CN102299307A - Electrode anode material and preparation method thereof - Google Patents
Electrode anode material and preparation method thereof Download PDFInfo
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- CN102299307A CN102299307A CN2011102589267A CN201110258926A CN102299307A CN 102299307 A CN102299307 A CN 102299307A CN 2011102589267 A CN2011102589267 A CN 2011102589267A CN 201110258926 A CN201110258926 A CN 201110258926A CN 102299307 A CN102299307 A CN 102299307A
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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 an electrode anode material and a preparation method thereof, and aims to improve the safety of a lithium ion battery and reduce production cost. The electrode anode material is a composite material consisting of a substrate and a coating layer for coating the substrate, wherein the substrate is a graphite material with the carbon content of over 99.9 percent and is provided with nano micropores or nano pores; and the coating layer is a carbon material. The preparation method of the electrode anode material comprises the following steps of: oxidizing or reducing the graphite material, and performing solid-phase coating or liquid-phase coating on easily graphitized soft carbon or organic matter pyrolytic carbon. Compared with the prior art, the invention has the advantages that: the surface functional groups of a treating layer and/or the coating layer are controlled on the surface of the electrode anode material, and the treating layer and the coating layer are thin and uniform, so that the safety of the lithium ion battery is improved, the electrode anode material has high capacity and efficiency, the preparation process is simple, and the cost of the anode material is reduced.
Description
Technical field
The present invention relates to electrode material of a kind of battery and preparation method thereof, particularly a kind of negative material that is used for lithium ion battery and preparation method thereof.
Background technology
Along with the raising of fast development of national economy and living standards of the people, China grows with each passing day to the dependency degree of crude oil, Chinese energy safety has been constituted directly to threaten.In addition, the price fluctuation of crude oil also directly has influence on development and national economy, forces people to have to seek and the development new forms of energy.The development of electrokinetic cell and electric automobile is placed in more and more important position, and the key factor of restriction electric motor car large-scale application is an electrokinetic cell.Lithium ion battery with its high-energy-density, high voltage, pollution-free, greater than the excellent properties of aspects such as the long circulation life of 500 circulations, fast charging and discharging and the cost of manufacture that reduces day by day, progressively become the first-selected battery of electric motor car in following 10～20 years.It is more expensive that but its shortcoming is a price.In addition, the volume of power-type lithium ion battery is bigger, and security performance is the phase strain differential also.This shows that price and security performance are that the main bottleneck of lithium ion battery as electrokinetic cell used in restriction.Negative material is one of main material of lithium ion battery, and its price produces significant effects to the final price of battery, and its stability in electrolyte and heat conductivity also have very big influence to the fail safe of battery.The prior art for preparing lithium ion battery negative material often needs complicated modification to handle, and production cost is higher, has restricted the development of lithium-ion-power cell.
Summary of the invention
The purpose of this invention is to provide a kind of electrode negative material and preparation method thereof, the technical problem that solve is the fail safe that improves lithium ion battery, reduces production costs.
The present invention is by the following technical solutions: a kind of electrode negative material, form composite material by matrix and its coating layer of coating, described matrix is that phosphorus content is in the graphite type material more than 99.9%, be shaped as sphere, axial ratio and be more than one of 1.0～4.5 spherical bulk of class and sheet, matrix contains nanometer micropore or nanoaperture, nanometer micropore or nanoaperture are of a size of 10～500nm, and porosity is 0.5～20%, and real density is 2.0～2.26g/cm
3Described coating layer is a non-graphitic carbon material, the quality of coating layer be substrate quality greater than 0 to 20%; The mean particle size D of described composite material
50Be 3.0～50.0 μ m, specific area is 1.0～20.0m
2/ g, the composite material powder compacted density is 1.50～2.15g/cm
3Described graphite type material is more than one of natural crystalloid graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite; Described non-graphitic carbon material is easy graphited soft carbon, organic substance pyrolytic carbon or vapour deposition carbon; In coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and the heavy aromatic hydrocarbon that described easily graphited soft carbon is 30～300 ℃ of softening points more than one; Described organic substance is more than one in high molecular polymer polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile, or the conductive polymer polymer is a polythiophene, polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
A kind of preparation method of electrode negative material may further comprise the steps: graphite type material is handled in one, oxidation/reduction, the speed of graphite type material with 0.1～100 ℃/min is heated up, simultaneously with 0.05～10m
3The flow of/h feeds the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, and temperature reaches 100～1000 ℃; Described graphite type material is more than one of natural crystalloid graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite; Two, be cooled to below 100 ℃, stop to feed the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas; Three, be graphite matrix with the graphite type material after oxidation/reduction processing, carry out solid phase coating or liquid phase and coat easily graphited soft carbon or organic substance pyrolytic carbon, pyrolysis becomes non-graphitic carbon material, obtains the electrode negative material, the quality of coating layer be the graphite matrix quality greater than 0 to 20%; In coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and the heavy aromatic hydrocarbon that easy graphited soft carbon is 30～300 ℃ of softening points more than one; Described organic substance is more than one in high molecular polymer polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile, or the conductive polymer polymer is a polythiophene, polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
Of the present inventionly adopt heating below 100 ℃ or vacuum drying method to make electrode negative material moisture below 0.1% to described electrode negative material.
Of the present invention described electrode negative material is removed magnetic, remove magnetic 1～20 time, magnetic flux density is 3000～30000Gs, and treatment temperature is 10～80 ℃, and it is 3～180 times/second that electromagnetic hammer H hits frequency, sieves then, obtains mean particle size D
50It is the electrode negative material of 3.0～50.0 μ m.
When graphite type material is handled in oxidation of the present invention/reduction, to rotate the furnace chamber of oxidation/reduction graphite type material greater than 0 to 20rpm rotating speed.
When graphite type material is handled in oxidation of the present invention/reduction, when temperature reaches 100～1000 ℃, be incubated greater than 0 to 6h.
Feed natural temperature reduction way in compressed-air actuated mode or the stove between the heat-conducting layer of cooling employing of the present invention in furnace wall and furnace wall.
The clad material that solid phase of the present invention coats is 1～20% of a graphite matrix quality, mixing velocity is 100～500r/min, mix and coat 5～180min, or fusion rotating speed 500～3000r/min, the gap is 0.01～1.0cm, fusion temperature is 20～80 ℃, merges to coat 10～200min, is cooled to room temperature naturally.
Liquid phase of the present invention coats, dissolved organic matter liquid-phase mixing with graphite matrix and graphite matrix quality 0.1～20%, mix stirring 10～120min with the speed of 2000～8000r/min, described liquid-phase mixing solvent is water or organic solvent, the quality of solvent is 0.8～2.0 times of graphite matrix quality, mixing temperature is 10～90 ℃, and under 80～300 ℃ of conditions, 1-30h is handled in oven dry.
A kind of preparation method of electrode negative material may further comprise the steps: graphite type material is handled in one, oxidation/reduction, the speed of graphite type material with 0.1～100 ℃/min is heated up, simultaneously with 0.05～10m
3The flow of/h feeds the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, and temperature reaches 100～1000 ℃, is incubated greater than 0 to 6h; Two, gas phase coats, and feeds the gas of carbon containing, and the feeding amount is 0.05-15m
3/ h keeps behind the 0.1-5h stopping to feed the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas below the descent of temperature to 100 ℃; The gas of described carbon containing is methane, acetylene, ethene, CO
2, in natural gas, liquefied petroleum gas, benzene and the thiophene more than one.
The present invention compared with prior art, conventional surface cladding tech is not adopted on the surface of electrode negative material, but at the surface functional group of surperficial control and treatment layer and/or coating layer, processing layer and coating layer are thin and even, have improved its stability and heat conductivity in electrolyte, have improved the fail safe of lithium ion battery, the electrode negative material also has the capacity height, the characteristics that efficient is high, preparation technology is simple, has reduced the cost of negative material.
Description of drawings
Fig. 1 is the SEM figure of the electrode negative material of embodiment 1.
Fig. 2 is the charging and discharging capacity-voltage curve of the electrode negative material of embodiment 1.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.Electrode negative material of the present invention, form composite material by matrix and its coating layer of coating, matrix is that phosphorus content is in the graphite type material more than 99.9%, be shaped as sphere, axial ratio and be more than one of 1.0～4.5 spherical bulk of class and sheet, matrix contains nanometer micropore or nanoaperture, nanometer micropore or nanoaperture are of a size of 10～500nm, and porosity (unit volume of nanometer micropore or nanoaperture volume/matrix) is 0.5～20%, and real density is 2.0～2.26g/cm
3Coating layer is a non-graphitic carbon material, coating layer account for substrate quality greater than 0 to 20%.The mean particle size D of composite material
50Be 3.0～50.0 μ m, specific area is 1.0～20.0m2/g, and the composite material powder compacted density is 1.85～2.15g/cm
3
Described graphite type material is more than one of natural crystalloid graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite.
Described non-graphitic carbon material is easy graphited soft carbon, organic substance pyrolytic carbon or vapour deposition carbon.
In coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and the heavy aromatic hydrocarbon that described easily graphited soft carbon is 30～300 ℃ of softening points more than one.
Described organic substance is high molecular polymer and conductive polymer polymer.Described high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile.Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
The preparation method of electrode negative material of the present invention obtains the electrode negative material by graphite type material being carried out oxidation/reduction, modification and coating, remove magnetic screening step, may further comprise the steps:
One, graphite type material is handled in oxidation and/or reduction, is the furnace chamber that 2.8～45.0 μ m graphite type material are put into revolving burner with granularity, with the rotating speed rotation furnace chamber of 0～20rpm, with the speed intensification of 0.1～100 ℃/min, simultaneously with 0.05～10m
3The flow of/h feeds the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, and when temperature reached 100～1000 ℃, insulation 0～6h carried out oxidation/reduction to graphite type material and handles.
Described graphite type material is more than one of natural crystalloid graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite.
Described oxidation and/or reducing gas are oxygen, air, chlorine Cl
2, bromine gas Br
2Or fluorine gas F
2, described inert gas is nitrogen or argon gas.
Two, adopt and to feed compressed air between the heat-conducting layer in furnace wall and furnace wall and carry out in temperature reduction way or the stove below the natural temperature reduction way to 100 ℃, stop to feed the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, obtain graphite matrix.
Three, the graphite matrix after oxidation and/or the reduction processing is carried out solid phase, liquid phase or gas phase and coat, obtain composite material.Clad material predecessor quality be the graphite matrix quality greater than 0 to 20%, adopt heating below 100 ℃, vacuumize or other prior aries to control the negative material moisture below 0.1%.
1, solid phase coats, the clad material predecessor is 1%～20% of a graphite matrix quality, use the accurate mixer of prior art, the mixing rotating speed is 100～500r/min, mixes to coat 5～180min, or mixture is put into the fusion machine of prior art, the fusion rotating speed is 500～3000r/min, and the gap is 0.01～1.0cm, and fusion temperature is 20～80 ℃, merge coating 10～200min, be cooled to room temperature naturally.By prior art heat treatment under 100～3000 ℃ of conditions, pyrolysis becomes non-graphitic carbon material.The clad material predecessor adopts easily graphited soft carbon, more than one in coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and the heavy aromatic hydrocarbon that easy graphited soft carbon is 30～300 ℃ of softening points.
2, liquid phase coats, and with the dissolved organic matter liquid-phase mixing of graphite matrix and graphite matrix quality 0.1～20%, adopts the high-speed stirred bucket of prior art, mixes with the speed of 2000～8000r/min and stirs 10～120min, obtains mixture.Solvent for use is water or organic solvent, and the quality of solvent is 0.8～2.0 times of graphite matrix quality, and mixing temperature is 10～90 ℃, adopts drying box, and under 80～300 ℃ of conditions, 1-30h is handled in oven dry.By prior art heat treatment under 100～3000 ℃ of conditions, pyrolysis becomes non-graphitic carbon material.Clad material adopts organic substance high molecular polymer and conductive polymer polymer.Described high molecular polymer is more than one in polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile.Described conductive polymer polymer is a polythiophene, and polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
3, the gas phase coating is after graphite type material being carried out oxidation/reduction processing, directly feeds the gas of carbon containing, and the feeding amount is 0.05-15m
3/ h keeps being cooled to naturally below 100 ℃ behind the 0.1-5h, stops to feed the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, and the predecessor that gas phase coats is that the gas of carbon containing is methane, acetylene, ethene, CO
2, in natural gas, liquefied petroleum gas, benzene and the thiophene more than one.
Four, composite material is removed magnetic, remove magnetic 1～20 time, magnetic flux density is 3000～30000Gs, and treatment temperature is 10～80 ℃, and the electromagnetic hammer striking frequency is 3～180 times/second, sieves then, obtains mean particle size D
50Be 3.0～50.0 μ m, obtain the electrode negative material.
When graphite type material is carried out oxidation/reduction and handled, after temperature reaches 100～1000 ℃, insulation 0～6h, form nanoaperture or nanometer micropore in the basis material, this micropore or hole can improve the conductivity of electrode material.
Adopt the Hitachi S4800 of Hitachi type scanning electron microscopy SEM that the electrode negative material that embodiment makes is observed.
Make the negative pole of Experimental cell of the electrode negative material of the present invention's preparation, electrode negative material and Kynoar and conductive black are mixed the mixed pulp that is dissolved in the mass concentration 10% that obtains behind the N-methyl pyrrolidone mutually according to 98: 2 mass ratio, evenly be coated on the thick Copper Foil of 10 μ m, compacting in flakes, make the carbon membrane of diameter 1cm then, in 120 ℃ of following 12h dry for standby of drying box.Pole piece with above-mentioned preparation is a work electrode, and metal lithium sheet is as auxiliary electrode and reference electrode, and adopting volume ratio is that EC, the DMC that mixes at 1: 1: 1, the concentration that the EMC solvent is made are the LiPF of 1mol/L
6As electrolyte, the preparation internal diameter is the simulated battery of Φ 12mm in being full of the glove box of argon gas.On the blue electric battery test system CT2001C of Wuhan Jin Nuo Electronics Co., Ltd., carry out the charge-discharge test of battery, charging/discharging voltage scope: 0.01V～2.0V, electric current is 0.2C, according to GB/T 24533-2009 silicon/carbon/graphite in lithium ion batteries class negative material method of testing test capacity and efficient.
The thermal stability of battery adopts the capability retention that 1C charges and discharge under 45 ℃ of conditions of high temperature to investigate, and capability retention is high more, and thermal stability is good more.
The technological parameter of embodiment 1-6 and Comparative Examples 1 is listed in table 1, for convenience relatively, embodiment 1-6 and Comparative Examples 1 to remove the magnetic technological parameter identical.The electric performance test of embodiment 1-6 and Comparative Examples 1 the results are shown in table 2.
As shown in Figure 1, with graphite matrix D
50=19.2um material carries out carrying out after surface oxidation/reduction is handled liquid phase and coats 0.5% polypyrrole, and the material specific area that obtains after 150 ℃ of heat treatment is 5.26m
2/ g, powder pressing are 1.90g/cm
3SEM shows, the graphite matrix particle is spherical and class spherical form, and surface oxidation and/or reduction processing layer and coating layer are even, and the surface is owing to carrying out oxidation and/or reducing and handle, surface group reduces, reduced the reaction under low current potential, Gu the Heat stability is good in electrolyte, the side reaction of electrolyte and oxidation and/or reduction processing layer and cover surface is few, the SEI film is stable, Gu the high temperature circulation of battery is good.100 all capability retentions are 95% under 45 ℃.
As shown in Figure 2, through the graphite type material that embodiment 1 handles, capacity is at 364.69mAh/g, and efficient is 90.18%.
Method of the present invention not only has the simple advantage of treatment process, and as can be seen from Table 2, the electrode negative material of method preparation of the present invention also has the capacity height, the characteristics that efficient is high.
The technological parameter of table 1 embodiment 1-6 and Comparative Examples 1
The electric performance test result of table 2 embodiment 1-6 and Comparative Examples 1
Claims (10)
1. an electrode negative material is formed composite material by matrix and its coating layer of coating, it is characterized in that:
Described matrix is that phosphorus content is in the graphite type material more than 99.9%, be shaped as sphere, axial ratio and be more than one of 1.0～4.5 spherical bulk of class and sheet, matrix contains nanometer micropore or nanoaperture, nanometer micropore or nanoaperture are of a size of 10～500nm, porosity is 0.5～20%, and real density is 2.0～2.26g/cm
3Described coating layer is a non-graphitic carbon material, the quality of coating layer be substrate quality greater than 0 to 20%; The mean particle size D of described composite material
50Be 3.0～50.0 μ m, specific area is 1.0～20.0m
2/ g, the composite material powder compacted density is 1.50～2.15g/cm
3Described graphite type material is more than one of natural crystalloid graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite; Described non-graphitic carbon material is easy graphited soft carbon, organic substance pyrolytic carbon or vapour deposition carbon; In coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and the heavy aromatic hydrocarbon that described easily graphited soft carbon is 30～300 ℃ of softening points more than one; Described organic substance is more than one in high molecular polymer polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile, or the conductive polymer polymer is a polythiophene, polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
2. the preparation method of an electrode negative material may further comprise the steps: one, graphite type material is handled in oxidation and/or reduction, the speed of graphite type material with 0.1～100 ℃/min is heated up, simultaneously with 0.05～10m
3The flow of/h feeds the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, and temperature reaches 100～1000 ℃; Described graphite type material is more than one of natural crystalloid graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite; Two, be cooled to below 100 ℃, stop to feed the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas; Three, be graphite matrix with the graphite type material after oxidation/reduction processing, carry out solid phase and coat easily graphited soft carbon or liquid phase coating organic substance pyrolytic carbon, pyrolysis becomes non-graphitic carbon material, obtains the electrode negative material, the quality of coating layer be the graphite matrix quality greater than 0 to 20%; In coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and the heavy aromatic hydrocarbon that easy graphited soft carbon is 30～300 ℃ of softening points more than one; Described organic substance is more than one in high molecular polymer polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and the polyacrylonitrile, or the conductive polymer polymer is a polythiophene, polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten in fen, polyhenylene, polyphenylene ethylene and the poly-two alkynes more than one.
3. the preparation method of electrode negative material according to claim 2 is characterized in that: adopt heating below 100 ℃ or vacuum drying method to make electrode negative material moisture below 0.1% to described electrode negative material.
4. the preparation method of electrode negative material according to claim 2, it is characterized in that: remove magnetic sieving after the described electrode negative material drying, remove magnetic 1～20 time, magnetic flux density is 3000～30000Gs, treatment temperature is 10～80 ℃, the electromagnetic hammer striking frequency is 3～180 times/second, sieves then, obtains mean particle size D
50It is the electrode negative material of 3.0～50.0 μ m.
5. the preparation method of electrode negative material according to claim 2 is characterized in that: when graphite type material is handled in described oxidation/reduction, to rotate the furnace chamber of oxidation/reduction graphite type material greater than 0 to 20rpm rotating speed.
6. the preparation method of electrode negative material according to claim 2 is characterized in that: when graphite type material is handled in described oxidation/reduction, when temperature reaches 100～1000 ℃, be incubated greater than 0 to 6h.
7. the preparation method of electrode negative material according to claim 2 is characterized in that: feed natural temperature reduction way in compressed-air actuated mode or the stove between the heat-conducting layer of described cooling employing in furnace wall and furnace wall.
8. the preparation method of electrode negative material according to claim 2, it is characterized in that: the clad material that described solid phase coats is 1～20% of a graphite matrix quality, mixing velocity is 100～500r/min, mix and coat 5～180min, or merge rotating speed 500～3000r/min, and the gap is 0.01～1.0cm, fusion temperature is 20～80 ℃, merge coating 10～200min, be cooled to room temperature naturally.
9. the preparation method of electrode negative material according to claim 2, it is characterized in that: described liquid phase coats, dissolved organic matter liquid-phase mixing with graphite matrix and graphite matrix quality 0.1～20%, mix stirring 10～120min with the speed of 2000～8000r/min, described liquid-phase mixing solvent is water or organic solvent, and the quality of solvent is 0.8～2.0 times of graphite matrix quality, and mixing temperature is 10～90 ℃, under 80～300 ℃ of conditions, 1-30h is handled in oven dry.
10. the preparation method of an electrode negative material may further comprise the steps: one, graphite type material is handled in oxidation and/or reduction, the speed of graphite type material with 0.1～100 ℃/min is heated up, simultaneously with 0.05～10m
3The flow of/h feeds the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas, and temperature reaches 100～1000 ℃, is incubated greater than 0 to 6h; Two, gas phase coats, and feeds the gas of carbon containing, and the feeding amount is 0.05-15m
3/ h keeps behind the 0.1-5h stopping to feed the mist of oxidation/reducing gas or oxidation/reducing gas and inert gas below the descent of temperature to 100 ℃; The gas of described carbon containing is methane, acetylene, ethene, CO
2, in natural gas, liquefied petroleum gas, benzene and the thiophene more than one.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110258926.7A CN102299307B (en) | 2011-09-03 | 2011-09-03 | Electrode anode material and preparation method thereof |
| KR1020137000662A KR101439068B1 (en) | 2011-09-03 | 2011-12-02 | Negative electrode material of electrode and preparing method therefor |
| JP2013530531A JP5509458B2 (en) | 2011-09-03 | 2011-12-02 | Negative electrode material and manufacturing method thereof |
| PCT/CN2011/002024 WO2013029211A1 (en) | 2011-09-03 | 2011-12-02 | Negative electrode material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110258926.7A CN102299307B (en) | 2011-09-03 | 2011-09-03 | Electrode anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN102299307A true CN102299307A (en) | 2011-12-28 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011370A1 (en) * | 2002-07-30 | 2004-02-05 | Jfe Chemical Corporation | Composite graphite material and its production method, negative plate material using same, negative plate, and lithium ion secondary cell |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| CN101323447A (en) * | 2008-07-21 | 2008-12-17 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite powder of lithium ionic cell cathode and preparation thereof |
| CN101916847A (en) * | 2010-08-19 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material for lithium ion power battery and preparation method thereof |
| CN101916846A (en) * | 2010-08-19 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode composite material and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3305995B2 (en) * | 1996-12-26 | 2002-07-24 | 日立化成工業株式会社 | Graphite particles for lithium secondary battery negative electrode |
| US6391495B1 (en) * | 1998-11-25 | 2002-05-21 | Samsung Display Devices Co., Ltd. | Negative active material for lithium secondary battery, method of preparing the same and lithium secondary battery comprising the same |
| JP2001143691A (en) * | 1999-11-12 | 2001-05-25 | Osaka Gas Co Ltd | Graphite carbon material, method for manufacturing the same, negative electrode material for lithium secondary cell and lithium secondary cell |
| JP2002222650A (en) | 2001-01-25 | 2002-08-09 | Hitachi Chem Co Ltd | Black lead nature particle for negative electrode of non-aqueous electrolytic solution secondary battery and its manufacturing process, negative electrode of the non-aqueous electrolytic solution secondary battery and the non-aqueous electrolytic solution secondary battery |
| JP2002241117A (en) * | 2001-02-13 | 2002-08-28 | Osaka Gas Co Ltd | Graphite based carbon material, manufacturing method therefor, negative electrode material for lithium secondary battery, and lithium secondary battery |
| JP2003168429A (en) * | 2001-11-29 | 2003-06-13 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| CN100338802C (en) * | 2005-04-20 | 2007-09-19 | 深圳市贝特瑞电子材料有限公司 | Cathode material of lithium ion cell and preparation method thereof |
| CN100350654C (en) * | 2005-04-20 | 2007-11-21 | 深圳市贝特瑞电子材料有限公司 | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof |
| CN1913200B (en) | 2006-08-22 | 2010-05-26 | 深圳市贝特瑞电子材料有限公司 | Silicon carbone compound negative polar material of lithium ion battery and its preparation method |
| JP5623198B2 (en) * | 2010-09-06 | 2014-11-12 | 株式会社Ｎｔｔファシリティーズ | Non-aqueous electrolyte battery |
-
2011
- 2011-09-03 CN CN201110258926.7A patent/CN102299307B/en active Active
- 2011-12-02 JP JP2013530531A patent/JP5509458B2/en active Active
- 2011-12-02 KR KR1020137000662A patent/KR101439068B1/en active IP Right Grant
- 2011-12-02 WO PCT/CN2011/002024 patent/WO2013029211A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011370A1 (en) * | 2002-07-30 | 2004-02-05 | Jfe Chemical Corporation | Composite graphite material and its production method, negative plate material using same, negative plate, and lithium ion secondary cell |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| CN101323447A (en) * | 2008-07-21 | 2008-12-17 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite powder of lithium ionic cell cathode and preparation thereof |
| CN101916847A (en) * | 2010-08-19 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material for lithium ion power battery and preparation method thereof |
| CN101916846A (en) * | 2010-08-19 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode composite material and preparation method thereof |
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Also Published As
| Publication number | Publication date |
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| WO2013029211A1 (en) | 2013-03-07 |
| CN102299307B (en) | 2014-01-01 |
| JP5509458B2 (en) | 2014-06-04 |
| KR101439068B1 (en) | 2014-09-05 |
| KR20130046423A (en) | 2013-05-07 |
| JP2013542559A (en) | 2013-11-21 |
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