CN103887482B - The preparation method of a kind of sulphur/graphene oxide-lithium metasilicate composite negative pole material - Google Patents
The preparation method of a kind of sulphur/graphene oxide-lithium metasilicate composite negative pole material Download PDFInfo
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- CN103887482B CN103887482B CN201410138387.7A CN201410138387A CN103887482B CN 103887482 B CN103887482 B CN 103887482B CN 201410138387 A CN201410138387 A CN 201410138387A CN 103887482 B CN103887482 B CN 103887482B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 present invention relates to the preparation method of a kind of sulphur/Graphene-lithium metasilicate composite negative pole material, the method comprises the steps: that (1) prepare lithium metasilicate; (2) vulcanized sodium is joined in deionized water, by ultrasonic dispersion, material is dissolved completely, surface-active DTAB is added in deionized water, under room temperature, stir and make it to dissolve completely, above-mentioned two solution are mixed in reaction vessel; By above-mentioned reaction vessel constant temperature in water-bath, slowly drip the appropriate concentrated sulfuric acid, continue constant temperature, under vigorous stirring, add graphene oxide solution, cooling; Said mixture is obtained to sulphur/graphene oxide through centrifugal, washing, after dry; (3) above-mentioned lithium metasilicate is mixed with sulphur/graphene oxide, gained mixture machinery ball milling, obtains product. Sulphur/Graphene-lithium metasilicate composite negative pole material prepared by the present invention, by having the silicon lithium material and sulphur/graphene oxide Material cladding with high conductivity and cyclical stability of high-energy-density, makes material have the feature of high-energy-density and high stability concurrently.
Description
Technical field
The present invention relates to the preparation method of a kind of sulphur/graphene oxide-lithium metasilicate composite negative pole material.
Background technology
In numerous regenerative resources, to have specific energy large because of it for lithium ion battery, has extended cycle life, and security performance is good, without publicThe advantages such as evil become a kind of desirable selection. Electrode material is the key factor that determines performance of lithium ion battery, business in the marketThe carbon negative pole material of industry has approached its theoretical capacity (372mAhg-1), thereby limit further developing of lithium ion battery.Therefore, find a kind of good cycling stability, lithium ion battery negative material that energy density is high, for widening lithium ion batteryUse field is significant.
Researcher is devoted to find a kind of non-carbon negative pole material of alternative material with carbon element always in recent years, and main research comprises nitrogenCompound, silica-base material, tin-based material and other alloy materials etc. It is large that alloy material of cathode has specific capacity, and embedding lithium current potential is high,Electrolyte sensitiveness is low, the advantages such as good conductivity, but alloy material of cathode volumetric expansion in charge and discharge process causes activityMaterial efflorescence, electrically contacts forfeiture, and battery performance worsens. Silicon, as negative material, can form Li with lithium12Si7、Li13Si4、Li7Si13And Li22Si4Up to 4200mAh/g, thereby become the focus of people's research Deng, theoretical capacity. But due to close-packed structure,Silicon volumetric expansion in charge and discharge process is large, material efflorescence is serious, and nano-silicon and thin film silicon cost of manufacture are high in addition, and these are all madeApproximately its application in lithium ion battery.
Summary of the invention
The invention provides the preparation method of a kind of sulphur/graphene oxide-lithium metasilicate composite negative pole material, the negative pole that uses the method to prepareMaterial, has higher specific capacity and cyclical stability.
To achieve these goals, the preparation method of a kind of sulphur/graphene oxide-lithium metasilicate composite negative pole material provided by the invention,The method comprises the steps:
(1) prepare lithium metasilicate
By nanometer silicon monoxide, lithium oxalate in mass ratio for (2-3): 1 ratio is mixed and is ground and evenly obtains mixture, shouldMixture is placed in reactor, in reactor, passes into helium, and is warming up to after 500-750 DEG C with the heating rate of 3-5 DEG C/minReaction 10-20h, obtains lithium metasilicate, cooling for subsequent use;
(2) prepare sulphur/graphene oxide
Vulcanized sodium is joined in deionized water, by ultrasonic dispersion, it is dissolved completely, obtain solution A, by surfactantDTAB adds in deionized water, under room temperature, stirs and makes it to dissolve completely, obtains solution B, wherein surfaceThe weight ratio of the sulphur in activating agent and solution A is (0.05-0.1): 1, solution A is mixed in reaction vessel with solution B;
By above-mentioned reaction vessel constant temperature 30-60min in 50-60 DEG C of water-bath, slowly drip the appropriate concentrated sulfuric acid, obtain solution C, willSolution C continues constant temperature 2-5h, adds the graphene oxide solution of 0.15g/ml, wherein graphene oxide and molten under vigorous stirringThe weight ratio of the sulphur in liquid C is (3-5): 1, continue to be cooled to room temperature after reaction 1-2h;
Obtained mixture is obtained to sulphur/graphene oxide through the washing of centrifugal, ethanol, after dry at 60～80 DEG C of temperature;
(3) be 10:(2-3 in mass ratio by above-mentioned lithium metasilicate and sulphur/graphene oxide) ratio mix, gained mixture existsMechanical ball milling 12-24h under 400-500r/min rotating speed, obtains sulphur/graphene oxide-lithium metasilicate composite negative pole material.
Sulphur/Graphene-lithium metasilicate composite negative pole material prepared by the present invention, leads having the silicon lithium material of high-energy-density and having heightElectrically and sulphur/graphene oxide Material cladding of cyclical stability, make material have the feature of high-energy-density and high stability concurrently, makeMust this composite negative pole material have compared with height ratio capacity and longer service life during for lithium ion battery.
Detailed description of the invention
Embodiment mono-
Nanometer silicon monoxide, lithium oxalate are mixed and are ground in mass ratio evenly obtaining mixture for the ratio of 2:1, by mixtureBe placed in reactor, in reactor, pass into helium, and react 20h after being warming up to 500 DEG C with the heating rate of 3 DEG C/min,To lithium metasilicate, cooling for subsequent use.
Vulcanized sodium is joined in deionized water, by ultrasonic dispersion, material is dissolved completely, obtain solution A, by surface-activeDTAB adds in ionized water, under room temperature, stirs and makes it to dissolve completely, obtains solution B, and wherein live in surfaceThe weight ratio of the sulphur in property agent and solution A is 0.05:1, and above-mentioned two solution are being mixed in reaction vessel.
By above-mentioned reaction vessel constant temperature 60min in 50 DEG C of water-baths, slowly drip the appropriate concentrated sulfuric acid, obtain solution C, by solutionC continues constant temperature 2h, adds the graphene oxide solution of 0.15g/ml, wherein in graphene oxide and solution C under vigorous stirringThe weight ratio of sulphur be 3:1, continue to be cooled to room temperature after reaction 1h; By centrifugal said mixture process, ethanol washing, at 60 DEG CAfter dry at temperature, obtain sulphur/graphene oxide.
The ratio that is 10:2 with sulphur/graphene oxide mass ratio by above-mentioned lithium metasilicate is mixed, and gained mixture is at 400r/min rotating speedLower mechanical ball milling 24h, obtains product.
Embodiment bis-
Nanometer silicon monoxide, lithium oxalate are mixed and are ground in mass ratio evenly obtaining mixture for the ratio of 3:1, by mixtureBe placed in reactor, in reactor, pass into helium, and react 10h after being warming up to 750 DEG C with the heating rate of 5 DEG C/min,To lithium metasilicate, cooling for subsequent use.
Vulcanized sodium is joined in deionized water, by ultrasonic dispersion, material is dissolved completely, obtain solution A, by surface-activeDTAB adds in ionized water, under room temperature, stirs and makes it to dissolve completely, obtains solution B, and wherein live in surfaceThe weight ratio of the sulphur in property agent and solution A is 0.1:1, and above-mentioned two solution are being mixed in reaction vessel.
By above-mentioned reaction vessel constant temperature 30min in 60 DEG C of water-baths, slowly drip the appropriate concentrated sulfuric acid, obtain solution C, by solutionC continues constant temperature 5h, adds the graphene oxide solution of 0.15g/ml, wherein in graphene oxide and solution C under vigorous stirringThe weight ratio of sulphur be 5:1, continue to be cooled to room temperature after reaction 2h; By centrifugal said mixture process, ethanol washing, at 80 DEG CAfter dry at temperature, obtain sulphur/graphene oxide.
The ratio that is 10:3 with sulphur/graphene oxide mass ratio by above-mentioned lithium metasilicate is mixed, and gained mixture is at 500r/min rotating speedLower mechanical ball milling 12h, obtains product.
Comparative example
Taking Si powder as major ingredient, taking graphite powder as auxiliary material, the granularity of Si powder and graphite powder is all less than 20 μ m, by Si powder and graphitePowder be in mass ratio 95: 5 mix after put into steel ball grinder, steel ball grinder is vacuumized and with argon replaces in triplicateAfter be filled with again argon gas as protection gas, by be filled with protection gas ball grinder be placed in planetary ball mill, ball radius is 15-5mm,Be 500 revs/min of lower ball millings 80 hours at rotating speed, make granularity and be less than 20 μ m lithium ion battery negative silicon based composite materials.
Above-described embodiment one, two and comparative example products therefrom, respectively as active electrode material, are assembled into 2032 type button electricityLoop test is carried out in pond. The composition and ratio of electrode material is: active material: conductive agent: PVdF=8:1:1 (mass ratio); To electrodeFor lithium metal; Electrolyte is 1mol/LLiPF6EC/DMC (volume ratio is 1:1) solution; Barrier film is Cellgard2400 microporeBarrier film. Be at 25 DEG C, to carry out electric performance test, the after tested material of this embodiment mono-and two and the product of comparative example at probe temperatureCompare, the capacity that charges and discharge first improves 20-25%, brings up to service life more than 2 times.
Claims (1)
1. a preparation method for sulphur/graphene oxide-lithium metasilicate composite negative pole material, the method comprises the steps:
(1) prepare lithium metasilicate
By nanometer silicon monoxide, lithium oxalate in mass ratio for (2-3): 1 ratio is mixed and is ground and evenly obtains mixture, this mixture is placed in to reactor, in reactor, pass into helium, and react 10-20h after being warming up to 500-750 DEG C with the heating rate of 3-5 DEG C/min, obtain lithium metasilicate, cooling for subsequent use;
(2) prepare sulphur/graphene oxide
Vulcanized sodium is joined in deionized water, by ultrasonic dispersion, it is dissolved completely, obtain solution A, surfactant DTAB is added in deionized water, under room temperature, stir and make it to dissolve completely, obtain solution B, wherein the weight ratio of the sulphur in surfactant and solution A is (0.05-0.1): 1, solution A is mixed in reaction vessel with solution B;
By above-mentioned reaction vessel constant temperature 30-60min in 50-60 DEG C of water-bath, slowly drip the appropriate concentrated sulfuric acid, obtain solution C, solution C is continued to constant temperature 2-5h, under vigorous stirring, add the graphene oxide solution of 0.15g/ml, wherein the weight ratio of the sulphur in graphene oxide and solution C is (3-5): 1, continue to be cooled to room temperature after reaction 1-2h;
Obtained mixture is obtained to sulphur/graphene oxide through the washing of centrifugal, ethanol, after dry at 60～80 DEG C of temperature;
(3) be 10:(2-3 in mass ratio by above-mentioned lithium metasilicate and sulphur/graphene oxide) ratio mix, gained mixture mechanical ball milling 12-24h under 400-500r/min rotating speed, obtains sulphur/graphene oxide-lithium metasilicate composite negative pole material.
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| JP5464653B2 (en) * | 2009-11-27 | 2014-04-09 | 日立マクセル株式会社 | Non-aqueous secondary battery and manufacturing method thereof |
| CN101913616B (en) * | 2010-08-13 | 2012-08-22 | 北京科技大学 | Preparation method of lithium silicate material with high purity |
| CN102709533A (en) * | 2012-06-12 | 2012-10-03 | 广州市香港科大霍英东研究院 | Preparation method of lithium sulphur battery anode material with high power and high specific capacity |
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Effective date of registration: 20160401 Address after: 013650 the Inner Mongolia Autonomous Region Xinghe County, Wulanchabu City Xing Mong Kok Industrial Park Applicant after: Wulanchabu Dasheng Graphite New Material Co., Ltd. Address before: 518000, Lianhua Road 1116, Lianhua Road, Futian District, Guangdong, Shenzhen, 34-505 Applicant before: Wang Yang |
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