CN106450186A - Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application - Google Patents

Preparation method for lithium manganese silicate/carbon composite material used as positive electrode material of lithium ion battery, and positive electrode slurry and application Download PDF

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CN106450186A
CN106450186A CN201610883942.8A CN201610883942A CN106450186A CN 106450186 A CN106450186 A CN 106450186A CN 201610883942 A CN201610883942 A CN 201610883942A CN 106450186 A CN106450186 A CN 106450186A
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lithium
sio
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CN106450186B (en
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张娟
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Jiangsu Polytron Technologies Inc
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Nanjing Silicon Source Technology Development Co Ltd
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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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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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Abstract

The invention relates to a preparation method for a lithium manganese silicate/carbon composite material used as a positive electrode material of a lithium ion battery. The preparation method comprises the following steps: the surface of silicon dioxide is coated with an amorphous carbon layer; then a chemical etching reaction is performed to etch off a part of SiO<2> to generate a composite material with a yolk-egg shell structure, wherein by virtue of the SiO<2> composite material with the structure, the dimensions of lithium manganese silicate granules can be reduced while a lithium source and a manganese source can be dispersed into the SiO<2> main body through a carbon layer; the carbon layer on the surface of the SiO<2> can prevent the generated lithium manganese silicate from agglomerating; next, the SiO<2>@void@C composite material, the manganese salt and the lithium salt are added into a water solution based on certain proportion to be mixed uniformly; then the obtained solution is heated and volatilized to obtain a solid body, and high-temperature processing is performed under inert atmosphere protection to obtain the lithium manganese silicate/carbon composite material. The prepared lithium manganese silicate is uniform in granule dispersion without obvious agglomeration, and relatively small in granule sizes; and meanwhile, the surface is coated with the uniform amorphous carbon layer.

Description

A kind of preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite, Anode sizing agent and application
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, and in particular to a kind of lithium ion cell positive material The preparation method of material manganous silicate lithium/carbon composite material.
Background technology
Can charging-discharging lithium ion battery due to have the advantages that energy density is high, power density is big, safe and environment-friendly, wide General apply in communication, portable computer and mobile electron energy storage device.As lithium ion battery is in the extensive of mobile electron field Application, lithium ion battery is considered as the optimum selection of large-scale energy storage device and batteries of electric automobile.But large-scale energy storage sets Standby and power big battery has higher requirement to the energy density of lithium ion battery and power density, and therefore exploitation has The positive and negative electrode material of height ratio capacity is crucial.
Widely studied at present and application positive electrode mainly has the LiMO of layer structure2（M=Co、Ni、Mn）And spinelle The LiMn of structure2O4、LiNixMnyO4.However, this different materials has respective shortcoming, high cost, synthesis condition harshness, safety Performance is low.
At present, in polyanionic compound, olivine-type LiFePO4Material relies on good cycle performance, cost Low and safe the advantages of, obtain a wide range of applications.But LiFePO4Can only one Li of deintercalation in materials theory+, theoretical Specific capacity is 170mAh g-1, it is difficult to meet the demand of energy storage device and power big battery to high power capacity.At present, polyanion Type silicate anodal material Li2MSiO4(M=Fe, Mn, Co, Ni), due to two lithium ions of deintercalation, theoretical specific capacity being 330 mAh g-1, abundant raw material, low cost and high security etc., widely paid close attention to.
Li2MnSiO4As Olivine-type Cathode Material in Li-ion Batteries, with theoretical specific capacity height, Stability Analysis of Structures, cheap And advantages of environment protection, it is considered to be the anode material for lithium-ion batteries of following great application prospect, and be hopeful to apply In electrokinetic cell and large-scale energy storage device.However, Li2MnSiO4Have that electronic conductivity is poor, low ionic mobility, by In the Jiang Taile phenomenon of manganese ion, the crystalline structure of material is caused the shortcomings of changing, to constrain its application.At present, Li2MnSiO4Synthetic method mainly have solid phase method, sol-gel process and hydro-thermal method, its prepare manganese silicate of lithium generally existing hold Measure the problems such as low and cycle performance is poor.
Content of the invention
The purpose of the present invention is primarily directed to the deficiencies in the prior art, and the low problem of manganese silicate of lithium capacity provides one kind Method prepared by lithium manganese silicate anode material, the manganese silicate of lithium granule synthesized by the method is little, the uniform carbon of one layer of Surface coating Layer, and without obvious agglomeration, electric conductivity and the electrochemical cycle stability of manganese silicate of lithium can be effectively improved.
The first aspect of the invention：
A kind of preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite, including yolk-eggshell structure SiO2The preparation of@void C composite and the preparation of manganous silicate lithium/carbon composite material, comprise the steps：
1st step, by SiO2Granule is added in organic or inorganic solvent, then under agitation, is added carbon source, stirred；
2nd step, the solution for obtaining is evaporated removing solvent, and the solid for obtaining is after grinding, then through calcining, obtains SiO2@C composite；
3rd step, by the SiO for obtaining2@C composite is performed etching under alkalescence or acid condition, then through over cleaning, drying Afterwards, yolk-eggshell structure SiO is obtained2@void@C composite；
4th step, according to a certain percentage by SiO2@void@C, manganese source compound and Li source compound are added in distilled water, stirring After uniform, evaporation makes water volatilize, then is ground after being dried, and obtains precursor powder；
5th step, the precursor powder for obtaining is carried out the pre-heat treatment；
6th step, after the powder mull that the 5th step is obtained, tabletting, then after being calcined, obtains manganese silicate of lithium/carbon composite wood Material.
In the 1st described step, SiO2The granule size of granule is 50～200nm；The quality of the carbon source of carbon source is titanium dioxide 10～50% amounts of siliceous amount are the 10～50% of silicon dioxide quality；Described organic or inorganic solvent be ethanol, isopropanol, third A kind of or arbitrarily multiple combination in ketone, ethanol-acetone solution, ethylene glycol, Polyethylene Glycol or water；Carbon source be glucose, One kind or any in sucrose, citric acid, polyvinyl alcohol, beta-schardinger dextrin-, Lactose, polysaccharide, ascorbic acid, tartaric acid or VC Multiple combination.
In the 2nd described step, the operation temperature of evaporative removal solvent is 50～80 DEG C；Calcination process be in indifferent gas bromhidrosis 2～10h is calcined in atmosphere at 500～800 DEG C；Described inert protective atmosphere is in nitrogen, argon or argon-hydrogen gaseous mixture Plant or multiple combination.
In the 3rd described step, 1～240 min of etch period, dry run is to dry 1～8h at 50～150 DEG C；Institute In the acidity that states or alkalescence condition, described acid is 5～20% Fluohydric acid., and described alkali is the hydroxide of 0.1～5mol/L Sodium.
In the 4th described step, Li source compound, manganese source compound and SiO2SiO in@void@C2Mol ratio be 1～3： 0.5～1.5：0.5～1.5；Li source compound is a kind of or arbitrarily many in lithium carbonate, Lithium hydrate, lithium acetate or lithium oxalate The combination that plants；Manganese source compound is the one kind in manganese carbonate, manganese acetate, manganous hydroxide, mangano-manganic oxide or manganese dioxide or appoints Meaning multiple combination.
In the 4th described step, it is 50～80 DEG C that evaporation makes the temperature range of material in water volatilization process；Dry run is true 1～8h is dry in empty drying baker at 60～120 DEG C.
In the 5th described step, the pre-heat treatment is to process 2～10h at 300～400 DEG C in inert gas atmosphere.
In the 6th described step, calcining be inert gas atmosphere protection under in 600～800 DEG C of 2～12h of temperature lower calcination, Obtain manganous silicate lithium/carbon composite material.
According to the second aspect of the invention：
The lithium ion battery anode glue size of the manganous silicate lithium/carbon composite material that above-mentioned method is prepared into.
According to the third aspect of the present invention：
Application of the above-mentioned anode sizing agent in lithium ion battery is prepared.
Beneficial effect
The present invention mainly coats one layer of amorphous carbon layer in silica surface, is then reacted by chemical etching again, etching Fall a part of SiO2Which is made to generate the SiO with yolk-eggshell structure2@void@C composite, the composite on the one hand can To reduce the size of manganese silicate of lithium granule, another aspect lithium source, manganese source can be diffused into SiO by carbon-coating2Main body, SiO2Surface Carbon-coating can prevent generate manganese silicate of lithium reunite, the dispersibility of manganese silicate of lithium can be effectively improved, such that it is able to keep good Conductive network, and show stable electrochemistry cycle performance.
Description of the drawings
Fig. 1 is the SiO for preparing in embodiment 12The SEM electron microscope of@void@C composite.
Fig. 2 is the SEM electron microscope of the manganous silicate lithium/carbon composite material for preparing in embodiment 1.
Fig. 3 is the charging and discharging curve figure of the manganous silicate lithium/carbon composite material for preparing in embodiment 1.
Specific embodiment
The preparation of lithium-ion battery anode material lithium manganese silicate/carbon composite that the present invention is provided is broadly divided into two big steps Suddenly：The first step is yolk-eggshell structure SiO2The preparation of@void C composite, second step is manganous silicate lithium/carbon composite material Preparation.
In the first step, by SiO2Granule is added in organic or inorganic solvent, then under agitation, is added carbon source, stirred Mix uniformly, then the solution for obtaining is evaporated solvent is removed, the solid for obtaining is after grinding, then through calcining, obtains SiO2@C composite, in this step, can make SiO2One layer of carbon-coating of particles coat, SiO2The carbon-coating on surface can prevent to generate Manganese silicate of lithium reunite, the dispersibility of manganese silicate of lithium can be effectively improved, such that it is able to keep good conductive network, and shown Stable electrochemistry cycle performance.SiO2The granule size of granule is 50～200nm；The consumption of carbon source is silicon dioxide quality 10～50%；Described organic or inorganic solvent is ethanol, isopropanol, acetone, ethanol-acetone solution, ethylene glycol, Polyethylene Glycol Or a kind of or arbitrarily multiple combination in water；Carbon source is glucose, sucrose, citric acid, polyvinyl alcohol, beta-schardinger dextrin-, breast One kind or any multiple combination in sugar, polysaccharide, ascorbic acid, tartaric acid or VC.Next, needing the side by etching Formula makes SiO2Enough spaces are left between carbon-coating, on the one hand can reduce the size of manganese silicate of lithium granule, another aspect lithium Source, manganese source can be diffused into SiO by carbon-coating2Main body, reduces the reunion of manganese silicate of lithium material.In the step, described acidity Or in alkalescence condition, described acid is 5～20% Fluohydric acid., described alkali is the sodium hydroxide of 0.1～5mol/L.In addition, Can adopt through hydroxyl silicon oil modified SiO2Granule can promote carbon source on surface as raw material after surface modification Covered effect, improve positive electrode charge-discharge performance.
In second step, the preparation of manganous silicate lithium/carbon composite material be according to a certain percentage by SiO2@void@C, manganese source Compound and Li source compound are added in distilled water, wherein Li source compound, manganese source compound and SiO2SiO in@void@C2's Mol ratio can be 1～3：0.5～1.5：0.5～1.5, SiO2SiO in@void@C2Amount can be by thermogravimetric analysiss come really Fixed, after stirring, evaporation makes water volatilize, then is ground after being dried, and obtains precursor powder, then before obtaining Drive through grinding after body powder carries out the pre-heat treatment, after tabletting, then after being calcined, obtain manganous silicate lithium/carbon composite material.Lithium Source compound is a kind of or arbitrarily multiple combination in lithium carbonate, Lithium hydrate, lithium acetate or lithium oxalate；Manganese source compound is One kind or any multiple combination in manganese carbonate, manganese acetate, manganous hydroxide, mangano-manganic oxide or manganese dioxide.
Embodiment 1
Step one, yolk-eggshell structure SiO2The preparation of@void@C composite
(1) SiO of the granule size for 100nm or so is weighed2Granule 10g, adds in distilled water 100g, and the work in magnetic agitation With lower addition 3g glucose.Stirring 3h makes its mix homogeneously.
(2) above-mentioned solution is stirred at 60 DEG C and is volatilized up to solvent completely, by the solid of gained in agate mortar Grinding, is subsequently transferred in tube furnace, under inert atmosphere protection, calcines 4h, obtain SiO at 750 DEG C2@C composite.
(3) 10g SiO is subsequently weighed2@C composite is added to 100 ml concentration for 1mol L-1NaOH solution in, 2h being reacted under magnetic agitation, subsequently cleaned with distilled water and be collected by centrifugation for several times, be transferred in air dry oven, dries at 80 DEG C 3h.Obtain yolk-eggshell structure SiO2@void@C composite.
Step 2, the preparation of manganous silicate lithium/carbon composite material
(1) Lithium hydrate, manganese acetate being weighed be dissolved in 50ml distilled water, until being completely dissolved, adds SiO under magnetic stirring2@ Void@C, the mol ratio for making SiO2 in Li source compound, manganese source compound and SiO2@void@C is 2：1：1, subsequently at 60 DEG C Lower stirring is volatilized completely up to solvent, is transferred in vacuum drying oven and dries 4h at 80 DEG C, is more thoroughly dry.Subsequently Solid grind into powder in agate mortar will be obtained, will obtain precursor powder.
(2) by the precursor powder for obtaining, it is transferred in tube furnace, is placed in pretreatment 5h in 400 DEG C of inert atmospheres.
(3) pretreated product is fully ground uniformly, tabletting, then under inert atmosphere protection, in 750 DEG C of temperature Lower calcining 6h, obtains manganous silicate lithium/carbon composite material.
Embodiment 2
Step one, yolk-eggshell structure SiO2The preparation of@void@C composite
(1) SiO of the granule size for 200nm or so is weighed2Granule 10g, adds in distilled water 100g, and the work in magnetic agitation With lower addition 2g glucose.Stirring 3h makes its mix homogeneously.Above-mentioned solution is stirred at 60 DEG C and is volatilized up to solvent completely, The solid of gained is ground in agate mortar, is subsequently transferred in tube furnace, under inert atmosphere protection, forge at 750 DEG C 4h is burnt, obtains SiO2@C composite.
(2) 10g SiO is subsequently weighed2@C composite is added to 100 ml mass fractions, React 2h under magnetic stirring, subsequently cleaned with distilled water and be collected by centrifugation for several times, be transferred in air dry oven, do at 80 DEG C Dry 3h.Obtain yolk-eggshell structure SiO2@void@C composite.
Step 2, the preparation of manganous silicate lithium/carbon composite material
(1) Lithium hydrate, manganese acetate being weighed be dissolved in 50ml distilled water, until being completely dissolved, adds SiO under magnetic stirring2@ Void@C, the mol ratio for making SiO2 in Li source compound, manganese source compound and SiO2@void@C is 2：1：1, subsequently at 60 DEG C Lower stirring is volatilized completely up to solvent, is transferred in vacuum drying oven and dries 4h at 80 DEG C, is more thoroughly dry.Subsequently Solid grind into powder in agate mortar will be obtained, will obtain precursor powder.
(2) by the precursor powder for obtaining, it is transferred in tube furnace, is placed in pretreatment 5h in 500 DEG C of inert atmospheres.
(3) pretreated product is fully ground uniformly, tabletting, then under inert atmosphere protection, in 650 DEG C of temperature Lower calcining 6h, obtains manganous silicate lithium/carbon composite material.
Embodiment 3
Step one, yolk-eggshell structure SiO2The preparation of@void@C composite
(1) SiO of the granule size for 80nm or so is weighed2Granule 10g, adds in distilled water 100g, and the work in magnetic agitation With lower addition 5g glucose.Stirring 3h makes its mix homogeneously.
(2) above-mentioned solution is stirred at 60 DEG C and is volatilized up to solvent completely, by the solid of gained in agate mortar Grinding, is subsequently transferred in tube furnace, under inert atmosphere protection, calcines 4h, obtain SiO at 750 DEG C2@C composite.
(3) subsequently weighing 10g SiO2@C composite 100 ml concentration is added to for 2mol L-1NaOH solution in, 1h being reacted under magnetic agitation, subsequently cleaned with distilled water and be collected by centrifugation for several times, be transferred in air dry oven, dries at 80 DEG C 3h.Obtain yolk-eggshell structure SiO2@void@C composite.
Step 2, the preparation of manganous silicate lithium/carbon composite material
(1) Lithium hydrate, manganese acetate being weighed be dissolved in 50ml distilled water, until being completely dissolved, adds SiO under magnetic stirring2@ Void@C, the mol ratio for making SiO2 in Li source compound, manganese source compound and SiO2@void@C is 2：1：1, subsequently at 60 DEG C Lower stirring is volatilized completely up to solvent, is transferred in vacuum drying oven and dries 4h at 80 DEG C, is more thoroughly dry.Subsequently Solid grind into powder in agate mortar will be obtained, will obtain precursor powder.
(2) by the precursor powder for obtaining, it is transferred in tube furnace, is placed in pretreatment 5h in 400 DEG C of inert atmospheres.
(3) pretreated product is fully ground uniformly, tabletting, then under inert atmosphere protection, in 800 DEG C of temperature Lower calcining 8h, obtains manganous silicate lithium/carbon composite material.
Embodiment 4
Difference with embodiment 3 be first to SiO2Granule is using hydroxyl silicon oil modified.
Step one, yolk-eggshell structure SiO2The preparation of@void@C composite
(1) SiO of the granule size for 80nm or so is weighed2Granule 10g, adds in distilled water 100g, is adjusted using sulphuric acid and suspends The pH of liquid is 4.5, adds hydroxy silicon oil 5g, is filtered, and spend Ion Cleaning filter cake, then filter cake is mixed in after stirring 1h In 100g water, and 5g glucose is added in the presence of magnetic agitation.Stirring 3h makes its mix homogeneously.
(2) above-mentioned solution is stirred at 60 DEG C and is volatilized up to solvent completely, by the solid of gained in agate mortar Grinding, is subsequently transferred in tube furnace, under inert atmosphere protection, calcines 4h, obtain SiO at 750 DEG C2@C composite.
(3) subsequently weighing 10g SiO2@C composite 100 ml concentration is added to for 2mol L-1NaOH solution in, 1h being reacted under magnetic agitation, subsequently cleaned with distilled water and be collected by centrifugation for several times, be transferred in air dry oven, dries at 80 DEG C 3h.Obtain yolk-eggshell structure SiO2@void@C composite.
Step 2, the preparation of manganous silicate lithium/carbon composite material
(1) Lithium hydrate, manganese acetate being weighed be dissolved in 50ml distilled water, until being completely dissolved, adds under magnetic stirring SiO2@void@C, makes SiO in Li source compound, manganese source compound and SiO2@void@C2Mol ratio be 2：1：1, subsequently At 60 DEG C, stirring is volatilized completely up to solvent, is transferred in vacuum drying oven and dries 4h at 80 DEG C, is more thoroughly dry. Solid grind into powder in agate mortar will be subsequently obtained, will obtain precursor powder.
(2) by the precursor powder for obtaining, it is transferred in tube furnace, is placed in pretreatment 5h in 400 DEG C of inert atmospheres.
(3) pretreated product is fully ground uniformly, tabletting, then under inert atmosphere protection, in 800 DEG C of temperature Lower calcining 8h, obtains manganous silicate lithium/carbon composite material.
Reference examples 1
Difference with embodiment 3 is：Not to SiO2Granule adopts carbon coating.
Step one, SiO2Material etch
(1) SiO of the granule size for 80nm or so is weighed2Granule 10g, adds in distilled water 100g, and the work in magnetic agitation Its mix homogeneously is made with lower stirring 3h.
(2) above-mentioned solution is stirred at 60 DEG C and is volatilized up to solvent completely, by the solid of gained in agate mortar Grinding, is subsequently transferred in tube furnace, under inert atmosphere protection, calcines 4h, obtain SiO at 750 DEG C2Material.
(3) 10g SiO is subsequently weighed2Material is added to 100 ml concentration for 2mol L-1NaOH solution in, stir in magnetic force Lower reaction 1h is mixed, is subsequently cleaned with distilled water and be collected by centrifugation for several times, be transferred in air dry oven, at 80 DEG C, dry 3h.? SiO to after etching processing2Material.
Step 2, the preparation of manganese silicate of lithium material
(1) Lithium hydrate, manganese acetate being weighed be dissolved in 50ml distilled water, until being completely dissolved, adds etching under magnetic stirring SiO after process2Material, makes the SiO after lithium source, manganese source and etching processing2The mol ratio of material is 2：1：1, subsequently at 60 DEG C Lower stirring is volatilized completely up to solvent, is transferred in vacuum drying oven and dries 4h at 80 DEG C, is more thoroughly dry.Subsequently Solid grind into powder in agate mortar will be obtained, will obtain precursor powder.
(2) by the precursor powder for obtaining, it is transferred in tube furnace, is placed in pretreatment 5h in 400 DEG C of inert atmospheres.
(3) pretreated product is fully ground uniformly, tabletting, then under inert atmosphere protection, in 800 DEG C of temperature Lower calcining 8h, obtains manganese silicate of lithium material.
Reference examples 2
Difference with embodiment 3 is：In SiO2In the preparation of@C composite, the step of etching is provided without.
Step one, SiO2The preparation of@C composite
(1) SiO of the granule size for 80nm or so is weighed2Granule 10g, adds in distilled water 100g, and the work in magnetic agitation With lower addition 5g glucose.Stirring 3h makes its mix homogeneously.
(2) above-mentioned solution is stirred at 60 DEG C and is volatilized up to solvent completely, by the solid of gained in agate mortar Grinding, is subsequently transferred in tube furnace, under inert atmosphere protection, calcines 4h, obtain SiO at 750 DEG C2@C composite.
Step 2, the preparation of manganous silicate lithium/carbon composite material
(1) Lithium hydrate, manganese acetate being weighed be dissolved in 50ml distilled water, until being completely dissolved, adds under magnetic stirring SiO2@C composite, makes lithium source, manganese source and SiO2SiO in@C-material2Mol ratio be 2：1：1, subsequently stirring at 60 DEG C Until solvent volatilizees completely, be transferred in vacuum drying oven and 4h dry at 80 DEG C, more thoroughly dry.To subsequently obtain Solid grind into powder in agate mortar, obtains precursor powder.
(2) by the precursor powder for obtaining, it is transferred in tube furnace, is placed in pretreatment 5h in 400 DEG C of inert atmospheres.
(3) pretreated product is fully ground uniformly, tabletting, then under inert atmosphere protection, in 800 DEG C of temperature Lower calcining 8h, obtains manganous silicate lithium/carbon composite material.
Cycle performance test has been carried out to made positive electrode, with lithium piece as negative pole, 1mol L-1LiPF6It is dissolved in 1：1（Body Product ratio）As electrolyte in the ethylene carbonate of mixing and dimethyl carbonate, Celgard2400 selected by barrier film, in inert atmosphere Glove box in complete the assembling of button cell.Using battery test system, in the multiplying power of 0.1C and the voltage of 1.5～4.8V Charge-discharge performance test is carried out under scope.After 50 circulations, discharge capacity and discharge capacitance are as follows：
Can see from table, the manganous silicate lithium/carbon composite material that the present invention is provided is applied to be had preferably during anode electrode Charge-discharge performance, discharge capacity is in 200 more than mAh/g first for which, and after 50 circulations, capacitance may remain in 85% More than；Embodiment 3 can be seen with respect to reference examples 1, by using carbon source to SiO2After granule is coated, can be permissible The manganese silicate of lithium for generating is prevented to reunite, improve material property；Embodiment 3 is with respect to reference examples 2 as can be seen that by adopting to two After the step of oxide etch, on the one hand composite can reduce the size of manganese silicate of lithium granule, another aspect lithium source, manganese source SiO can be diffused into by carbon-coating2Main body, improves the charge-discharge performance of material；By to SiO in embodiment 42Granule is changed Property, material covered effect can be improved, improve charge-discharge performance.

Claims (10)

1. a kind of preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite, it is characterised in that including egg Huang-eggshell structure SiO2The preparation of@void C composite and the preparation of manganous silicate lithium/carbon composite material, comprise the steps：
1st step, by SiO2Granule is added in organic or inorganic solvent, then under agitation, is added carbon source, stirred；
2nd step, the solution for obtaining is evaporated removing solvent, and the solid for obtaining is after grinding, then through calcining, obtains SiO2@C composite；
3rd step, by the SiO for obtaining2@C composite is performed etching under alkalescence or acid condition, then through over cleaning, drying Afterwards, yolk-eggshell structure SiO is obtained2@void@C composite；
4th step, according to a certain percentage by SiO2@void@C, manganese source compound and Li source compound are added in distilled water, stirring After uniform, evaporation makes water volatilize, then is ground after being dried, and obtains precursor powder；
5th step, the precursor powder for obtaining is carried out the pre-heat treatment；
6th step, after the powder mull that the 5th step is obtained, tabletting, then after being calcined, obtains manganese silicate of lithium/carbon composite wood Material.
2. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levy and be, in the 1st described step, SiO2The granule size of granule is 50～200nm；The quality of carbon source is silicon dioxide quality 10～50%；Described organic or inorganic solvent is ethanol, isopropanol, acetone, ethanol-acetone solution, ethylene glycol, Polyethylene Glycol Or a kind of or arbitrarily multiple combination in water；Carbon source is glucose, sucrose, citric acid, polyvinyl alcohol, beta-schardinger dextrin-, breast One kind or any multiple combination in sugar, polysaccharide, ascorbic acid, tartaric acid or VC.
3. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levy and be, in the 2nd described step, the operation temperature of evaporative removal solvent is 50～80 DEG C；Calcination process be in indifferent gas bromhidrosis 2～10h is calcined in atmosphere at 500～800 DEG C；Described inert protective atmosphere is in nitrogen, argon or argon-hydrogen gaseous mixture Plant or multiple combination.
4. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levy and be, in the 3rd described step, 1～240 min of etch period, dry run is to dry 1～8h at 50～150 DEG C；Described Acidity or alkalescence condition in, described acid is 5～20% Fluohydric acid., and described alkali is the sodium hydroxide of 0.1～5mol/L.
5. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levy and be, in the 4th described step, Li source compound, manganese source compound and SiO2SiO in@void@C2Mol ratio be 1～3： 0.5～1.5：0.5～1.5；Li source compound is a kind of or arbitrarily many in lithium carbonate, Lithium hydrate, lithium acetate or lithium oxalate The combination that plants；Manganese source compound is the one kind in manganese carbonate, manganese acetate, manganous hydroxide, mangano-manganic oxide or manganese dioxide or appoints Meaning multiple combination.
6. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levy and be, in the 4th described step, it is 50～80 DEG C that evaporation makes the temperature range of material in water volatilization process；Dry run is true 1～8h is dry in empty drying baker at 60～120 DEG C.
7. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levying and being, in the 5th described step, the pre-heat treatment is 2～10h to be processed at 300～400 DEG C in inert gas atmosphere.
8. the preparation method of lithium-ion battery anode material lithium manganese silicate/carbon composite according to claim 1, which is special Levy and be, in the 6th described step, calcining be inert gas atmosphere protection under in 600～800 DEG C of 2～12h of temperature lower calcination, Obtain manganous silicate lithium/carbon composite material.
9. the lithium-ion electric of the manganous silicate lithium/carbon composite material that the method described in any one of claim 1～8 is prepared into is included Pond anode sizing agent.
10. application of the lithium ion battery anode glue size described in claim 9 in lithium ion battery is prepared.
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