% of binding agent gross weight, resin type
One or more combination of the additive in lignin, pitch and Colophonium, the thermosetting resin is by epoxy resin
Constitute with phenolic resin, the quality of epoxy resin accounts for 30%-90%.
2. carbon electrode, its feature made by the graphite composite carbon electrode material for lead-acid battery according to claim 1
It is：The binding agent is by 15% group of the epoxy resin 50% in terms of mass fraction, phenolic resin 20%, Colophonium 15% and lignin
Into.
3. carbon electrode, its feature made by the graphite composite carbon electrode material for lead-acid battery according to claim 1
It is：Described carbon dust or graphite paper are 800-1200 DEG C of expanded graphite powder of sulphuric acid intercalation high temperature or graphite paper.
4. carbon electrode, its feature made by the graphite composite carbon electrode material for lead-acid battery according to claim 1
It is：The thickness of carbon electrode is 0.1 millimeter to 10 millimeters.
5. carbon electrode, its feature made by the graphite composite carbon electrode material for lead-acid battery according to claim 1
It is：The Copper Foil or copper cash for accounting for compound cumulative volume 5 to 40% is embedded in compound, then carries out hot-press solidifying.
6. carbon electrode, its feature made by the graphite composite carbon electrode material for lead-acid battery according to claim 1
It is：In the composite graphite paper that resin solution immersion graphite paper is obtained, the embedded Copper Foil for accounting for composite graphite paper cumulative volume 5 to 40%
Or hot-press solidifying is carried out again after copper cash formation Copper Foil or copper cash graphite paper sandwich structure.
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| CN108123137B (en) * | 2016-11-26 | 2020-06-26 | 中国科学院大连化学物理研究所 | Partially graphitized activated carbon-based composite additive, preparation method thereof, negative electrode and application thereof |
| CN109705695A (en) * | 2017-10-26 | 2019-05-03 | 深圳光启高等理工研究院 | Wave penetrating paint and preparation method thereof |
| CN108063265B (en) * | 2017-12-06 | 2021-04-06 | 莱尔(深圳)新能源有限公司 | Preparation method of air electrode |
| CN108520950A (en) * | 2018-04-13 | 2018-09-11 | 刘文会 | A kind of production method of electrode new material for electric vehicle |
| CN111261840B (en) * | 2018-11-30 | 2021-02-26 | 中国科学院大连化学物理研究所 | Integrated lead-carbon battery carbon electrode and preparation and application thereof |
| CN111261841B (en) * | 2018-11-30 | 2021-01-05 | 中国科学院大连化学物理研究所 | Lead-carbon battery electrode and preparation and application thereof |
| CN111082048B (en) * | 2019-12-16 | 2021-02-05 | 浙江绿源电动车有限公司 | Graphene lead-carbon battery positive plate lead paste and method for preparing battery by adopting same |
| CN111082049B (en) * | 2019-12-16 | 2021-02-05 | 浙江绿源电动车有限公司 | Graphene lead-carbon battery cathode lead paste plate and preparation method thereof |
| CN114927651B (en) * | 2022-02-15 | 2024-04-26 | 浙江铅锂智行科技有限公司 | Preparation method and preparation system of lead-acid storage battery electrode |
| SE545992C2 (en) * | 2022-08-17 | 2024-04-09 | Stora Enso Oyj | A method for producing a carbon material from lignin and a negative electrode comprising the carbon material |
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