CN108054357A - Power lithium-ion battery coal base composite negative pole material and preparation method thereof - Google Patents

Power lithium-ion battery coal base composite negative pole material and preparation method thereof Download PDF

Info

Publication number
CN108054357A
CN108054357A CN201711280108.0A CN201711280108A CN108054357A CN 108054357 A CN108054357 A CN 108054357A CN 201711280108 A CN201711280108 A CN 201711280108A CN 108054357 A CN108054357 A CN 108054357A
Authority
CN
China
Prior art keywords
coal base
ion battery
negative pole
power lithium
pole material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201711280108.0A
Other languages
Chinese (zh)
Inventor
王兴蔚
王北平
侯佼
马少宁
侯春平
龚波林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningxia Boulter Technology Co Ltd
Original Assignee
Ningxia Boulter Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningxia Boulter Technology Co Ltd filed Critical Ningxia Boulter Technology Co Ltd
Priority to CN201711280108.0A priority Critical patent/CN108054357A/en
Publication of CN108054357A publication Critical patent/CN108054357A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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 invention discloses a kind of power lithium-ion battery coal base composite negative pole material and preparation method thereof, technical problems to be solved are to reduce production cost, and environmental protection is suitble to large-scale industrialized production.The power lithium-ion battery coal base composite negative pole material of the present invention, for the graphitization anthracite for being 75~90% using degree of graphitization as matrix, matrix is coated with mesoporous carbon, and mesoporous carbon coating layer quality is the 2.0~7.5% of substrate quality.The power lithium-ion battery preparation method of coal base composite negative pole material of the present invention, comprises the following steps：It crushes, dispensing mixing, green compact, high temperature graphitization, cladding cures, pyrolysis.Compared with prior art, the present invention power lithium-ion battery has high power capacity, high-rate charge-discharge capability with coal base composite negative pole material, long circulation life, environmentally friendly, preparation method is simple, easy control of process conditions, and production cost is low, is suitble to large-scale industrialized production.

Description

Power lithium-ion battery coal base composite negative pole material and preparation method thereof
Technical field
The present invention relates to a kind of new energy materials, particularly a kind of lithium ion battery cathode material and its preparation side Method.
Background technology
The lithium ion battery of commercialization at present is mainly using graphite-like carbon material as negative electrode active material, including natural stone Ink and two major class of Delanium.Native graphite is used as the negative material of lithium ion battery, has specific discharge capacity height, processing performance The advantages of good, but its high temperature performance is bad, at the same with the poor compatibility of organic electrolyte, graphite flake layer easily occurs for whens charge and discharge It removes, influences high rate during charging-discharging and cycle life.The prior art is using spheroidization processing, surface low-level oxidation, surface bag It covers, the modified method of surface organic and element doping, although the surface texture of native graphite can be improved to a certain extent And chemical property, corrosion of the electrolyte to graphite synusia is reduced, effectively improves natural graphite negative electrode material first charge-discharge efficiency And cycle life, but to its rate charge-discharge performance, the improvement of high temperature performance is limited, this so that the more difficult satisfaction of native graphite is dynamic Power lithium ion battery is to the requirement of high power and high safety performance.
Compared to native graphite, mainly using petroleum coke, needle coke as raw material, pitch combines artificial plumbago negative pole material Agent, through calcining, dispensing, kneading, die mould, roasting, graphitization, machining and be made, although artificial plumbago negative pole material discharge ratio Capacity is compared relatively low, but since it is with good cyclical stability, excellent high temperature performance, good security performance, is The negative material that current driving force lithium ion battery is most widely used in the market.But the artificial plumbago negative pole material system of the prior art Standby system, the prices of raw materials are high, and technological process is complicated, makes production cost higher, meanwhile, with power lithium ion battery To high-energy density, high-power growth requirement, force artificial plumbago negative pole material that need to be put by constantly modified further improve Capacitance and high-rate charge-discharge capability, reduce cost.
For anthracite as good carbon materials, main component is carbon, and wherein aromatic hydrocarbons structure or aromatic hydrocarbon molecule occupy larger Ratio, and these aromatic hydrocarbons structures or aromatic hydrocarbon molecule can also be converted into graphite material under suitable condition, be that one kind is more managed That thinks prepares the raw material of Delanium.Since graphitization anthracite is similar to natural micro crystal graphite growth mechanism, the two tool There is similar microstructure, graphite crystal is small, and isotropic structure causes with the negative material of its preparation in cycle life, fast There is extremely excellent performance, while raw material sources are extensive and cheap ensure ion cathode material lithium in terms of fast charge and discharge With relatively low production cost.In addition, anthracite Coke density be higher than bituminous coal coke, while have both graphitized carbon with it is non-graphitized It shows hard carbon behavior when the performance advantage of carbon, treatment temperature are less than 2000 DEG C, and higher than 2500 DEG C when shows soft carbon row For that can realize the control to graphitization anthracite degree of graphitization and structure by optimization design high temperature graphitization technique, so as to get Material maintain larger graphite linings pitch structure and hard carbon performance, can not only greatly improve the embedding of ion cathode material lithium Lithium space increases electrode reversible specific capacity, additionally it is possible to expand diffusion admittance of the lithium ion in graphite linings, improve lithium-ion negative pole High-rate charge-discharge capability, cyclical stability and the low temperature electrochemical performance of material.Therefore using anthracite as the high property of base material Can ion cathode material lithium research and development, can be expected to solve power lithium-ion battery in energy density, charge-discharge velocity, be produced into The bottleneck problem of present aspect.
The prior art is mainly combined on the research using anthracite as the lithium ion battery negative material of base material by purifying It is prepared by high temperature modified mode.A kind of spherical porous artificial plumbago negative pole is disclosed in China Patent Publication No. 106099105A After anthracite ball milling, removal of impurities, scattered, cladding, high-temperature heat treatment, the porous ball of purity more than 99.9% is prepared in material Shape artificial plumbago negative pole material although material 0.5C reversible capacities can reach 390mAh/g, uses pickling in dedoping step Purifying easily pollutes the environment, and is unfavorable for industrialization.A kind of coal base is disclosed in China Patent Publication No. 104681786A to bear Pole material, preparation method and lithium ion battery, the purifying of coal sill are deposited using purification gas reaction is passed through in graphitizing process It is perishable and purify non-uniform problem in equipment, while the preparation-obtained material reversible capacity of this method is in 350mAh/g Left and right, it is difficult to meet high demand of the power lithium-ion battery to energy density.
The content of the invention
It, the object of the present invention is to provide a kind of power lithium-ion battery coal base composite negative pole material and preparation method thereof The technical issues of solution is to reduce production cost, and environmental protection is suitble to large-scale industrialized production.
The present invention uses following technical scheme：A kind of power lithium-ion battery coal base composite negative pole material, with graphitization The graphitization anthracite spent for 75~90% is matrix, and matrix is coated with mesoporous carbon, and mesoporous carbon coating layer quality is matrix matter The 2.0~7.5% of amount；Mesoporous carbon is using phenolic resin as carbon precursor, and the both sexes three block of ethyoxyl and propoxyl group composition is total to Polymers is pore-forming additive, is formed through high temperature pyrolysis solvent evaporation induced self-assembly.
The power lithium-ion battery coal base composite negative pole material average grain diameter D50 of the present invention is 17.0~22.0 μm, than Surface area is 5.78~7.24m2/g。
The aperture of the mesoporous carbon nano-pore of the present invention is in below 50nm.
The anthracite of the present invention uses Ningxia Tai Xi coals.
A kind of power lithium-ion battery preparation method of coal base composite negative pole material, comprises the following steps：
First, crush
At room temperature, quality phosphorus content is more than to 97% anthracite, is crushed, until average grain diameter D50 is 2.0~8.0 μm, obtain anthracite micro mist；
2nd, dispensing mixes
By anthracite micro mist, can carbonisable binder and light metal halogen in mass ratio 100：2.0~20.0：1.0~7.5, Solid phase physical mixed is carried out, mixing temperature is 25~200 DEG C, and heating rate is 0~5 DEG C/min, and rotating speed is 300~1100rpm, 30~180min of incorporation time, obtains mixed material；It is described can carbonisable binder for furane resins, epoxy resin, polyvinyl alcohol, One or more of polyacrylonitrile, butadiene-styrene rubber, asphalt and coal tar pitch；The light metal halogen for sodium chloride, sodium fluoride, One or more of sodium bromide, potassium chloride, potassium fluoride and potassium bromide；
3rd, green compact
Mixed material is forged and pressed, forging and stamping pressure is 10~100MPa, when forge time is 0.5~10 small, obtains diameter 300 The green body of × height 200mm；
4th, high temperature graphitization
Green body is placed in stove, is passed through protective gas, flow is 1.0~2.5m3/ h, with the heating of 5~15 DEG C/min Speed is warming up to 2000~3000 DEG C, and the retention time is 3~9h, carries out high temperature graphitization processing, then the natural cooling in stove It to room temperature, crushes and screens, obtains coal base negative material presoma；
5th, cladding cures
By coal base negative material presoma, resol resin, pore-forming additive in mass ratio 100：5.0~15.0： 0.5~5.0, the solution obtained in alcoholic solvent is scattered in, the mass concentration of solution is 20~50%, speed of agitator 300~ 1000r/min, 30~60min of mixing time, carry out liquid phase mixing, and liquid phase mixing solidify afterwards obtain being coated with phenolic resin Coal base negative material presoma；The both sexes triblock copolymer that the pore-forming additive forms for ethyoxyl and propoxyl group；
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in stove, under the atmosphere of protective gas, stream It measures as 0.4~1.4m3/ h, with 1.5~5 DEG C/min of heating rate, until 800~1100 DEG C, 0.5~2.5h of time of pyrolysis temperature, Isothermal pyrolysis processing is carried out, then the cooled to room temperature in stove, crushing and classification, obtain power lithium-ion battery and answered with coal base Close negative material.
The method anthracite of the present invention uses Ningxia Tai Xi coals.
Crushing Universalpulverizer, mechanical crusher, airslide disintegrating mill, the micronizer of the method and step one of the present invention Or ball mill pulverizer；The step 2 solid phase mixing equipment is using the double heating kneading machines of double stirrings, V types mixer, roller mixing Machine, cone-type mixer or mechanical fusion machine；The forging equipment that the step 3 forging and stamping use is forcing press, hydraulic press, single arm type Open die forging liquid pneumatic hammer, double-arm open die forging liquid pneumatic hammer or tablet press machine；Green body is placed in intermediate frequency sense by the step 4 high temperature graphitization It answers in graphitizing furnace；The step 6 pyrolysis, high-temperature atmosphere is placed in by the coal base negative material presoma for being coated with phenolic resin In stove.
The protective gas of the method and step four of the present invention is one in nitrogen, helium, neon, argon gas, Krypton and xenon Kind or more；The protective gas of the step 6 is one or more of nitrogen, helium, neon, argon gas, Krypton and xenon.
The method and step four of the present invention crushes and screens rear average grain diameter D50 as 15.0~20.0 μm；The step 6 crushes Classification, average grain diameter D50 are 17.0~22.0 μm.
The pore-forming additive of the method and step five of the present invention is P123 and F127；The alcoholic solvent is methanol, ethyl alcohol, isopropyl Alcohol more than one, volume fraction be more than 60%；The solidification temperature is 110~150 DEG C, hardening time for 6.0~ 12.0h。
Compared with prior art, the present invention power lithium-ion battery has high power capacity, high power with coal base composite negative pole material Rate charge-discharge performance, long circulation life, environmentally friendly, preparation method is simple, easy control of process conditions, and production cost is low, It is suitble to large-scale industrialized production.
Description of the drawings
Fig. 1 is the coal base negative material presoma X-ray diffraction spectrogram of the embodiment of the present invention 4.
Fig. 2 is the coal base composite negative pole material 500X SEM pictures of the embodiment of the present invention 4.
Fig. 3 is the coal base composite negative pole material 8000X SEM pictures of the embodiment of the present invention 4.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Power lithium-ion battery coal base composite negative pole material (coal base composite negative pole material, the composite negative pole material of the present invention Material, composite material), for the graphitization anthracite for being 75~90% using degree of graphitization as matrix, matrix is coated with mesoporous carbon, mesoporous Carbon coating layer quality is the 2.0~7.5% of substrate quality, and composite material average grain diameter D50 is 17.0~22.0 μm, specific surface area For 5.78~7.24m2/g.Mesoporous carbon is the both sexes three block of ethyoxyl and propoxyl group composition using phenolic resin as carbon precursor Copolymer is pore-forming additive, is formed through high temperature pyrolysis solvent evaporation induced self-assembly, the aperture of mesoporous carbon nano-pore is in 50nm Hereinafter, pore-size distribution order height, high mechanical strength, thermal stability are good.Since mesoporous carbon is that base is coated in preparation process On body, the specific surface area of composite material can characterize indirectly illustrates that mesoporous carbon exists and than expression condition.Anthracite is using peaceful Xia Taixi coals have low ash, low-sulfur, low-phosphorous, golf calorific value, high specific resistance, high lump coal rate, high chemism, the recycling of high cleaned coal The characteristics of rate and high mechanical properties.
The present invention power lithium-ion battery coal base composite negative pole material preparation method, matrix using Ningxia Tai Xi coals as Raw material, light metal halogen purification additive and can carbonisable binder effect under, through crush shaping, dispensing, green compact, pyrographite The higher second particle coal base negative material presoma of purity is prepared in change, and coal base negative material presoma is again through crushing and screening Afterwards under alcoholic solvent effect, the both sexes triblock copolymer pore-creating with resol resin, ethyoxyl and propoxyl group composition adds Agent even in liquid phase is added to disperse, cured, pyrolysis processing, the power lithium-ion battery that mesoporous carbon coating matrix is finally prepared is used Coal base composite negative pole material.It concretely comprises the following steps：
First, crush
Under room temperature (20 DEG C), quality phosphorus content is more than to 97% anthracite, is crushed, until average grain diameter D50 is 2.0 ~8.0 μm, obtain anthracite micro mist.
Breaking method is mechanical crushing, air-flow crushing or grinds.Universalpulverizer, mechanical crushing can be selected in equipment Machine, airslide disintegrating mill, micronizer or ball mill pulverizer.
Anthracite is used to be derived from a wealth of sources for raw material, it is cheap, contribute to reduction power lithium-ion battery coal base compound The production cost of negative material.Preferably Ningxia Tai Xi coals in anthracite, Ningxia Tai Xi coals have low ash, low-sulfur, low-phosphorous, occurred frequently The characteristics of heat, high specific resistance, high lump coal rate, high chemism, high clean coal recovery and high mechanical properties.
It is 2.0~8.0 μm of size distributions anthracite to be crushed, D50 is presented, and may advantageously facilitate high temperature solid-state purified reaction It carries out, improves purification purity and uniformity；Meanwhile be conducive to be formed the graphite microcrystal of isotropic distribution in graphitizing process Grain promotes the formation with rock-steady structure secondary granulation particle.Anthracite has both graphitized carbon and the performance of ungraphitised carbon is excellent Gesture, the high temperature graphitization technique that the method for the present invention uses can realize the control to its degree of graphitization and structure, make anthracite graphite There is excellent high-rate charge-discharge capability, cyclical stability and low temperature electrochemical performance after change.
2nd, dispensing mixes
By anthracite micro mist, can carbonisable binder and light metal halogen in mass ratio 100：2.0~20.0：1.0~7.5, Solid phase physical mixed is carried out, mixing temperature is 25~200 DEG C, and heating rate is 0~5 DEG C/min, and rotating speed is 300~1100rpm, 30~180min of incorporation time is sufficiently mixed uniformly, obtains mixed material.
Can carbonisable binder for furane resins, epoxy resin, polyvinyl alcohol, polyacrylonitrile, butadiene-styrene rubber, asphalt and One or more of coal tar pitch.
Light metal halogen is one or more of sodium chloride, sodium fluoride, sodium bromide, potassium chloride, potassium fluoride and potassium bromide.
Solid phase mixing equipment using the double heating kneading machines of double stirrings, V-Mixer, drum mixer, cone-type mixer or Mechanical fusion machine.
The purpose of this step be by anthracite micro mist, can carbonisable binder and light metal halogen realized according to stoichiometric ratio Uniformly mixing is conducive to the uniformity of the uniformity and final product chemically reacted during high temperature graphitization.Mass ratio be It converts on the basis of stoichiometric ratio, to be conveniently operated.
3rd, green compact
Mixed material is forged and pressed, forging and stamping pressure is 10~100MPa, when forge time is 0.5~10 small, obtains diameter 300 The green body of × height 200mm.
The forging equipment used is forged and pressed as forcing press, hydraulic press, single arm type open die forging liquid pneumatic hammer, double-arm open die forging liquid gas Hammer or tablet press machine.
Green compact processing makes mixture material combine closely, be conducive to that solid-state diffusion during high temperature graphitization reacts into Row can not only promote the effect of high temeperature chemistry purification, be additionally beneficial to that tap density is big, the formation of stable structure second particle.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through protective gas, with the heating rate of 5~15 DEG C/min, 2000~3000 DEG C are warming up to, the retention time is 3~9h, carries out high temperature graphitization processing, room is then naturally cooled in stove Temperature crushes and screens, and obtains coal base negative material presoma.
Protective gas one or more of for nitrogen, helium, neon, argon gas, Krypton and xenon, flow for 1.0~ 2.5m3/h。
After high temperature graphitization, coal base negative material presoma degree of graphitization is 75~90%, and quality phosphorus content reaches More than 99.90%, rear average grain diameter D50 is crushed and screened as 15.0~20.0 μm.
In the high temperature graphitization stage, by controlling graphitization heating rate, temperature and time, anthracite is in light metal halogen Under effect, the impurity of hardly possible volatilization is removed by reacting the volatile halide mode of generation；Anthracite graphitization is given birth to simultaneously Into isotropic distribution, graphite layers away from larger graphite microcrystal particle, weight can mutually occur under the action of carbonisable binder Row, is further formed the excellent second particle of stable structure, chemical property.
In anthracite graphitizing process, using light metal halogen as purification additive, it can be generated under the conditions of graphitizable high temperature Gaseous state halogen ion and the impurity reaction of difficult volatilization in mixed material generate volatile halide, realize same with high temperature graphitization Shi Chunhua is cooperateed in same step and purified, and effectively promotes the purity and uniformity of mixed material.Can carbonisable binder with graphite Change temperature-rise period, constantly can coat and penetrate into coal sill surface and hole, decomposed with graphitization process and remove other Hetero atom, remaining carbon atom or with the carbon atom in coal sill mutually occur reset formed have stablize chemical bonding structure Interlayer, interlayer will be graphitized the concatenation restructuring of anthracite micro mist, through crushing and screening realization secondary granulation.
Using the coal base negative material presoma that anthracite is obtained as raw material, by isotropic distribution and the stone of low degree of graphitization Black microcrystal grain and infiltration and the graphitized binder composition for being coated on graphite microcrystal pellet pores and surface.Wherein, graphite Microcrystal grain macro manifestations are isotropic, and the structure that can effectively improve power lithium-ion battery coal base composite negative pole material is steady It is qualitative, suitable for lithium ion during high power charging-discharging insertion it is embedding go out.Low degree of graphitization can make graphite microcrystal particle obtain compared with Big graphite layers are away from can not only improve the embedding lithium space of ion cathode material lithium, to increase electrode reversible specific capacity, moreover it is possible to Diffusion admittance of the lithium ion in graphite linings is enough expanded, improves electrode high rate capability.Binding agent is graphitized formed cladding The good compatibility of layer and electrolyte, can effectively hinder organic solvent molecule to be inserted into coal base graphite flake layer, improve lithium ion and bear The cyclical stability of pole material.
5th, cladding cures
By coal base negative material presoma, resol resin, pore-forming additive in mass ratio 100：5.0~15.0： 0.5~5.0, the solution obtained in alcoholic solvent is scattered in, the mass concentration of solution is 20~50%, speed of agitator 300~ 1000r/min, 30~60min of mixing time, carry out liquid phase mixing, and liquid phase mixing solidify afterwards obtain being coated with phenolic resin Coal base negative material presoma.
The both sexes triblock copolymer that pore-forming additive forms for ethyoxyl and propoxyl group, preferably P123 and F127, In, the molecular formula EO of P12320PO70EO20, the molecular formula EO of F127106PO70EO106, EO expression ethyoxyls, PO expression propoxyl group.
Alcoholic solvent for methanol, ethyl alcohol, isopropanol more than one, volume fraction be more than 60%.
Cure the curing process using the prior art, preferable solidification temperature is 110~150 DEG C, hardening time for 6.0~ 12.0h。
The coated curing in coal base negative material presoma surface has phenolic resin, can further be handled by high temperature pyrolysis, Mesoporous carbon coating layer is formed under pore-forming additive effect, improves the chemical property of persursor material, wherein, curing process is In order to which resol resin keeps intrinsic properties, to ensure the uniformity of clad.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, in the gas of protective gas Under atmosphere, with 1.5~5 DEG C/min of heating rate, until 800~1100 DEG C, 0.5~2.5h of time of pyrolysis temperature, carries out isothermal pyrolysis Processing, then the cooled to room temperature in stove, crushing and classification, average grain diameter D50 are 17.0~22.0 μm, obtain power lithium Ion battery coal base composite negative pole material.
Protective gas one or more of for nitrogen, helium, neon, argon gas, Krypton and xenon, flow for 0.4~ 1.4m3/h。
In the mesoporous carbon coating layer of coal base negative material presoma Surface Creation after pyrolysis processing, mesoporous carbon nano-pore aperture exists Below 50nm, gained composite material specific surface area are 5.78~7.24m2/ g, since mesoporous carbon is coated in preparation process On matrix, the specific surface area and pore volume for symbolizing clad can not be separated, but the specific surface area of composite material can indirect table Sign illustrates that mesoporous carbon exists and than expression condition.
Using resol resin as coal base negative material carbon coating presoma, the both sexes three of ethyoxyl and propoxyl group composition Block copolymer is pore-forming additive, and solvent evaporation induced self-assembly forms high through-hole rate mesoporous carbon under the conditions of high temperature pyrolysis, Nano surface pore structure volume change internal stress simultaneously, can provide more during high rate charge-discharge is absorbed for electrochemical reaction More reacting environment.
Using resol resin liquid phase coating at coal base negative material presoma surface, cured, high temperature pyrolysis After reason, mesoporous carbon coating layer can be formed under pore-forming additive effect, the pore structure of mesoporous carbon not only can greatly buffer dynamic Bulk effect of the power lithium ion battery with coal base composite negative pole material during high power charging-discharging, while have good micro- Lithium mechanism and excellent absorbent are stored up in hole, and high through-hole rate does not interfere with Ion transfer of the electrolyte in mesoporous carbon, effectively Improve specific discharge capacity, rate charge-discharge performance and the cryogenic property of power lithium-ion battery coal base composite negative pole material.
The power lithium-ion battery coal base composite negative pole material that the method for the present invention is prepared, by national standard GB212-91《Proximate analysis of coal》The method of middle formulation, testing the purity of coal base negative material presoma, (" purity " be Quality phosphorus content percentage in material).It is measured with the XRD-7000X x ray diffractometer xs of Japanese Shimadzu Corporation and characterization coal base is born Pole material precursor degree of graphitization and XRD spectrum (degree of graphitization=[d (002) -3.354]/[3.44-3.354]).With Japanese electricity The JSM-7200F type scanning electronic microscope observation coal base negative material presoma patterns of sub- J Co., Ltd. EOL.It is stepped with the U.S. Can promise Technology Co., Ltd. CARVER4350 type compacted densities instrument test power lithium-ion battery coal base composite negative pole material Powder body compacted density.It is used with the NOVA 4000E specific-surface area detection instruments test power lithium-ion battery of Kang Ta instrument companies of the U.S. Coal base composite negative pole material specific surface area.
With the power lithium-ion battery that Examples 1 to 6 obtains coal base composite negative pole material and the negative material of comparative example Cathode is made as negative electrode active material, carries out half-cell test.By negative electrode active material, conductive agent carbon black SP, binding agent PVDF mass ratioes 92:3:5, solvent is made with N-Methyl pyrrolidone NMP and is applied to after mixing on copper foil, 110 DEG C of dryings 10 are small Shi Hou, spreading and punching are to electrode, with 1molL-1LiPF6/DMC+DEC+EC (volume ratios 1 with metal lithium sheet:1:1) Electrolyte is done, in the German Braun MBRAUN glove boxes of high-purity argon gas protection, CR2032 experimental button cells are made.It uses force The CT2001A type Bluepoint battery test systems of Chinese city Lan electricity electronics limited company, measure 1C discharge capacity mAh/g for the first time, Efficiency % for the first time is discharged using power lithium-ion battery with the 100th week 1C discharge capacity of coal base composite negative pole material and the 1st week 1C 100 weeks circulation volume conservation rate % are calculated in the ratio between capacity.
Embodiment 1
First, crush
It is the anthracite micro mist that average grain diameter D50 is 2.0 μm with Universalpulverizer crushing by anthracite Ningxia Tai Xi coals.
2nd, dispensing mixes
Anthracite micro mist 1000g, furane resins 20.0g, sodium chloride 10.0g are weighed respectively and is added to drum mixer, are risen Warm rate is 0 DEG C/min, and rotating speed 1100rpm mixes 180min at 25 DEG C, obtains mixed material.
3rd, green compact
Mixed material is forged and pressed to the base of 10h acquisition 300 × height of diameter 200mm using forcing press under pressure 10MPa Body.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through nitrogen, flow 1.0m3/ h, with the heating of 5 DEG C/min Speed is warming up to 2000 DEG C, is graphitized 9h, and the cooled to room temperature in stove crushes and screens, and obtaining average grain diameter D50 is 15.0 μm of coal base negative material presoma.
5th, cladding cures
By coal base negative material presoma, the resol resin of coal base negative material forerunner weight 5%, coal base is born The pore-forming additive P123 of pole material precursor quality 0.5%, addition, which is distributed in methanol solvate, is configured to solution, the matter of solution It is 20%, the mechanical agitation 60min under rotating speed 300r/min to measure concentration, carries out liquid phase mixing, will be mixed after suction filtration solution Mixture is positioned in vacuum drying chamber, is less than 208Pa in vacuum degree, is cured 12.0h at 110 DEG C of temperature, obtain being coated with phenol The coal base negative material presoma of urea formaldehyde.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, is passed through nitrogen, flow is 0.4m3/ h is warming up to 800 DEG C with 1.5 DEG C/min of heating rate, isothermal pyrolysis processing 2.5h, cooled to room temperature in stove, powder Broken classification, after crossing 200 mesh sieves, average grain diameter D50 is 17.0~22.0 μm, obtains power lithium-ion battery coal base composite negative pole Material.
After tested, the coal base negative material presoma purity of embodiment 1 is 99.91%, degree of graphitization 75%, test knot Fruit, which summarizes, is shown in Table 1.
Power lithium-ion battery is 5.78m with coal base composite negative pole material specific surface area2/ g, powder body compacted density are 1.40g/cm3.The electrochemical property test of simulated battery, discharge capacity is 356.2mAh/g to 1C for the first time, and efficiency is for the first time 92.3%, 100 weeks circulation volume conservation rate >=94.2%, test result, which summarizes, is shown in Table 2.
Embodiment 2
First, crush
It is the anthracite micro mist that average grain diameter D50 is 3.0 μm with Universalpulverizer crushing by anthracite Ningxia Tai Xi coals.
2nd, dispensing mixes
Anthracite micro mist 1000g, furane resins 56.0g, sodium fluoride 23.0g are weighed respectively and is added to cone-type mixer, are risen Warm rate is 1 DEG C/min, and rotating speed 900rpm mixes 150min at 50 DEG C, obtains mixed material.
3rd, green compact
Mixed material is forged and pressed to the green body of 8h acquisition 300 × height of diameter 200mm using hydraulic press under pressure 28MPa.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through helium, flow 1.3m3/ h, with the heating of 7 DEG C/min Speed is warming up to 2200 DEG C, is graphitized 8h, and the cooled to room temperature in stove crushes and screens, and obtaining average grain diameter D50 is 16.0 μm of coal base negative material presoma.
5th, cladding cures
By coal base negative material presoma, the resol resin of coal base negative material forerunner weight 7%, coal base is born The pore-forming additive P123 of pole material precursor quality 1.4%, addition, which is distributed in methanol solvate, is configured to solution, the matter of solution It is 25%, the mechanical agitation 54min under rotating speed 440r/min to measure concentration, carries out liquid phase mixing, will be mixed after suction filtration solution Mixture is positioned in vacuum drying chamber, is less than 208Pa in vacuum degree, is cured 10.0h at 120 DEG C of temperature, obtain being coated with phenol The coal base negative material presoma of urea formaldehyde.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, is passed through helium, flow is 0.6m3/ h is warming up to 900 DEG C with 2.0 DEG C/min of heating rate, isothermal pyrolysis processing 2.0h, cooled to room temperature in stove, powder Broken classification, after crossing 200 mesh sieves, average grain diameter D50 is 17.0~22.0 μm, obtains power lithium-ion battery coal base composite negative pole Material.
After tested, the coal base negative material presoma purity of embodiment 2 is 99.93%, degree of graphitization 78%, test knot Fruit, which summarizes, is shown in Table 1.
Power lithium-ion battery is 5.82m with coal base composite negative pole material specific surface area2/ g, powder body compacted density are 1.38g/cm3.The electrochemical property test of simulated battery, discharge capacity is 370.5mAh/g to 1C for the first time, and efficiency is for the first time 93.5%, 100 weeks circulation volume conservation rate >=97.3%, test result, which summarizes, is shown in Table 2.
Embodiment 3
First, crush
It is the anthracite micro mist that average grain diameter D50 is 5.0 μm with airslide disintegrating mill crushing by anthracite Ningxia Tai Xi coals.
2nd, dispensing mixes
Anthracite micro mist 1000g, polyvinyl alcohol 92g, sodium bromide 36g are weighed respectively, are added to mechanical fusion machine, heating speed Rate is 2 DEG C/min, and rotating speed 700rpm mixes 120min at 100 DEG C, obtains mixed material.
3rd, green compact
Mixed material is forged and pressed into 6h under pressure 46MPa using single arm type open die forging liquid pneumatic hammer and obtains diameter 300 × height The green body of 200mm.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through neon, flow 1.6m3/ h, with the heating of 9 DEG C/min Speed is warming up to 2400 DEG C, is graphitized 7h, and the cooled to room temperature in stove crushes and screens, and obtaining average grain diameter D50 is 17.0 μm of coal base negative material presoma.
5th, cladding cures
By coal base negative material presoma, the resol resin of coal base negative material forerunner weight 9%, coal base is born The pore-forming additive P123 of pole material precursor quality 2.3%, addition, which is distributed in alcohol solvent, is configured to solution, the matter of solution It is 35%, the mechanical agitation 48min under rotating speed 580r/min to measure concentration, carries out liquid phase mixing, will be mixed after suction filtration solution Mixture is positioned in vacuum drying chamber, is less than 208Pa in vacuum degree, is cured 9.0h at 130 DEG C of temperature, obtain being coated with phenol The coal base negative material presoma of urea formaldehyde.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, is passed through neon, flow is 0.8m3/ h is warming up to 950 DEG C with 3.0 DEG C/min of heating rate, isothermal pyrolysis processing 1.5h, cooled to room temperature in stove, powder Broken classification, after crossing 200 mesh sieves, average grain diameter D50 is 17.0~22.0 μm, obtains power lithium-ion battery coal base composite negative pole Material.
After tested, the coal base negative material presoma purity of embodiment 3 is 99.95%, degree of graphitization 83%, test knot Fruit, which summarizes, is shown in Table 1.
Power lithium-ion battery is 6.42m with coal base composite negative pole material specific surface area2/ g, powder body compacted density are 1.36g/cm3.The electrochemical property test of simulated battery, discharge capacity is 375.3mAh/g to 1C for the first time, and efficiency is for the first time 93.0%, 100 weeks circulation volume conservation rate >=100.3%, test result, which summarizes, is shown in Table 2.Circulation volume conservation rate is within 100 weeks Now it is more than 100%, is since after composite material 1C charge and discharge cycles 100 weeks, ascendant trend occurs in capacity, shows that composite material exists Structure remained stable during high rate charge-discharge, the nano surface pore structure of clad mesoporous carbon is electro-active by charge and discharge, is in Reveal good micropore storage lithium, and mesoporous carbon intrinsic property high mechanical strength, thermal stability are good, and composite material is made to be filled in big multiplying power Do not occur hole under electric discharge to cave in.
Embodiment 4
First, crush
It is the anthracite micro mist that average grain diameter D50 is 5.0 μm with micronizer crushing by anthracite Ningxia Tai Xi coals.
2nd, dispensing mixes
Anthracite micro mist 1000g, polyacrylonitrile 128.0g, potassium chloride 49.0g are weighed respectively and is added to V-Mixer, are risen Warm rate is 3 DEG C/min, and rotating speed 700rpm mixes 90min at 125 DEG C, obtains mixed material.
3rd, green compact
Mixed material is forged and pressed into 4h under pressure 64MPa using single arm type open die forging liquid pneumatic hammer and obtains diameter 300 × height The green body of 200mm.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through argon gas, flow 1.9m3/ h, with the heating of 11 DEG C/min Speed is warming up to 2600 DEG C, is graphitized 5.5h, and the cooled to room temperature in stove crushes and screens, and obtaining average grain diameter D50 is 18.0 μm of coal base negative material presoma.
As shown in Figure 1, anthracite Ningxia Tai Xi coals are carbonized after high temperature graphitization and graphite transition, diffraction Main diffraction peak is consistent with graphitized carbon in collection of illustrative plates.
5th, cladding cures
By coal base negative material presoma, the resol resin of coal base negative material forerunner weight 11%, coal base The pore-forming additive P127 of negative material forerunner weight 3.2%, addition, which is distributed in alcohol solvent, is configured to solution, solution Mass concentration is 35%, the mechanical agitation 42min under rotating speed 720r/min, liquid phase mixing is carried out, after being mixed after suction filtration solution Mixture be positioned in vacuum drying chamber, in vacuum degree less than 208Pa, cure 9.0h at 130 DEG C of temperature, obtain being coated with phenol The coal base negative material presoma of urea formaldehyde.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, is passed through argon gas, flow is 1.0m3/ h is warming up to 950 DEG C with 3.5 DEG C/min of heating rate, isothermal pyrolysis processing 1.5h, cooled to room temperature in stove, powder Broken classification, after crossing 200 mesh sieves, average grain diameter D50 is 17.0~22.0 μm, obtains power lithium-ion battery coal base composite negative pole Material.
After tested, the coal base negative material presoma purity of embodiment 4 is 99.97%, degree of graphitization 85%, test knot Fruit, which summarizes, is shown in Table 1.
Power lithium-ion battery is 6.72m with coal base composite negative pole material specific surface area2/ g, powder body compacted density are 1.35g/cm3.The electrochemical property test of simulated battery, discharge capacity is 385.2mAh/g to 1C for the first time, and efficiency is for the first time 95.5%, 100 weeks circulation volume conservation rate >=105.3%, test result, which summarizes, is shown in Table 2.Circulation volume conservation rate is within 100 weeks Now it is more than 100%, is since after composite material 1C charge and discharge cycles 100 weeks, ascendant trend occurs in capacity, shows that composite material exists Structure remained stable during high rate charge-discharge, the nano surface pore structure of clad mesoporous carbon after charge and discharge is electro-active, Good micropore storage lithium is showed, and mesoporous carbon intrinsic property high mechanical strength, thermal stability are good, make composite material in big multiplying power Do not occur hole under charge and discharge to cave in.
As shown in Figures 2 and 3, the coating mesoporous carbon-coating in coal base negative material surface, nano-pore are evenly distributed, and aperture exists Below 50nm, pore-size distribution is orderly, can effectively buffer composite negative pole material, the volume effect during high power charging-discharging Should, while there is good micropore storage lithium mechanism and excellent absorbent.
Embodiment 5
First, crush
It is the anthracite micro mist that average grain diameter D50 is 5.0 μm with ball mill pulverizer crushing by anthracite Ningxia Tai Xi coals.
2nd, dispensing mixes
Anthracite micro mist 1000g, butadiene-styrene rubber 164.0g, sodium chloride 62.0g are weighed respectively, are added to the double heating of double stirrings Kneading machine, heating rate are 4 DEG C/min, and rotating speed 500rpm mixes 60min at 175 DEG C, obtains mixed material.
3rd, green compact
Mixed material is forged and pressed into 2h under pressure 82MPa using double-arm open die forging liquid pneumatic hammer and obtains diameter 300 × height The green body of 200mm.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through Krypton, flow 2.2m3/ h, with the heating of 13 DEG C/min Speed is warming up to 2800 DEG C, is graphitized 4h, and the cooled to room temperature in stove crushes and screens, and obtaining average grain diameter D50 is 19.0 μm of coal base negative material presoma.
5th, cladding cures
By coal base negative material presoma, the resol resin of coal base negative material forerunner weight 13%, coal base The pore-forming additive P127 of negative material forerunner weight 4.1%, addition, which is distributed in isopropanol solvent, is configured to solution, solution Mass concentration for 45%, the mechanical agitation 36min under rotating speed 860r/min, carry out liquid phase mixing, filtering will mixing after solution Mixture afterwards is positioned in vacuum drying chamber, is less than 208Pa in vacuum degree, is cured 8.0h at 140 DEG C of temperature, coated There is the coal base negative material presoma of phenolic resin.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, is passed through Krypton, flow is 1.2m3/ h is warming up to 1000 DEG C with 4.5 DEG C/min of heating rate, isothermal pyrolysis processing 1.0h, cooled to room temperature in stove, Crushing and classification, after crossing 200 mesh sieves, average grain diameter D50 is 17.0~22.0 μm, obtains power lithium-ion battery coal base Compound Negative Pole material.
After tested, the coal base negative material presoma purity of embodiment 5 is 99.97%, degree of graphitization 88%, test knot Fruit, which summarizes, is shown in Table 1.
Power lithium-ion battery is 7.02m with coal base composite negative pole material specific surface area2/ g, powder body compacted density are 1.30g/cm3.The electrochemical property test of simulated battery, discharge capacity is 370.4mAh/g to 1C for the first time, and efficiency is for the first time 92.5%, 100 weeks circulation volume conservation rate >=96.8%, test result, which summarizes, is shown in Table 2.
Embodiment 6
First, crush
It is the anthracite micro mist that average grain diameter D50 is 8.0 μm with airslide disintegrating mill crushing by anthracite Ningxia Tai Xi coals.
2nd, dispensing mixes
Anthracite micro mist 1000g, mass ratio 80 are weighed respectively:20 asphalt and coal tar pitch mixture 200.0g, chlorine Change sodium 75.0g, be added to the double heating kneading machines of double stirrings, heating rate is 5 DEG C/min, rotating speed 300rpm, is mixed at 200 DEG C 30min is closed, obtains mixed material.
3rd, green compact
Mixed material is forged and pressed into 0.5h under pressure 1002MPa using tablet press machine and obtains 300 × height of diameter 200mm's Green body.
4th, high temperature graphitization
Green body is placed in Medium frequency induction graphitizing furnace, is passed through xenon, flow 2.5m3/ h, with the heating of 15 DEG C/min Speed is warming up to 3000 DEG C, is graphitized 3h, and the cooled to room temperature in stove crushes and screens, and obtaining average grain diameter D50 is 20.0 μm of coal base negative material presoma.
5th, cladding cures
By coal base negative material presoma, the resol resin of coal base negative material forerunner weight 15%, coal base The pore-forming additive P127 of negative material forerunner weight 5.0%, addition, which is distributed in isopropanol solvent, is configured to solution, solution Mass concentration for 50%, the mechanical agitation 30min under rotating speed 1000r/min, carry out liquid phase mixing, filtering will mixing after solution Mixture afterwards is positioned in vacuum drying chamber, is less than 208Pa in vacuum degree, is cured 6.0h at 150 DEG C of temperature, coated There is the coal base negative material presoma of phenolic resin.
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace, is passed through xenon, flow is 1.4m3/ h is warming up to 1100 DEG C with 5.0 DEG C/min of heating rate, isothermal pyrolysis processing 0.5h, cooled to room temperature in stove, Crushing and classification, after crossing 200 mesh sieves, average grain diameter D50 is 17.0~22.0 μm, obtains power lithium-ion battery coal base Compound Negative Pole material.
After tested, the coal base negative material presoma purity of embodiment 6 is 99.99%, degree of graphitization 90%, test knot Fruit, which summarizes, is shown in Table 1.
Power lithium-ion battery is 7.24m with coal base composite negative pole material specific surface area2/ g, powder body compacted density are 1.28g/cm3.The electrochemical property test of simulated battery, discharge capacity is 367.2mAh/g to 1C for the first time, and efficiency is for the first time 93.5%, 100 weeks circulation volume conservation rate >=92.3%, test result, which summarizes, is shown in Table 2.
Comparative example (uncoated mesoporous carbon)
By the cathode material of the coal base negative material presoma obtained after 4 step 4 high temperature graphitization of embodiment as a comparison case Material.
After tested, the negative material specific surface area of comparative example is 4.24m2/ g, powder body compacted density are 1.58 g/cm3.Mould Intend the electrochemical property test of battery, discharge capacity is 340.2mAh/g to 1C for the first time, and efficiency is 94.4% for the first time, is cycled within 100 weeks Capacity retention ratio >=86.4%, test result, which summarizes, is shown in Table 2.
Embodiment is compared with comparative example, it can be seen that by coal base negative material presoma Surface Creation mesoporous carbon bag Coating since nanometer micropore is distributed in mesoporous carbon surface, significantly improves composite material specific surface area, is not influencing composite material On the premise of processing performance, more reacting environment can be provided for electrochemical reaction, and nanometer micropore is stored up with good micropore Lithium mechanism can promote the charging and discharging capacity of composite material.
The present invention selects anthracite to prepare raw material for Delanium, derives from a wealth of sources, cheap, advantageously reduces power lithium The production cost of ion battery coal base composite negative pole material particularly selects Ningxia Tai Xi coals, with low ash, low-sulfur, low The characteristics of phosphorus, golf calorific value, high specific resistance, high lump coal rate, high chemism, high clean coal recovery and high mechanical properties, high temperature Solid phase purification purity is high, and technology difficulty is small, and pole is beneficial to the cyclical stability and security of composite material.Anthracite graphitizing process In, light metal halogen is selected on the premise of no extension technological process, to further improve composite wood as purification additive The purity of material avoids acid during prior art chemical purification to the pollution of environment and is passed through reaction gas at high temperature Purifying technique is complicated, equipment is perishable and the non-uniform problem of purification.It is formed after coal base negative material presoma graphitization Graphite microcrystal particle, macro manifestations are for isotropic and with larger graphite layers away from can effectively improve power lithium-ion battery With the structural stability and specific discharge capacity of coal base composite negative pole material, be conducive to the embedding of lithium ion during high power charging-discharging Enter it is embedding go out.Using resol resin as carbon coating coal base negative material presoma, the both sexes three of ethyoxyl and propoxyl group composition Block copolymer is pore-forming additive, and mesoporous carbon is formed on power lithium-ion battery coal base composite negative pole material surface, mesoporous Carbon pores structure not only can greatly bulk effect of the buffering composite material during high power charging-discharging, while have good Micropore storage lithium mechanism and excellent absorbent, improve the electric discharge ratio of power lithium-ion battery coal base composite negative pole material Capacity, rate charge-discharge performance and cryogenic property.The both sexes three block of anthracite and ethyoxyl and propoxyl group composition is selected in cooperation Copolymer is pore-forming additive, and preparation method of the invention is easy to control, it is easy to accomplish industrialized production, from raw material to technique side The equal cost of method is relatively low, not only reduces power lithium-ion battery cost, while meets height of the power lithium-ion battery to energy density Demand.
The coal base negative material presoma purity and degree of graphitization test result of 1 embodiment of table summarize
The physical property and chemical property test result of 2 embodiment of table and comparative example summarize

Claims (10)

1. a kind of power lithium-ion battery coal base composite negative pole material, it is characterised in that：The power lithium-ion battery coal For the graphitization anthracite that base composite negative pole material is 75~90% using degree of graphitization as matrix, matrix is coated with mesoporous carbon, is situated between Hole carbon coating layer quality is the 2.0~7.5% of substrate quality；Mesoporous carbon is the ethyoxyl and third using phenolic resin as carbon precursor The both sexes triblock copolymer of oxygroup composition is pore-forming additive, is formed through high temperature pyrolysis solvent evaporation induced self-assembly.
2. power lithium-ion battery according to claim 1 coal base composite negative pole material, it is characterised in that：The power Lithium ion battery coal base composite negative pole material average grain diameter D50 is 17.0~22.0 μm, and specific surface area is 5.78~7.24m2/ g。
3. power lithium-ion battery according to claim 1 coal base composite negative pole material, it is characterised in that：It is described mesoporous The aperture of carbon nano-pore is in below 50nm.
4. power lithium-ion battery according to claim 1 coal base composite negative pole material, it is characterised in that：It is described smokeless Coal uses Ningxia Tai Xi coals.
5. a kind of power lithium-ion battery preparation method of coal base composite negative pole material, comprises the following steps：
First, crush
At room temperature, quality phosphorus content is more than to 97% anthracite, is crushed, until average grain diameter D50 is 2.0~8.0 μm, is obtained To anthracite micro mist；
2nd, dispensing mixes
By anthracite micro mist, can carbonisable binder and light metal halogen in mass ratio 100：2.0~20.0：1.0~7.5, it carries out Solid phase physical mixed, mixing temperature are 25~200 DEG C, and heating rate is 0~5 DEG C/min, and rotating speed is 300~1100rpm, is mixed 30~180min of time, obtains mixed material；It is described can carbonisable binder for furane resins, epoxy resin, polyvinyl alcohol, poly- third One or more of alkene nitrile, butadiene-styrene rubber, asphalt and coal tar pitch；The light metal halogen is sodium chloride, sodium fluoride, bromination One or more of sodium, potassium chloride, potassium fluoride and potassium bromide；
3rd, green compact
Mixed material is forged and pressed, forging and stamping pressure is 10~100MPa, when forge time is 0.5~10 small, obtains diameter 300 × height Spend the green body of 200mm；
4th, high temperature graphitization
Green body is placed in stove, is passed through protective gas, flow is 1.0~2.5m3/ h, with the heating rate of 5~15 DEG C/min, 2000~3000 DEG C are warming up to, the retention time is 3~9h, carries out high temperature graphitization processing, room is then naturally cooled in stove Temperature crushes and screens, and obtains coal base negative material presoma；
5th, cladding cures
By coal base negative material presoma, resol resin, pore-forming additive in mass ratio 100：5.0~15.0：0.5~ 5.0, it is scattered in the solution obtained in alcoholic solvent, the mass concentration of solution is 20~50%, 300~1000r/min of speed of agitator, 30~60min of mixing time carries out liquid phase mixing, and liquid phase mixes solidify afterwards, obtains being coated with the coal base cathode material of phenolic resin Material precursor；The both sexes triblock copolymer that the pore-forming additive forms for ethyoxyl and propoxyl group；
6th, it is pyrolyzed
The coal base negative material presoma for being coated with phenolic resin is placed in stove, under the atmosphere of protective gas, flow is 0.4~1.4m3/ h, with 1.5~5 DEG C/min of heating rate, until 800~1100 DEG C, 0.5~2.5h of time of pyrolysis temperature, carries out Isothermal pyrolysis processing, then the cooled to room temperature in stove, crushing and classification, obtain power lithium-ion battery coal base Compound Negative Pole material.
6. the power lithium-ion battery according to claim 5 preparation method of coal base composite negative pole material, feature exist In：The anthracite uses Ningxia Tai Xi coals.
7. the power lithium-ion battery according to claim 5 preparation method of coal base composite negative pole material, feature exist In：Crushing Universalpulverizer, mechanical crusher, airslide disintegrating mill, micronizer or the ball mill pulverizer of the step 1； The step 2 solid phase mixing equipment is using the double heating kneading machines of double stirrings, V-Mixer, drum mixer, cone-type mixer Or mechanical fusion machine；The forging equipment that step 3 forging and stamping use for forcing press, hydraulic press, single arm type open die forging liquid pneumatic hammer, Double-arm open die forging liquid pneumatic hammer or tablet press machine；The step 4 high temperature graphitization, green body is placed in Medium frequency induction graphitizing furnace； The step 6 pyrolysis, the coal base negative material presoma for being coated with phenolic resin is placed in high-temperature atmosphere furnace.
8. the power lithium-ion battery according to claim 5 preparation method of coal base composite negative pole material, feature exist In：The protective gas of the step 4 is one or more of nitrogen, helium, neon, argon gas, Krypton and xenon；The step Rapid six protective gas is one or more of nitrogen, helium, neon, argon gas, Krypton and xenon.
9. the power lithium-ion battery according to claim 5 preparation method of coal base composite negative pole material, feature exist In：The step 4 crushes and screens rear average grain diameter D50 as 15.0~20.0 μm；The step 6 crushing and classification, average grain diameter D50 is 17.0~22.0 μm.
10. the power lithium-ion battery according to claim 5 preparation method of coal base composite negative pole material, feature exist In：The pore-forming additive of the step 5 is P123 and F127；The alcoholic solvent for methanol, ethyl alcohol, isopropanol more than one, Volume fraction is more than 60%；The solidification temperature is 110~150 DEG C, and hardening time is 6.0~12.0h.
CN201711280108.0A 2017-12-06 2017-12-06 Power lithium-ion battery coal base composite negative pole material and preparation method thereof Withdrawn CN108054357A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711280108.0A CN108054357A (en) 2017-12-06 2017-12-06 Power lithium-ion battery coal base composite negative pole material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711280108.0A CN108054357A (en) 2017-12-06 2017-12-06 Power lithium-ion battery coal base composite negative pole material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108054357A true CN108054357A (en) 2018-05-18

Family

ID=62122809

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711280108.0A Withdrawn CN108054357A (en) 2017-12-06 2017-12-06 Power lithium-ion battery coal base composite negative pole material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108054357A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110112389A (en) * 2019-05-09 2019-08-09 中南大学 A kind of preparation method of the ultra-fine ashless coal of new energy cathode
CN110600715A (en) * 2019-10-17 2019-12-20 石家庄尚太科技有限公司 Graphite cathode composite material of lithium ion battery and preparation method thereof
CN110620236A (en) * 2019-10-15 2019-12-27 湖南中科星城石墨有限公司 Three-phase composite negative electrode material for lithium ion battery and preparation method thereof
CN111146418A (en) * 2019-12-24 2020-05-12 中国科学院山西煤炭化学研究所 High-energy-density lithium ion battery cathode material and preparation method thereof
CN111293295A (en) * 2020-01-13 2020-06-16 宁夏博尔特科技有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN111362260A (en) * 2018-12-26 2020-07-03 宁波杉杉新材料科技有限公司 High-compaction graphite negative electrode material of lithium ion battery and preparation method of high-compaction graphite negative electrode material
CN111864206A (en) * 2019-04-30 2020-10-30 贝特瑞新材料集团股份有限公司 Hard carbon negative electrode material, preparation method thereof, pole piece comprising hard carbon negative electrode material and lithium ion battery
CN112017870A (en) * 2020-08-28 2020-12-01 新奥石墨烯技术有限公司 Coal-based porous carbon, preparation method and application thereof, and lithium ion capacitor
CN112142468A (en) * 2020-09-30 2020-12-29 中钢集团新型材料（浙江）有限公司 Method for making graphite seal
CN113451575A (en) * 2020-03-24 2021-09-28 比亚迪股份有限公司 Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery
CN114044513A (en) * 2021-11-11 2022-02-15 博尔特新材料(银川)有限公司 Preparation method of coal-based graphite/carbon composite negative electrode material for power type lithium ion battery
CN114709393A (en) * 2022-04-11 2022-07-05 深圳市翔丰华科技股份有限公司 Preparation method of negative electrode material for sodium ion battery
CN115504449A (en) * 2022-06-10 2022-12-23 四川大学 Method and material for F-doped modified phenolic resin base

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101931077A (en) * 2010-05-31 2010-12-29 长沙星城微晶石墨有限公司 Anode material for lithium-ion battery and preparation method
CN102110805A (en) * 2009-12-29 2011-06-29 洛阳月星新能源科技有限公司 Anode material for lithium-ion battery prepared by anthracite and preparation method thereof
CN104681786A (en) * 2015-03-04 2015-06-03 深圳市贝特瑞新能源材料股份有限公司 Coal-based anode material, preparation method and lithium-ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102110805A (en) * 2009-12-29 2011-06-29 洛阳月星新能源科技有限公司 Anode material for lithium-ion battery prepared by anthracite and preparation method thereof
CN101931077A (en) * 2010-05-31 2010-12-29 长沙星城微晶石墨有限公司 Anode material for lithium-ion battery and preparation method
CN104681786A (en) * 2015-03-04 2015-06-03 深圳市贝特瑞新能源材料股份有限公司 Coal-based anode material, preparation method and lithium-ion battery

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362260A (en) * 2018-12-26 2020-07-03 宁波杉杉新材料科技有限公司 High-compaction graphite negative electrode material of lithium ion battery and preparation method of high-compaction graphite negative electrode material
CN111362260B (en) * 2018-12-26 2022-03-01 宁波杉杉新材料科技有限公司 High-compaction graphite negative electrode material of lithium ion battery and preparation method of high-compaction graphite negative electrode material
CN111864206B (en) * 2019-04-30 2023-11-03 贝特瑞新材料集团股份有限公司 Hard carbon negative electrode material, preparation method thereof, pole piece containing hard carbon negative electrode material and lithium ion battery
CN111864206A (en) * 2019-04-30 2020-10-30 贝特瑞新材料集团股份有限公司 Hard carbon negative electrode material, preparation method thereof, pole piece comprising hard carbon negative electrode material and lithium ion battery
CN110112389B (en) * 2019-05-09 2022-07-22 中南大学 Preparation method of superfine ashless coal for new energy negative electrode
CN110112389A (en) * 2019-05-09 2019-08-09 中南大学 A kind of preparation method of the ultra-fine ashless coal of new energy cathode
CN110620236A (en) * 2019-10-15 2019-12-27 湖南中科星城石墨有限公司 Three-phase composite negative electrode material for lithium ion battery and preparation method thereof
CN110600715A (en) * 2019-10-17 2019-12-20 石家庄尚太科技有限公司 Graphite cathode composite material of lithium ion battery and preparation method thereof
CN111146418A (en) * 2019-12-24 2020-05-12 中国科学院山西煤炭化学研究所 High-energy-density lithium ion battery cathode material and preparation method thereof
CN111293295B (en) * 2020-01-13 2021-08-03 博尔特新材料(银川)有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN111293295A (en) * 2020-01-13 2020-06-16 宁夏博尔特科技有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN113451575A (en) * 2020-03-24 2021-09-28 比亚迪股份有限公司 Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery
CN113451575B (en) * 2020-03-24 2022-09-09 比亚迪股份有限公司 Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery
CN112017870A (en) * 2020-08-28 2020-12-01 新奥石墨烯技术有限公司 Coal-based porous carbon, preparation method and application thereof, and lithium ion capacitor
CN112142468B (en) * 2020-09-30 2022-05-10 中钢新型材料股份有限公司 Method for making graphite seal
CN112142468A (en) * 2020-09-30 2020-12-29 中钢集团新型材料（浙江）有限公司 Method for making graphite seal
CN114044513A (en) * 2021-11-11 2022-02-15 博尔特新材料(银川)有限公司 Preparation method of coal-based graphite/carbon composite negative electrode material for power type lithium ion battery
CN114044513B (en) * 2021-11-11 2023-11-24 博尔特新材料(银川)有限公司 Preparation method of coal-based graphite/carbon composite anode material for power lithium ion battery
CN114709393A (en) * 2022-04-11 2022-07-05 深圳市翔丰华科技股份有限公司 Preparation method of negative electrode material for sodium ion battery
CN115504449A (en) * 2022-06-10 2022-12-23 四川大学 Method and material for F-doped modified phenolic resin base
CN115504449B (en) * 2022-06-10 2023-11-03 四川大学 F-doped modified phenolic resin based method and material

Similar Documents

Publication Publication Date Title
CN108054357A (en) Power lithium-ion battery coal base composite negative pole material and preparation method thereof
CN110615423B (en) Preparation method of silicon-based composite negative electrode material of lithium battery
JP7185764B2 (en) Silicon oxide/carbon composite negative electrode material, its preparation method and lithium ion battery
CN106981657B (en) A kind of graphite cathode material and preparation method thereof
CN106654235B (en) Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material
CN103708437B (en) Soft carbon negative material of lithium ion battery, preparation method of soft carbon negative material and lithium ion battery
CN105261734B (en) A kind of composite negative electrode material of lithium ion battery, preparation method and applications
CN102169985B (en) Preparation method of lithium ion battery carbon anode material
CN104600258B (en) Composite negative electrode material of lithium ion battery and preparation method thereof
CN111224078A (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode
CN105958070A (en) Preparation method for artificial graphite negative electrode material for lithium ion battery
CN109704323A (en) Electrode material and secondary battery
CN113540426B (en) Negative electrode material, and electrochemical device and electronic device comprising same
CN111244400B (en) Silicon-oxygen-carbon composite material, lithium ion battery, and preparation method and application of silicon-oxygen-carbon composite material
CN104143641B (en) A kind of interphase negative material and preparation method thereof
CN105932281A (en) Preparation method for graphite anode material of lithium ion battery
CN103840161A (en) Method for preparing lithium battery negative electrode material, and lithium battery negative electrode sheet
CN115744872B (en) Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof
KR20210068497A (en) Lithium ion battery negative active material, lithium ion battery negative electrode, lithium ion battery, battery pack and battery power vehicle
CN101417794A (en) Production manufacturing method of high rate lithium ionic cell cathode F series material
CN114044513A (en) Preparation method of coal-based graphite/carbon composite negative electrode material for power type lithium ion battery
CN108448114A (en) A kind of soft carbon negative electrode material of lithium ion battery and preparation method thereof
CN114988391A (en) Preparation method and application of hard carbon negative electrode material
CN111864206B (en) Hard carbon negative electrode material, preparation method thereof, pole piece containing hard carbon negative electrode material and lithium ion battery
CN110970599B (en) Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 750011 factory building No.20, zone a, Pioneer Park, Jinfeng Industrial Park, Yinchuan City, Ningxia Hui Autonomous Region

Applicant after: Bolt new materials (Yinchuan) Co.,Ltd.

Address before: 750011 Room 303, science and technology building, Yinchuan TMT breeding center, Tongda South Street, Jinfeng District, Yinchuan City, Ningxia Hui Autonomous Region

Applicant before: NINGXIA BOLT TECHNOLOGY Co.,Ltd.

CB02 Change of applicant information
WW01 Invention patent application withdrawn after publication

Application publication date: 20180518

WW01 Invention patent application withdrawn after publication