CN102299307B - Electrode anode material and preparation method thereof - Google Patents
Electrode anode material and preparation method thereof Download PDFInfo
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- CN102299307B CN102299307B CN201110258926.7A CN201110258926A CN102299307B CN 102299307 B CN102299307 B CN 102299307B CN 201110258926 A CN201110258926 A CN 201110258926A CN 102299307 B CN102299307 B CN 102299307B
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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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- 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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- 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 for lithium ion battery and preparation method thereof.
Background technology
Along with the fast development of national economy and the raising of living standards of the people, China grows with each passing day to the dependency degree of crude oil, Chinese energy safety is formed directly and threatens.In addition, the price fluctuation of crude oil also directly has influence on the development of national economy, forces people to have to find 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 electrokinetic cell.Lithium ion battery, with the excellent properties of the aspects such as its high-energy-density, high voltage, pollution-free, the long circulation life that is greater than 500 circulations, fast charging and discharging and the cost of manufacture increasingly reduced, progressively becomes the first-selected battery of electric motor car in following 10～20 years.It is more expensive that but its shortcoming is price.In addition, the volume of power-type lithium ion battery is larger, and security performance is the phase strain differential also.As can be seen here, 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 important impact to the final price of battery, and its stability in electrolyte and heat conductivity also have a great impact the fail safe of battery.Prior art prepares lithium ion battery negative material and often needs complicated modification, 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 anode 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 anode 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 more than one of the spherical bulk of class spherical, that axial ratio is 1.0～4.5 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
3; Described coating layer is non-graphitic carbon material, and what the quality of coating layer was substrate quality is 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
3; Described graphite type material is more than one of natural Scaly 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 matter pyrolysis charcoal or vapour deposition carbon; More than one in coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and heavy aromatic hydrocarbon that described easily graphited soft carbon is 30～300 ℃ of softening points; Described organic substance is more than one in high molecular polymer polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and polyacrylonitrile, or the conductive polymer polymer is polythiophene, polyaniline, polyacetylene, polypyrrole, coalescence benzene, poly-bite more than one in fen, polyhenylene, polyphenylene ethylene and poly-two alkynes.
A kind of preparation method of electrode anode material comprises the following steps: one, oxidation/reduction is processed graphite type material, and the speed by graphite type material with 0.1～100 ℃/min heats up, simultaneously with 0.05～10m
3the flow of/h passes into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas, and temperature reaches 100～1000 ℃; Described graphite type material is more than one of natural Scaly graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite; Two, be cooled to below 100 ℃, stop passing into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas; Three, take the graphite type material of oxidation/reduction after processing is graphite matrix, carry out solid phase coating or liquid phase coating easily graphited soft carbon or organic matter pyrolysis charcoal, pyrolysis becomes non-graphitic carbon material, obtains electrode anode material, the quality of coating layer be the graphite matrix quality be greater than 0 to 20%; More than one in coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and heavy aromatic hydrocarbon that easy graphited soft carbon is 30～300 ℃ of softening points; Described organic substance is more than one in high molecular polymer polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly(ethylene oxide), Kynoar, acrylic resin and polyacrylonitrile, or the conductive polymer polymer is polythiophene, polyaniline, polyacetylene, polypyrrole, coalescence benzene, poly-bite more than one in fen, polyhenylene, polyphenylene ethylene and poly-two alkynes.
Of the present inventionly to described electrode anode material, adopt heating below 100 ℃ or vacuum drying method to make the electrode anode material moisture below 0.1%.
Of the present invention described electrode anode material is removed to magnetic, except 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, is then sieved, and obtains mean particle size D
50it is the electrode anode material of 3.0～50.0 μ m.
When oxidation/reduction of the present invention is processed graphite type material, to be greater than the furnace chamber of 0 to 20rpm rotating speed rotation oxidation/reduction graphite type material.
When oxidation/reduction of the present invention is processed graphite type material, when temperature reaches 100～1000 ℃, insulation is greater than 0 to 6h.
Cooling of the present invention adopts between the heat-conducting layer in furnace wall and furnace wall the mode of naturally lowering the temperature in compressed-air actuated mode or stove that passes into.
The clad material that solid phase of the present invention coats is 1～20% of graphite matrix quality, mixing velocity is 100～500r/min, mix and coat 5～180min, or fusion rotating speed 500～3000r/min, gap is 0.01～1.0cm, fusion temperature is 20～80 ℃, merges and coats 10～200min, naturally is cooled to room temperature.
Liquid phase coating of the present invention, graphite matrix is mixed with the dissolved organic matter liquid phase of graphite matrix quality 0.1～20%, speed mix and blend 10～120min with 2000～8000r/min, it is water or organic solvent with solvent that described liquid phase is mixed, the quality of solvent is 0.8～2.0 times of graphite matrix quality, mixing temperature is 10～90 ℃, under 80～300 ℃ of conditions, and drying and processing 1-30h.
A kind of preparation method of electrode anode material comprises the following steps: one, oxidation/reduction is processed graphite type material, and the speed by graphite type material with 0.1～100 ℃/min heats up, simultaneously with 0.05～10m
3the flow of/h passes into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas, and temperature reaches 100～1000 ℃, and insulation is greater than 0 to 6h; Two, gas phase coats, and passes into the gas of carbon containing, and intake is 0.05-15m
3/ h, keep after 0.1-5h, below descent of temperature to 100 ℃, stopping passing into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas; The gas of described carbon containing is methane, acetylene, ethene, CO
2, more than one in natural gas, liquefied petroleum gas, benzene and thiophene.
The present invention compared with prior art, the surface of electrode anode material does not adopt conventional surface cladding tech, but control the surface functional group of processing layer and/or coating layer on surface, 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, it is high that electrode anode material also has a capacity, the characteristics that efficiency is high, preparation technology is simple, has reduced the cost of negative material.
The accompanying drawing explanation
Fig. 1 is the SEM figure of the electrode anode material of embodiment 1.
Fig. 2 is the charging and discharging capacity-voltage curve of the electrode anode material of embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.Electrode anode 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 more than one of the spherical bulk of class spherical, that axial ratio is 1.0～4.5 and sheet, matrix contains nanometer micropore or nanoaperture, nanometer micropore or nanoaperture are of a size of 10～500nm, porosity (unit volume of nanometer micropore or nanoaperture volume/matrix) is 0.5～20%, and real density is 2.0～2.26g/cm
3.Coating layer is non-graphitic carbon material, and what coating layer accounted for substrate quality is 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 Scaly 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 matter pyrolysis charcoal or vapour deposition carbon.
More than one in coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and heavy aromatic hydrocarbon that described easily graphited soft carbon is 30～300 ℃ of softening points.
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 polyacrylonitrile.Described conductive polymer polymer is polythiophene, and polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten more than one in fen, polyhenylene, polyphenylene ethylene and poly-two alkynes.
The preparation method of electrode anode material of the present invention, by graphite type material being carried out to oxidation/reduction, modification coating, except magnetic sieves step, obtaining electrode anode material, comprises the following steps:
One, graphite type material is processed in oxidation and/or reduction, by granularity, is the furnace chamber that 2.8～45.0 μ m graphite type material are put into revolving burner, 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 passes into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas, when temperature reaches 100～1000 ℃, is incubated 0～6h, and graphite type material is carried out to the oxidation/reduction processing.
Described graphite type material is more than one of natural Scaly 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 between the heat-conducting layer in furnace wall and furnace wall and pass into below the mode to 100 of naturally lowering the temperature in mode that compressed air lowered the temperature or stove ℃, stop passing into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas, obtain graphite matrix.
Three, the graphite matrix after oxidation and/or reduction processing is carried out to solid phase, liquid phase or gas phase and coat, obtain composite material.Clad material predecessor quality be the graphite matrix quality be 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 graphite matrix quality, use the accurate mixer of prior art, the mixing rotating speed is 100～500r/min, mixes and coats 5～180min, or mixture is put into to the fusion machine of prior art, the fusion rotating speed is 500～3000r/min, and gap is 0.01～1.0cm, and fusion temperature is 20～80 ℃, merge and coat 10～200min, naturally be cooled to room temperature.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 heavy aromatic hydrocarbon that easy graphited soft carbon is 30～300 ℃ of softening points.
2, liquid phase coating, mix graphite matrix with the dissolved organic matter liquid phase of graphite matrix quality 0.1～20%, adopt the high-speed stirred bucket of prior art, and the speed mix and blend 10～120min with 2000～8000r/min, obtain 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, under 80～300 ℃ of conditions, and drying and processing 1-30h.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 polyacrylonitrile.Described conductive polymer polymer is polythiophene, and polyaniline, polyacetylene, polypyrrole, coalescence benzene poly-are bitten more than one in fen, polyhenylene, polyphenylene ethylene and poly-two alkynes.
3, the gas phase coating is after graphite type material is carried out to the oxidation/reduction processing, directly passes into the gas of carbon containing, and intake is 0.05-15m
3/ h keeps naturally being cooled to below 100 ℃ after 0.1-5h, stops passing into the mist of oxidation/reduction gas or oxidation/reduction gas and inert gas, and the predecessor that gas phase coats is that the gas of carbon containing is methane, acetylene, ethene, CO
2, more than one in natural gas, liquefied petroleum gas, benzene and thiophene.
Four, composite material is removed to 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, is then sieved, and obtains mean particle size D
50be 3.0～50.0 μ m, obtain electrode anode material.
Graphite type material is carried out to oxidation/reduction while processing, after temperature reaches 100～1000 ℃, is incubated 0～6h, form nanoaperture or nanometer micropore in basis material, this micropore or hole can improve the conductivity of electrode material.
The electrode anode material that adopts the Hitachi S4800 of Hitachi type scanning electron microscopy SEM to make embodiment is observed.
The electrode anode material prepared with the present invention is made the negative pole of experimental cell, electrode anode material is dissolved in to the mixing slurry of the mass concentration 10% obtained after 1-METHYLPYRROLIDONE mutually with Kynoar and conductive black according to the mass ratio mixing of 98: 2, evenly be coated on the Copper Foil that 10 μ m are thick, compacting in flakes, then make the carbon membrane of diameter 1cm, in 120 ℃ of lower 12h dry for standby of drying box.The pole piece of above-mentioned preparation of take is work electrode, and metal lithium sheet is as auxiliary electrode and reference electrode, adopts the LiPF that volume ratio is the EC, the DMC that mix at 1: 1: 1, the EMC solvent is made concentration is 1mol/L
6as electrolyte, prepare the simulated battery that internal diameter is Φ 12mm in being full of the glove box of argon gas.Carry out the charge-discharge test of battery on the indigo plant electricity battery test system CT2001C of Wuhan Jin Nuo Electronics Co., Ltd., 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 efficiency.
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 higher, and thermal stability is better.
The technological parameter of embodiment 1-6 and Comparative Examples 1 is listed in table 1, for convenient relatively, embodiment 1-6 and Comparative Examples 1 except 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, by graphite matrix D
50=19.2um material carries out after surface oxidation/reduction is processed carrying out the polypyrrole of liquid phase coating 0.5%, and the material specific area obtained after 150 ℃ of heat treatment is 5.26m
2/ g, powder pressing is 1.90g/cm
3sEM shows, the graphite matrix particle is spherical and the class spherical form, and surface oxidation and/or reduction processing layer and coating layer are even, and surface is owing to carrying out oxidation and/or reduction processing, 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.Under 45 ℃, 100 weeks capability retentions are 95%.
As shown in Figure 2, the graphite type material of processing through embodiment 1, capacity is at 364.69mAh/g, and efficiency is 90.18%.
Method of the present invention not only has the simple advantage for the treatment of process, and as can be seen from Table 2, it is high that electrode anode material prepared by method of the present invention also has a capacity, the characteristics that efficiency 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 (1)
1. the preparation method of an electrode anode material comprises the following steps:
One, graphite type material is processed in oxidation and/or reduction, by granularity, is the furnace chamber that 2.8～45.0 μ m graphite type material are put into revolving burner, to be greater than 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 passes into oxidation and/or reducing gas, or the mist of oxidation and/or reducing gas and inert gas, and when temperature reaches 100～1000 ℃, insulation is greater than 0～6h, forms nanoaperture or nanometer micropore;
Described graphite type material is more than one of natural Scaly graphite, natural cryptocrystal graphite, natural crystallization veiny graphite, Delanium, carbosphere and electrically conductive graphite;
Two, pass into compressed air between the heat-conducting layer of employing in furnace wall and furnace wall and be cooled to below 100 ℃, stop passing into oxidation and/or reducing gas, or the mist of oxidation and/or reducing gas and inert gas, graphite matrix obtained;
Three, the graphite matrix after oxidation and/or reduction are processed carries out the solid phase coating, heat treatment under 100～3000 ℃ of conditions, pyrolysis becomes non-graphitic carbon material, obtains composite material, wherein, the predecessor quality of clad material be the graphite matrix quality be greater than 0 to 20%; Adopt heating below 100 ℃ or vacuumize to control the composite material moisture below 0.1%;
Described solid phase coats, and graphite matrix and easy graphited soft carbon are put into to mixer, and mixing rotating speed is 100～500 r/min, mixes and coats 5～180min; Or graphite matrix and easy graphited soft carbon are put into to the fusion machine, and merging rotating speed is 500～3000 r/min, and gap is 0.01～1.0cm, and fusion temperature is 20～80 ℃, merges and coats 10～200min, naturally is cooled to room temperature;
More than one in coal tar pitch, petroleum asphalt, coal tar, petroleum industry mink cell focus and heavy aromatic hydrocarbon that described easily graphited soft carbon is 30～300 ℃ of softening points;
Four, composite material is removed to 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, is then sieved, and obtains mean particle size D
50it is the electrode anode material of 3.0～50.0 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110258926.7A CN102299307B (en) | 2011-09-03 | 2011-09-03 | Electrode anode material and preparation method thereof |
| JP2013530531A JP5509458B2 (en) | 2011-09-03 | 2011-12-02 | Negative electrode material and manufacturing method thereof |
| KR1020137000662A KR101439068B1 (en) | 2011-09-03 | 2011-12-02 | Negative electrode material of electrode and preparing method therefor |
| PCT/CN2011/002024 WO2013029211A1 (en) | 2011-09-03 | 2011-12-02 | Negative electrode material and preparation method therefor |
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| CN201110258926.7A CN102299307B (en) | 2011-09-03 | 2011-09-03 | Electrode anode material and preparation method thereof |
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| CN102299307B true CN102299307B (en) | 2014-01-01 |
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| JP6497462B1 (en) | 2018-03-30 | 2019-04-10 | 住友大阪セメント株式会社 | Lithium ion battery electrode material and lithium ion battery |
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| CN109671974A (en) * | 2018-12-10 | 2019-04-23 | 江苏天鹏电源有限公司 | A kind of low temperature fast charge long-life high power dynamic lithium battery |
| CN110380050B (en) * | 2019-06-06 | 2021-05-18 | 湖南中科星城石墨有限公司 | Mixing process for preparing high-tap microcrystalline graphite negative electrode material |
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| CN101916846B (en) * | 2010-08-19 | 2012-12-05 | 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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