CN104319373A - Simple preparation method of silicon-based lithium ion battery anode material - Google Patents
Simple preparation method of silicon-based lithium ion battery anode material Download PDFInfo
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- CN104319373A CN104319373A CN201410563039.4A CN201410563039A CN104319373A CN 104319373 A CN104319373 A CN 104319373A CN 201410563039 A CN201410563039 A CN 201410563039A CN 104319373 A CN104319373 A CN 104319373A
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- ion battery
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a lithium ion battery anode. The method comprises the following steps: step 1, dispersing silicon-based powder into an organic solvent to obtain a dispersion solution of the silicon-based powder; step 2, mixing polyacrylonitrile or asphalt polymer with the organic solvent, stirring the polyacrylonitrile or asphalt polymer and the organic solvent under a given temperature until the polyacrylonitrile or asphalt polymer is dissolved to obtain an organic solvent mixture; step 3, mixing the dispersion solution of the silicon-based powder and the organic solvent mixture to obtain a sizing agent; step 4, coating a current collector by the sizing agent with a predetermined thickness; step 5, drying; and step 6, sintering the dried current collector which is coated by the sizing agent under the given temperature to form the lithium ion battery anode. The preparation method has advantages of simple preparation process, low cost and easiness in realization.
Description
Technical field
The present invention proposes a kind of simply with the design philosophy of the silica-based powder lithium ion battery negative that is active material and preparation method.In particular to using silica-based powder as lithium ion battery negative pole active materials, the carbon fiber obtained after polymer sintering, as conductive materials and coherent network, prepares the straightforward procedure of electrode.
Background technology
Due to information industry, the communications industry, mobile device, electronic device, the fast development of electronic transit equipment, exploitation low-power consumption, jumbo portable power source is very urgent.Lithium ion battery then causes the research enthusiasm of people as indispensable role.Silicon materials are as lithium ion battery negative material, its theoretical capacity can reach 4200mAhg-1 (Journal of The Electrochemical Society, 151, A838.), being only second to lithium metal, is ten times more than of the graphite material generally applied now.Silicon materials can also provide very long discharge platform, ensure stable output voltage.Abundance very high in the earth's crust also makes silicon materials have more competitiveness.But, because huge volumetric expansion (~ 400%) (Nature nanotechnology, 3 can occur silicon materials in charging process, 31,2007.), this will cause material rapid efflorescence in charge and discharge process, thus cause capacity attenuation, final electrode failure.People have used various method to solve the problem of silicon materials in charge and discharge process, as taked nanometer materials (Nature nanotechnology, 3,31,2007; ChemSusChem; 6; 2144,2013.) or loose structure (Journal of power sources, 139; 314; 2005.) to alleviate dimensional effect, silicon materials (Journal of Materials Chemistry, 17 are protected with composite construction; 1321,2007.) etc.But for the material of nanostructure, the complicated and high cost of preparation hinders its commercialization, and meet match materials and uniformity also has much room for improvement.Chinese patent CN103762367 provides a kind of sodium alginate that adopts as the preparation method of the silica-based lithium ion battery negative of binding agent.Although this method can utilize binding agent to protect silicon materials, complicated process of preparation, and the insulating properties of sodium alginate binding agent can reduce electrode conductivity, hinder electric transmission.Chinese patent CN102623682A provides the preparation method of the silica-based carbon composite of a kind of lithium ion battery negative.This method take silica flour as major ingredient, with graphite powder or cotton-shaped carbon black for auxiliary material, carries out high-energy ball milling after mixing, obtains the powder that granularity is less than 20 μm and is lithium ion battery negative Si-C composite material.This method can improve the electric conductivity of electrode material, but silica flour and carbon dust just simply mix, and can not reduce the resistance of electronics in intergranular jump process; And in the process of further assembled battery, also to introduce the binding agent of insulation.And the preparation method of this patent, simple to operate, cost is low, is electric conducting material after polymer sintering, silica-based powder can be bonded together again, greatly will certainly promote its application in lithium ion battery.
Summary of the invention
The object of the invention is to provide the preparation method of a kind of silica-based powder as the lithium ion battery negative of active material.The method preparation technology is simple, and cost is low, is easy to realize.
The invention provides a kind of preparation method of lithium ion battery negative, comprise the steps:
Step 1: by silica-based powder dispersion in organic solvent, obtains the dispersion liquid of silica-based powder;
Step 2: polyacrylonitrile or asphalt polymer are mixed with organic solvent, and stir at a predetermined temperature until dissolve, obtain ORGANIC SOLVENT MIXTURES;
Step 3: by the dispersion liquid of silica-based powder and ORGANIC SOLVENT MIXTURES mixing, obtain slurry;
Step 4: slurry is coated on a collector with a predetermined thickness;
Step 5: dry;
Step 6: sintered at a predetermined temperature by the collector being coated with slurry of drying, forms lithium ion battery negative, completes preparation.
The invention has the beneficial effects as follows, have preparation technology simple, cost is low, is easy to the advantage realized.
Accompanying drawing explanation
In order to concrete technology contents of the present invention is described, be described in detail as follows below in conjunction with instantiation and diagram, wherein:
Fig. 1 is method flow diagram of the present invention;
Fig. 2 is the schematic diagram before and after the mixture sintering of silica-based powder and polymer;
Fig. 3 is that the SEM after the mixture sintering of silica-based powder and polymer schemes;
Fig. 4 is the charge/discharge cycle characteristics of sintering rear electrode sheet assembled battery.
Embodiment
Refer to shown in Fig. 1, the invention provides a kind of preparation method of lithium ion battery negative, it is simple that the method has preparation technology, and cost is low, is easy to the advantage realized.Comprise the steps:
Step 1: by silica-based powder dispersion in organic solvent, obtains the dispersion liquid of silica-based powder, and the material of described silica-based powder is silicon materials, silicon germanium material or silicon carbon material, or and mixing, this silica-base material is polycrystalline or monocrystal material.Silicon materials have the high feature of lithium ion capacity, can realize the preparation of high capacity lithium ion battery.Silicon germanium material has the high feature of lithium ionic mobility, contributes to the preparation realizing powerful lithium ion battery.Polysilicon based powdered material price is low, can realize low cost and prepare lithium ion battery.This silica-base material is added with graphite material, carbon black, Graphene, graphite fibre, copper powders or copper nano-wire, or and composite material.The material added can increase the conductivity of electrode, and the internal resistance of battery is reduced.Have pulverous in the material added, as carbon black, copper powders, can fill the space of silica-based dusty material to reduce electronic resistance; Have wire, as graphite fibre, copper nano-wire, can form conductive network in the electrodes, thus reduces resistance.This silica-based powder is of a size of 10nm-50 μm in the electrodes, and described organic solvent is dimethyl formamide or dimethylacetylamide, and silica-based powder can by ultrasonic good dispersion wherein;
Step 2: polyacrylonitrile (PAN) or asphalt polymer are mixed with organic solvent, and stir at a predetermined temperature until dissolve, obtain ORGANIC SOLVENT MIXTURES.PAN or asphalt polymer can dissolve in organic solvent completely, and form the liquid of thickness.Described whipping temp is 10-90 DEG C;
The ratio of described silica-based powder and polymer is 1: 9-9: 1.
Step 3: by the dispersion liquid of silica-based powder and ORGANIC SOLVENT MIXTURES mixing, obtain slurry.Slurry is the liquid of thickness.In the slurry, the effect of silica-based powder is the active material as lithium ion battery electrode material, and polymer is the binding agent as lithium ion battery electrode material;
Step 4: be coated on a collector with a predetermined thickness by slurry, coating process should ensure that slurry is uniformity at the thickness of various piece, more stable to ensure the performance of battery like this.Described collector is conventional lithium ion battery negative collector, and the material of this negative current collector is copper, and copper redox reaction can not occur in the voltage range of negative reaction, thus ensures that battery performance is stablized.On described collector, the thickness of coating sizing-agent is 10 μm of-1mm, and when being coated with thinner, cycle performance of battery is better, and when coating is thicker, battery capacity is higher, and selected coating thickness is selected after should weighing;
Step 5: dry.Organic solvent in slurry can volatilize by drying course completely, obtains the collector of solid;
Step 6: sintered at a predetermined temperature by the collector being coated with slurry of drying, forms lithium ion battery negative (consulting Fig. 3).Sintering process can change the structure (consulting Fig. 2) of PAN or asphalt polymer, the structure of polymer is become netted from chain, can more firmly silicon bonded based powders, and the component of sintering post-consumer polymer changes, conductivity becomes large, also can play electric action in the electrodes.Described sintering temperature is 300-800 DEG C, completes preparation.
Fig. 4 is the loop test result of the electrode assembling battery prepared by this method.Battery coulombic efficiency in all cyclic processes of head is lower, is 67%, but arrives 99% at the 5th week, and keeps stable in cyclic process afterwards.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for lithium ion battery negative, comprises the steps:
Step 1: by silica-based powder dispersion in organic solvent, obtains the dispersion liquid of silica-based powder;
Step 2: polyacrylonitrile or asphalt polymer are mixed with organic solvent, and stir at a predetermined temperature until dissolve, obtain ORGANIC SOLVENT MIXTURES;
Step 3: by the dispersion liquid of silica-based powder and ORGANIC SOLVENT MIXTURES mixing, obtain slurry;
Step 4: slurry is coated on a collector with a predetermined thickness;
Step 5: dry;
Step 6: sintered at a predetermined temperature by the collector being coated with slurry of drying, forms lithium ion battery negative, completes preparation.
2. the preparation method of lithium ion battery negative according to claim 1, the material of wherein said silica-based powder is silicon materials, silicon germanium material or silicon carbon material, or and mixing, this silica-base material is polycrystalline or monocrystal material, this silica-base material is added with graphite material, carbon black, Graphene, graphite fibre, copper powders or copper nano-wire, or and composite material.
3. the preparation method of lithium ion battery negative according to claim 2, wherein this silica-based powder is of a size of 10nm-50 μm.
4. the preparation method of lithium ion battery negative according to claim 1, wherein organic solvent is dimethyl formamide or dimethylacetylamide.
5. the preparation method of lithium ion battery negative according to claim 1, wherein said whipping temp is 10-90 DEG C.
6. the preparation method of lithium ion battery negative according to claim 1, the ratio of wherein said silica-based powder and polymer is 1: 9-9: 1, and described collector is conventional lithium ion battery negative collector, and the material of this negative current collector is copper.
7. the preparation method of lithium ion battery negative according to claim 1, wherein on collector, the thickness of coating sizing-agent is 10 μm of-1mm.
8. the preparation method of lithium ion battery negative according to claim 1, wherein said sintering temperature is 300-800 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109994723A (en) * | 2019-04-04 | 2019-07-09 | 常州大学 | A kind of SiOxThe preparation method of-G/PAA-PANi/Cu composite material |
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
| CN113574696A (en) * | 2019-02-08 | 2021-10-29 | 株式会社Lg新能源 | Negative electrode and lithium secondary battery comprising same |
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| US20040072067A1 (en) * | 2002-09-30 | 2004-04-15 | Hiroshi Minami | Lithium secondary battery and method for manufacturing thereof |
| CN101276908A (en) * | 2007-03-29 | 2008-10-01 | Tdk株式会社 | Production method of active material, and active material |
| CN103890915A (en) * | 2011-08-19 | 2014-06-25 | 威廉马歇莱思大学 | Anode battery materials and methods of making the same |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040072067A1 (en) * | 2002-09-30 | 2004-04-15 | Hiroshi Minami | Lithium secondary battery and method for manufacturing thereof |
| CN101276908A (en) * | 2007-03-29 | 2008-10-01 | Tdk株式会社 | Production method of active material, and active material |
| CN103890915A (en) * | 2011-08-19 | 2014-06-25 | 威廉马歇莱思大学 | Anode battery materials and methods of making the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113574696A (en) * | 2019-02-08 | 2021-10-29 | 株式会社Lg新能源 | Negative electrode and lithium secondary battery comprising same |
| CN113574696B (en) * | 2019-02-08 | 2024-08-02 | 株式会社Lg新能源 | Negative electrode and lithium secondary battery including the same |
| CN109994723A (en) * | 2019-04-04 | 2019-07-09 | 常州大学 | A kind of SiOxThe preparation method of-G/PAA-PANi/Cu composite material |
| CN109994723B (en) * | 2019-04-04 | 2022-01-04 | 常州大学 | SiO (silicon dioxide)xPreparation method of-G/PAA-PANI/Cu composite material |
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
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Application publication date: 20150128 |