CN107403917A - A kind of preparation of asphalt grout and the method that graphite cathode is prepared using the slurry - Google Patents

A kind of preparation of asphalt grout and the method that graphite cathode is prepared using the slurry Download PDF

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Publication number
CN107403917A
CN107403917A CN201710610042.0A CN201710610042A CN107403917A CN 107403917 A CN107403917 A CN 107403917A CN 201710610042 A CN201710610042 A CN 201710610042A CN 107403917 A CN107403917 A CN 107403917A
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China
Prior art keywords
asphalt
graphite
grout
solvent
asphalt grout
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Inventor
王四清
周飞
周亮良
孟庆伟
李方塘
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Zhongnan Diamond Co Ltd
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Zhongnan Diamond Co Ltd
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Priority to CN201710610042.0A priority Critical patent/CN107403917A/en
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The method that graphite cathode is prepared the invention discloses a kind of preparation of asphalt grout and using the slurry, asphalt grout is prepared with asphalt powder and solvent mixing and ball milling, and with the slurry vacuum impregnation constant temperature agitating and heating distill method coated graphite, then carbonize and graphitization be made composite.The preparation of asphalt grout provided by the invention and the method that graphite cathode material is prepared using the slurry, improve liquid phase coating method, simultaneously under the double action for heating and stirring, strengthen dissolving and the penetrating power of solvent, make graphite coat evenly, completely, obtained the graphite cathode material of excellent performance.

Description

A kind of preparation of asphalt grout and the method that graphite cathode is prepared using the slurry
Technical field
The present invention relates to lithium cell cathode material field, specifically, more particularly to the preparation and use of a kind of asphalt grout The method that the slurry prepares graphite cathode.
Background technology
Lithium ion battery is a kind of battery of environment-friendly and green, have compared with conventional batteries energy density is high, discharge voltage is high, The more advantage such as in light weight, its market are being grown at top speed always.Lithium cell cathode material mainly uses graphite cathode material at present Material, is divided into native graphite and petroleum coke Delanium again.Graphite is as negative material, powdered graphite extra-granular surface and inside Crystal structure differ greatly, with electrolyte reaction inhomogeneities difference it is larger, in charging process, solvation easily occurs Lithium ion is embedded in altogether, causes the expansion and avalanche of graphite linings, due to consuming more electrolyte, adds irreversible capacity, So as to have impact on cycle life.
Based on above reason, people are done a lot of work to graphite modified aspect, and to ensure to improve specific capacity, head is imitated and followed Ring performance.Common modification method has：Oxidation, cladding, plated film, doping.Wherein cladding process is most obvious in effect, in production more Have operability, thus it is most extensive in industrial applications.
The research of amorphous carbon, example, many using having is coated on carbon or powdered graphite surface, before amorphous carbon Driving body also has many kinds, and the covering material used includes the resinous material such as phenolic resin, polypropylene, and asphalt, coal The pitch class material such as tar asphalt.The wherein cladding of pitch class material, not only one layer of amorphous carbon in Surface coating, can also show The specific surface area of the reduction graphite of work, reduces the irreversible capacity in discharge process first, improves first effect.Research at present is most More, industrial applications are most ripe.
The method of pitch-coating carbon or powdered graphite substantially has three kinds, i.e. solid phase cladding, liquid phase coating and vapour deposition.Gu Mutually cladding is to be mixed using asphalt powder with carbon or powdered graphite, and completion cladding is stirred under normal temperature or heating condition, is adopted Production method is simple when being coated with solid phase, but the integrality of mixing uniformity and asphalt powder cladding is all difficult to protect in production process Card, therefore the quality of production is unstable；Gas phase cladding be using alkane, hydrocarbon gas at high temperature (700~1400 DEG C) decompose carbon and It is deposited on what the mode on carbon or powdered graphite surface was carried out, the condition of vapour deposition is harsher, and production cost is high, at present also It is not carried out industrialized production；Liquid phase mixing cladding, existing method will generally heat molten asphalt in 150~300 DEG C and carbon Or powdered graphite carries out kneading cladding, this mode covered effect is also bad, and mainly molten asphalt is difficult in kneading process Accomplish dispersed, reach uniform carbon coated or the purpose of powdered graphite particle surface.Also have and mix pitch with organic, infiltrate Evaporation solvent afterwards, then charing black lead, this mode covered effect is also bad, reason be in pitch each component nature difference compared with Greatly, it is difficult to preferably dissolve and disperse in a certain specific solvent, preferable leaching is also unable to reach under strong stirring Profit and covered effect, if amorphous carbon contains after asphalt content is increased in the case that bitumen solubility is inadequate and can cause charing again Measure the too high situation for causing material capacity relatively low.
The content of the invention
The purpose of the present invention is to improve liquid phase coating method, graphite coat is obtained evenly, completely, there is provided a kind of bituminous grout The preparation of material and the method that graphite cathode is prepared using the slurry.
To achieve these goals, technical scheme provided by the invention is：
A kind of preparation method of asphalt grout, comprises the following steps：
1) sheet or massive asphalt are taken, is roughly ground, crosses 80~150 mesh sieves；
2) by the asphalt powder after sieving and solvent by weight 1:9~9:1 mixing, stir, the solvent be benzene, Any of toluene, dimethylbenzene, ethylbenzene, petroleum ether, quinoline, acetone, chloroform, carbon tetrachloride, tetrahydrofuran, or any two Kind or two or more mixtures；
2) mixture to stir is transferred in sand mill, the abrading-ball for adding a diameter of 1mm carries out ball milling, asphalt powder End is 1 with mill ball quality ratio:1~1:3；
3) after ball milling 2h, the homogenizer for being more than 3000r/min with rotating speed disperses more than 20min, obtains asphalt grout.
In the preparation method of above-mentioned asphalt grout, it is preferred that in the step 1), pitch is higher than 80 DEG C using softening point The accessory substance of oil or coal, or the mid temperature pitch or modified coal tar pitch of said two devices, or the mixture of above-mentioned pitch.
Present invention also offers one kind graphite cathode is prepared using asphalt grout made from above-mentioned asphalt grout preparation method The method of material, comprises the following steps：
1) take asphalt grout made from a kind of preparation method of asphalt grout according to claim 1, under normal temperature with ball Carbon after change or powdered graphite mixing, and continue solubilization dilution agent, infiltrate 30min~60min under negative pressure of vacuum, pressure for- 0.1MP to -0.05MP；
2) stop after vacuumizing, start to be heated to mixture 50~250 DEG C, maintain 0.5~10h, and constant temperature stirs Mixing makes pitch all dissolve, and is coated on carbon or powdered graphite surface by solvent penetration, and be filled in particle voids；
3) continue to heat up, temperature was increased to 100~250 DEG C in 30 minutes, mixture is being mixed slowly and continuing to heat During solvent is distilled off, speed of agitator gradually reduces, after mixture is into pasty state stop stirring, solvent evaporated, distillation Solvent condensation recovery is in case recycle；After the completion of distillation, dry composite is obtained；
4) composite obtained after the completion of distillation is carbonized, or first graphitization after charing, that is, obtain graphite covered by asphalt Lithium cell cathode material.
In the above-mentioned method that graphite cathode material is prepared using asphalt grout, it is preferred that in the step 1), asphalt grout Asphalt grout and the mass ratio of carbon or powdered graphite are 1 when being mixed with carbon or powdered graphite:1~1:9.
In the above-mentioned method that graphite cathode material is prepared using asphalt grout, it is preferred that in the step 2), mixture adds The mode of heat heating is chuck electrical heating or oil heating, and programming rate is 0.5~10 DEG C/min.
In the above-mentioned method that graphite cathode material is prepared using asphalt grout, it is preferred that in the step 4), if before cladding Powdered graphite is used, then constant temperature handles 2h at about 1100 DEG C by the composite obtained after distillation, and is passed through nitrogen guarantor Shield makes its charing, is then reunited and breaks up, sieves, except magnetic, that is, obtains coated graphite negative material；If used before cladding Carbon dust, then by the composite obtained after distillation at about 1100 DEG C constant temperature handle 2h, and be passed through nitrogen protection make its charing, Graphitization processing then is carried out at 2600~3000 DEG C, that is, obtains coated graphite negative material.
A kind of preparation of asphalt grout provided by the invention and the method that graphite cathode is prepared using the slurry, improve liquid Phase method for coating, while under the double action for heating and stirring, strengthen dissolving and the penetrating power of solvent, make graphite coat Evenly, completely, and then the graphite cathode material of excellent performance is obtained.The preparation of the asphalt grout and prepare stone using the slurry In the method for black negative pole, multiple utilization, burning residual dregs processing, no noxious emission can be recovered by distillation in used solvent；Should Method is full and uniform real to carbon or powdered graphite surface using the dissolving and infiltration while heating and softening pitch using solvent Now coat, fine and close, the firm amorphous carbon layer formed after charing on powder surface, material is good with compatibility of electrolyte, can not Inverse capacity is low, and first charge-discharge coulombic efficiency is high, good cycling stability, has extended cycle life.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely illustrative and explained the present invention, is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to accurately scope or the value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.
In the present invention, described carbon dust be by Raw material processing of artificial stone oil coke or needle coke into non-graphitization processing Powder；Powdered graphite is to carry out the powder that special graphitization processing is process with above-mentioned carbon dust, or with native graphite or The powder of (whether carrying out graphitization processing again) or the mixing of above-mentioned powder-processed prepared by natural micro crystal graphite Thing.Vacuumize process is carried out in mixing apparatus, is to allow solvent and slurry preferably to penetrate into graphite top layer space, vacuum Degree control is in -0.1MP to -0.05MP.
Embodiment 1
1) asphalt that softening point is 80 DEG C is crushed, crosses 100 mesh sieves, take the lower asphalt powder of sieve standby；In a reservoir plus 24L benzene, 6kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 3 μm, grinding terminates, and will grinding Slurry afterwards is handled 15 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout of gained in step 2), mixed in a reservoir with 115kg nodularizations natural flake graphite, nodularization day Right crystalline flake graphite D50 is 14.5 μm, tap density 0.90g/cm3, specific surface area 5.3m2/ g, and 50L acetone solvents are added, while stirring Mix side to vacuumize, vacuum is -0.1MP, continues 30min, afterwards begins to warm up mixture, 30min temperature is raised to from normal temperature 57 DEG C, maintain 4h, lasting stirring cladding.30min then is used, temperature is uniformly raised to 110 DEG C from 57 DEG C at a slow speed, maintains this temperature 3h, it is evaporated under reduced pressure, reclaims the solvent of distillation, dry composite is obtained after the completion of distillation.
4) by above-mentioned composite at 1100 DEG C, constant temperature processing 2h, nitrogen protection is lower to be carbonized, graphite at 2600-3000 DEG C Change handle (or without graphitization processing), by the material disintegrating, screening, except magnetic be obtain coated graphite negative material.
Embodiment 2
1) asphalt that softening point is 120 DEG C is crushed, crosses 120 mesh sieves, take the lower asphalt powder of sieve standby；In a reservoir plus 36L toluene, 7kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 4 μm, grinding terminates, and will grinding Slurry afterwards is handled 20 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout obtained by step 2), mixed in a reservoir with the natural micro crystal graphite of 50kg nodularizations, nodularization is natural Micro crystal graphite D50 is 16.0m, tap density 0.95g/cm3, specific surface area 5.8m2/ g, and 60L chloroform solvents are added, side stirring While vacuumizing, vacuum -0.09MP, continue 40min, mixture is begun to warm up afterwards, 40min temperature is raised to 61 from normal temperature DEG C, maintain 4.5h, lasting stirring cladding.40min is used afterwards, and temperature is uniformly raised to 120 DEG C from 61 DEG C at a slow speed, maintains this temperature 4h, it is evaporated under reduced pressure, reclaims the solvent of distillation, dry composite is obtained after the completion of distillation.
4) by above-mentioned composite at 1080 degree, constant temperature processing 3h, nitrogen protection is lower to be carbonized, graphite at 2600-3000 DEG C Change handle (or without graphitization processing), by the material disintegrating, screening, except magnetic be obtain coated graphite negative material.
Embodiment 3
1) asphalt that softening point is 200 DEG C is crushed, crosses 150 mesh sieves, take the lower asphalt powder of sieve standby；In a reservoir plus 48L dimethylbenzene, 8kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 4.5 μm, grinding terminates, and will grind Slurry after mill is handled 25 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout obtained by step 2), mixed in a reservoir with 32kg artificial petroleum coke powders end, artificial stone oil coke Powder D50 is 14.2 μm, jolt ramming 0.82g/cm3, specific surface area 6.6m2/ g, and 70L carbon tetrachloride is added, take out while stirring true Sky, vacuum are -0.08MP, continue 10min, mixture is begun to warm up afterwards, and 5min temperature is raised to 77 DEG C from normal temperature, are maintained 5h, lasting stirring cladding.70min is used afterwards, temperature is uniformly raised to 130 DEG C from 77 DEG C at a slow speed, maintains this temperature 3.5h, normal pressure Distillation, reclaims the solvent of distillation, dry composite is obtained after the completion of distillation.
4) by above-mentioned composite at 1200 DEG C, constant temperature 2.5h, nitrogen protection is lower to be carbonized, afterwards stone at 2600-3000 DEG C Blackization processing, by the material disintegrating, screening, except magnetic be obtain coated graphite negative material.
Embodiment 4
1) asphalt that softening point is 250 DEG C is crushed, crosses 80 mesh sieves, take the lower asphalt powder of sieve standby.In a reservoir plus 18ml quinoline, 5kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 3.5 μm, grinding terminates, and will grind Slurry after mill is handled 10 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout of gained in step 2), mixed in a reservoir with 12kg needle coke powders, needle coke powder D50 For 18.0 μm, jolt ramming 0.81g/cm3, specific surface area 4.0m2/ g, and 70L petroleum ether solvents are added, vacuumize while stirring, vacuum Degree -0.09MP, continue 120min, mixture is begun to warm up afterwards, 90min clocks temperature is raised to 90 DEG C from normal temperature, maintains 8h, holds Continuous stirring cladding.8min is used afterwards, temperature is uniformly raised to 160 DEG C from 90 DEG C at a slow speed, maintains this temperature 4h, is evaporated under reduced pressure, and is returned The solvent of distillation is received, dry composite is obtained after the completion of distillation.
4) by above-mentioned composite at 1000 DEG C, constant temperature 6h, nitrogen protection is lower to be carbonized, at 2600-3000 DEG C at graphitization Reason, by the material disintegrating, screening, except magnetic be obtain coated graphite negative material.
Embodiment 5
1) asphalt that softening point is 120 DEG C is crushed, crosses 120 mesh sieves, take the lower asphalt powder of sieve standby；In a reservoir plus 36L toluene, 7kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 4 μm, grinding terminates, and will grinding Slurry afterwards is handled 20 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout of gained in step 2), mixed in a reservoir with 10.5kg nodularizations natural flake graphite, nodularization Natural flake graphite D50 is 20.0 μm, jolt ramming 0.92g/cm3, specific surface area 5.7m2/ g, and add 30L toluene ether solvents, normal pressure 10min is stirred, mixture is begun to warm up afterwards, 90min clocks temperature is raised to 100 DEG C from normal temperature, maintains 8h, lasting stirring bag Cover.8min is used afterwards, temperature is uniformly raised to 155 DEG C from 90 DEG C at a slow speed, maintains this temperature 4h, is evaporated under reduced pressure, is reclaimed distillation Solvent, dry composite is obtained after the completion of distillation.
4) by above-mentioned composite at 1130 DEG C, constant temperature processing 4h, nitrogen protection is lower to be carbonized, by the material disintegrating, screening, Except magnetic obtains coated graphite negative material.
Embodiment 6
1) asphalt that softening point is 200 DEG C is crushed, crosses 150 mesh sieves, take the lower asphalt powder of sieve standby；In a reservoir plus 48L dimethylbenzene, 8kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 4.5 μm, grinding terminates, and will grind Slurry after mill is handled 25 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout obtained by step 2), mixed in a reservoir with the natural micro crystal graphite of 8kg nodularizations, nodularization is naturally micro- Brilliant burnt graphite D50 is 25.0 μm, jolt ramming 0.75g/cm3, specific surface area 6.6m2/ g, and 80L xylene solvents are added, while stirring Vacuumizing, vacuum -0.05MP, continue 2h, mixture is begun to warm up afterwards, 30min clocks temperature is raised to 140 DEG C from normal temperature, Maintain 1h, lasting stirring cladding.25min is used afterwards, temperature is uniformly raised to 200 DEG C from 140 DEG C at a slow speed, maintains this temperature 5h, It is evaporated under reduced pressure, reclaims the solvent of distillation, dry composite is obtained after the completion of distillation.
4) by above-mentioned composite at 1180 DEG C, constant temperature 5.5h, nitrogen protection is lower to be carbonized, graphitization at 2600~3000 DEG C Handle (or without graphitization processing), by the material disintegrating, screening, except magnetic be obtain coated graphite negative material.
Embodiment 7
1) asphalt that softening point is 250 DEG C is crushed, crosses 80 mesh sieves, take the lower asphalt powder of sieve standby.In a reservoir plus 18ml quinoline, 5kg asphalt powders are then added, stirs, is configured to suspension at normal temperatures.
2) suspension is added in sand mill and ground, be ground to pitch granularity D50 as 3.5 μm, grinding terminates, and will grind Slurry after mill is handled 10 minutes with homogenizer, obtains asphalt grout.
3) by the asphalt grout of gained in step 2), mixed in a reservoir with 3.5kg needle coke powders, needle coke powder D50 is 17.0 μm, jolt ramming 0.84g/cm3, specific surface area 4.5m2/ g, and 40L diesel oil is added, vacuumize while stirring, vacuum- 0.1MP, continue 150min, mixture is begun to warm up afterwards, 40min clock temperature normal temperature is raised to 185 DEG C, maintains 2h, persistently stirs Mix cladding.20min is used afterwards, temperature is uniformly raised to 220 DEG C from 185 DEG C at a slow speed, maintains this temperature 3h, is evaporated under reduced pressure, recovery The solvent of distillation, dry composite is obtained after the completion of distillation.
(2) by above-mentioned composite at 1100 DEG C, constant temperature 3h, nitrogen protection is lower to be carbonized, at 2600-3000 DEG C at graphitization Reason, by the material disintegrating, screening, except magnetic be obtain coated graphite negative material.
In embodiment 1~7, it is related to the test of physical property, its measuring instrument is as follows：1), granularity uses Britain Malvern The MS2000 laser particle analyzers analysis of Instrument Ltd.'s production is measured；2), specific surface area uses the neat center analysis instrument of northern open score Device is measured with automation research institute ST-08A than Surface Tester；3), tap density uses the limited public affairs of the grand instrument and equipment of Shenzhen group The HY-100 tap density meters of department's production measure.In addition, it is necessary to explanation is：
1) mixing apparatus can vacuumize, and it is to allow solvent and slurry preferably to penetrate into graphite top layer sky to vacuumize Gap, vacuum should be in -0.1MP to -0.05MP；
2) mixing apparatus band form and illuminating lamp, observable internal mix situation, observe speed of agitator and stirring state；
3) mixing apparatus has colter type agitating paddle, 10~1000r/min of rotating speed, material can be made fully to exchange；
4) mixing apparatus is furnished with chuck heating function, 20~300 DEG C of heating temperature range, temperature error ± 1 DEG C, accurately may be used Adjust；
5) mixing apparatus, band are distilled to recover system, and recycling design is in case recycle；
6) it is graphite or ceramic crucible to carbonize boat or saggar, and boat loading depth is 5~200mm；
7) 1100 DEG C of carbonization process constant temperature, ± 100 DEG C, carbonization process leads to nitrogen protection, nitrogen gas purity more than 99.9%.
Graphite cathode material made from embodiment 1~7 is subjected to electrochemical property test, addition binding agent, thickening respectively Agent and solvent, are stirred slurrying, coated on copper foil, dry, roll-in film-making.Binding agent used can be dissolved in N- methyl pyrroles Kynoar (PVDF), the water miscible butadiene-styrene rubber of pyrrolidone are newborn (SBR), and carboxylic is added if using water-soluble binder Sodium carboxymethylcellulose pyce (CMC) makees thickener.Positive electrode used can be cobalt acid lithium, LiFePO4 or ternary material etc..It is used Electrolyte is LiPF6 (EC+EMC+DMC), and metal lithium sheet is that barrier film is using polyethylene (PE), polypropylene (PP), or two to electrode The bilayer or three layers of composite diaphragm, simulated battery of person assembles in the inert atmosphere glove box for fill high-purity argon gas, chemical property Being carried out in the new Weir BTS high accuracy batteries detecting system CT-3008-5V3A test cabinets in Shenzhen, discharge and recharge scope is 0-2.0V, Charge-discharge magnification 0.5C, test result are as shown in table 1.
The preparation of asphalt grout provided by the invention and the method that graphite cathode material is prepared using the slurry, improve liquid Phase method for coating, while under the double action for heating and stirring, strengthen dissolving and the penetrating power of solvent, make graphite coat Evenly, completely, the graphite cathode material of excellent performance has been obtained.
The performance test data of the asphalt grout coated graphite negative material of table 1
The preparation of the asphalt grout and prepared using the slurry in the method for graphite cathode, used solvent can pass through steaming Evaporate recovery repeatedly to utilize, burning residual dregs processing, no noxious emission；This method utilizes solvent using while heating and softening pitch Dissolving and infiltration, full and uniform that cladding is realized to carbon or powdered graphite surface, densification, heavily fortified point after charing in the formation of powder surface Solid amorphous carbon layer, material is good with compatibility of electrolyte, and irreversible capacity is low, and first charge-discharge coulombic efficiency is high, and circulation is steady It is qualitative good, have extended cycle life.

Claims (6)

1. a kind of preparation method of asphalt grout, comprises the following steps：
1) sheet or massive asphalt are taken, is roughly ground, crosses 80 ~ 150 mesh sieves；
2）By the asphalt powder after sieving and solvent by weight 1:9~9:1 mixing, stir, the solvent be benzene, toluene, Any of dimethylbenzene, ethylbenzene, petroleum ether, quinoline, acetone, chloroform, carbon tetrachloride, tetrahydrofuran, or any two kinds or two The mixture of the kind above；
2）The mixture to stir is transferred in sand mill, add a diameter of 1mm abrading-ball carry out ball milling, asphalt powder with Mill ball quality ratio is 1:1~1:3；
3）After ball milling 2h, the homogenizer for being more than 3000r/min with rotating speed disperses more than 20min, obtains asphalt grout.
A kind of 2. preparation method of asphalt grout according to claim 1, it is characterised in that：The step 1）In, pitch is adopted It is higher than 80 DEG C of oil or the accessory substance of coal, or the mid temperature pitch or modified coal tar pitch of said two devices with softening point, or it is above-mentioned The mixture of pitch.
3. asphalt grout made from a kind of preparation method using asphalt grout described in claim 1 prepares the side of graphite cathode Method, its feature comprise the following steps：
1）Take asphalt grout made from a kind of preparation method of asphalt grout according to claim 1, under normal temperature with after nodularization Carbon or powdered graphite mixing, and continue solubilization dilution agent, infiltrate 30min ~ 60min under negative pressure of vacuum, pressure be -0.1MP to - 0.05MP；
2）After stopping vacuumizes, start to be heated to mixture 50 ~ 250 DEG C, maintain 0.5 ~ 10h, and constant temperature stirring makes drip Blue or green all dissolvings, are coated on carbon or powdered graphite surface, and be filled in particle voids by solvent penetration；
3）Continue to heat up, temperature was increased to 100~250 DEG C in 30 minutes, mixture is being mixed slowly and continuing heating process In solvent is distilled off, speed of agitator gradually reduces, after mixture is into pasty state stop stirring, solvent evaporated, the solvent of distillation Condensation recovery is in case recycle；After the completion of distillation, dry composite is obtained；
4）The composite obtained after the completion of distillation is carbonized, or graphitization after first carbonizing, that is, obtain the lithium of graphite covered by asphalt Cell negative electrode material.
A kind of 4. method that graphite cathode is prepared using asphalt grout according to claim 3, it is characterised in that：The step Rapid 1）In, asphalt grout and the mass ratio of carbon or powdered graphite are 1 when asphalt grout mixes with carbon or powdered graphite:1~1:9.
A kind of 5. method that graphite cathode is prepared using asphalt grout according to claim 3, it is characterised in that：The step Rapid 2）In, the mode of mixture heat temperature raising is chuck electrical heating or oil heating, and programming rate is 0.5 ~ 10 DEG C/min.
A kind of 6. method that graphite cathode is prepared using asphalt grout according to claim 3, it is characterised in that：The step Rapid 4）In, if using powdered graphite before cladding, by the composite obtained after distillation, constant temperature is handled at about 1100 DEG C 2h, and be passed through nitrogen protection make its charing, then reunited and break up, sieve, except magnetic, that is, obtain coated graphite negative material； If using carbon dust before cladding, by the composite obtained after distillation, constant temperature handles 2h at about 1100 DEG C, and is passed through Nitrogen protection makes its charing, then carries out graphitization processing at 2600 ~ 3000 DEG C, that is, obtains coated graphite negative material.
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CN109378472A (en) * 2018-09-30 2019-02-22 上海科比斯实业有限公司 A kind of low specific surface area carbon material and preparation method thereof
CN109599546A (en) * 2018-12-05 2019-04-09 中南大学 Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same
CN109599546B (en) * 2018-12-05 2020-12-04 中南大学 Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same
CN110828798A (en) * 2019-10-31 2020-02-21 方大炭素新材料科技股份有限公司 Method for preparing lithium ion battery graphite negative electrode material by wet pressurizing coating
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CN112531168A (en) * 2020-12-03 2021-03-19 中国科学院山西煤炭化学研究所 Method for preparing lithium ion battery cathode material by liquid phase coating modification
CN112531168B (en) * 2020-12-03 2021-09-03 中国科学院山西煤炭化学研究所 Method for preparing lithium ion battery cathode material by liquid phase coating modification
CN115036481A (en) * 2022-06-21 2022-09-09 焦作熔创石墨科技有限公司 Shaping method and system of carbon negative electrode material

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