CN105609716A - Preparation method for carbon-silicon coated lithium iron phosphate composite material for lithium ion battery - Google Patents
Preparation method for carbon-silicon coated lithium iron phosphate composite material for lithium ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000197 pyrolysis Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 229940116007 ferrous phosphate Drugs 0.000 claims description 13
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 13
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910010710 LiFePO Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000009415 formwork Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- 239000000320 mechanical mixture Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for a carbon-silicon coated lithium iron phosphate composite material for a lithium ion battery. According to the prepared carbon-silicon coated lithium iron phosphate composite material for the lithium ion battery, the lithium iron phosphate is coated with a material obtained by compounding porous carbon and porous silicon that are prepared by adopting a specific process; consequently, carbon and silicon are uniformly distributed in lithium iron phosphate; due to the porous structures, the coating structure is more tight; therefore, when the composite material is used for the lithium ion battery, the lithium ion battery obtains relatively high conductivity and good cycling stability; and in addition, the lithium ion battery is relatively high in specific capacity and relatively long in service life.
Description
Affiliated technical field
The present invention relates to the preparation method of a kind of lithium ion battery carbon silicon coated lithium ferrous phosphate composite material.
Background technology
Lithium ion battery is as a kind of novel electrochmical power source, because its output voltage is high, specific energy is high, have extended cycle life, certainly putLittle, the safety of electricity, memory-less effect and environmental friendliness have become the emphasis of our times various countries in the development of new energy materials field. JustUtmost point active material is the key factor that affects performance of lithium ion battery always. Due to LiCoO2Shortage of resources, expensive, specialBe its poor stability, limited its application in electrokinetic cell field. LiFePO4 is because of its abundant raw material, and security is good, byExtensively think the first-selected positive electrode of lithium-ion-power cell of future generation. But lithium iron phosphate positive material also have one fatalShortcoming, that is exactly that electrical conductivity is low, and this shortcoming has greatly affected LiFePO4Application. Therefore in the urgent need to researching and developing a kind of conductionRate is high, the LiFePO of good cycle4(LiFePO 4) composite.
Summary of the invention
For overcoming above-mentioned deficiency, the invention provides the preparation side of a kind of lithium ion battery carbon silicon coated lithium ferrous phosphate composite materialMethod, the positive electrode that uses the method to prepare, has good electric conductivity.
To achieve these goals, the system of carbon silicon coated lithium ferrous phosphate composite material for a kind of lithium ion battery provided by the inventionPreparation Method, comprises the steps:
(1) prepare porous silicon
By ethyl orthosilicate pyrolysis in the ethylene glycol solution of the organic formwork that contains softex kw, preparation porousSilica, by the porous silica that contains template that obtains filter, centrifugal, clean, dry, then 500-700 in airDEG C temperature under the heat treatment carried out 3-7 hour remove template, obtain porous silica;
Be 1:5-5:1 mixed grinding by porous silica and magnesium powder according to mass ratio, then 700-900 DEG C of heating under inert atmospherePorous silicon is prepared in reductase 12-5 hour, and the product obtaining is cleaned through watery hydrochloric acid, removes the metal oxide in product and has beenThe metallic reducing agent of full response, dry, obtain porous silicon;
(2) prepare porous carbon materials
First by 1: 1-1: 3 weight ratio, by phenolic resins and ethylene glycol mixing and stirring, adds phenolic resins and second subsequentlyThe benzene sulfonyl chloride of glycol gross weight 8-10% mixes makes mixture, and mixture is poured in mould, at 50-70 DEG C, protectsTemperature 2-5h, by the sample demoulding after just solidifying, carries out deeply-curing processing to sample, is incubated 10-12h in the time of initial temperature 60-80 DEG C,Then 15 DEG C of insulation 6-8h of the every increase of temperature, are incubated 8～16h until temperature rises to 150-180 DEG C, again at N2Under protection, carry out carbonChange, rise to 600 DEG C by room temperature, insulation 1h, heating rate is 1-5 DEG C/min, cools to room temperature with the furnace after completing carbonization, finalStop for N2, obtain the porous carbon materials that average pore size is less than 300nm;
(3) prepare porous carbon/silicon composite
By above-mentioned porous silicon and porous carbon according to the ratio mechanical mixture of mass ratio 3:1-1:3, then by mixture with contain phenolic aldehyde treeThe formalin of fat is mixed, and carries out subsequently pyrolysis under inert atmosphere, and pyrolysis temperature is 800-1000 DEG C, and pyrolysis time is 5-8Hour, prepare porous silicon/carbon composite material;
(4) sintering obtains the coated lithium ferrous phosphate composite material of carbon silicon
By LiFePO4The lithium metasilicate aqueous solution that is placed in mass concentration and is 25-30% soaks 1-3h, and fully stirs, by solution waterDivide evaporation, by the LiFePO after soaking4Roasting 2-5h at 400-450 DEG C, at the LiFePO through roasting gained4In powder, addThe above-mentioned porous silicon/carbon composite material that to enter with respect to the content of LiFePO4 be 3-7wt%, after ball milling mixes in tube furnaceHeating, heating-up temperature is 1200-1500 DEG C, the heat time is 1-2h, obtains the coated ferrous phosphate lithium composite of carbon silicon after coolingMaterial.
The coated lithium ferrous phosphate composite material of carbon silicon for lithium ion battery prepared by the present invention, has adopted prepared by special process manyMaterial after hole carbon and porous silicon are compound is coated LiFePO 4, and carbon silicon is distributed in LiFePO 4 uniformly,Loose structure makes clad structure more tight especially, and therefore this composite, when for lithium ion battery, has higher leadingElectrical property and good cyclical stability, make lithium ion battery have high specific capacity and longer service life.
Detailed description of the invention
Embodiment mono-
Prepare porous silicon
By ethyl orthosilicate pyrolysis in the ethylene glycol solution of the organic formwork that contains softex kw, preparation porousSilica, by the porous silica that contains template that obtains filter, centrifugal, clean, dry, then in air 700DEG C temperature under the heat treatment carried out 3 hours remove template, obtain porous silica; By porous silica and magnesium powder according toMass ratio is 5:1 mixed grinding, and then under inert atmosphere, 900 DEG C of heat reductions are prepared porous silicon for 2 hours, by the product obtainingClean through watery hydrochloric acid, remove the metal oxide in product and be the metallic reducing agent of complete reaction, be dried, obtain porous silicon.
Prepare porous carbon materials
First press the weight ratio of 1: 3 by phenolic resins and ethylene glycol mixing and stirring, add subsequently phenolic resins and ethylene glycol totalThe benzene sulfonyl chloride of weight 10% mixes makes mixture, and mixture is poured in mould, at 70 DEG C, is incubated 5h, willThe sample demoulding after just solidifying, carries out deeply-curing processing to sample, in the time of 80 DEG C of initial temperatures, is incubated 12h, and then temperature is everyIncrease by 15 DEG C of insulation 6h, be incubated again 8h until temperature rises to 180 DEG C, at N2Under protection, carry out carbonization, rise to 600 by room temperatureDEG C, insulation 1h, heating rate is 5 DEG C/min, cools to room temperature with the furnace after completing carbonization, finally stops for N2, obtain averageAperture is less than the porous carbon materials of 300nm.
Prepare porous carbon/silicon composite
By above-mentioned porous silicon and porous carbon according to the ratio mechanical mixture of mass ratio 1:3, then by mixture with contain phenolic resinsFormalin mix, under inert atmosphere, carry out subsequently pyrolysis, pyrolysis temperature is 1000 DEG C, pyrolysis time is 5 hours, systemFor going out porous silicon/carbon composite material.
Sintering obtains the coated lithium ferrous phosphate composite material of carbon silicon
By LiFePO4Be placed in mass concentration and be 30% the lithium metasilicate aqueous solution and soak 1h, and fully stir, solution moisture content testing is steamedSend out, by the LiFePO after soaking4Roasting 2h at 450 DEG C, at the LiFePO through roasting gained4In powder, add with respect toThe content of LiFePO4 is the above-mentioned porous silicon/carbon composite material of 7wt%, heats heating after ball milling mixes in tube furnaceTemperature is 1500 DEG C, and the heat time is 1h, obtains the coated lithium ferrous phosphate composite material of carbon silicon after cooling.
Embodiment bis-
Prepare porous silicon
By ethyl orthosilicate pyrolysis in the ethylene glycol solution of the organic formwork that contains softex kw, preparation porousSilica, by the porous silica that contains template that obtains filter, centrifugal, clean, dry, then in air 500DEG C temperature under the heat treatment carried out 7 hours remove template, obtain porous silica; By porous silica and magnesium powder according toMass ratio is 1:5 mixed grinding, and then under inert atmosphere, 700 DEG C of heat reductions are prepared porous silicon for 5 hours, by the product obtainingClean through watery hydrochloric acid, remove the metal oxide in product and be the metallic reducing agent of complete reaction, be dried, obtain porous silicon.
Prepare porous carbon materials
First press the weight ratio of 1: 1 by phenolic resins and ethylene glycol mixing and stirring, add subsequently phenolic resins and ethylene glycol totalThe benzene sulfonyl chloride of weight 8% mixes makes mixture, and mixture is poured in mould, at 50 DEG C, is incubated 5h, at the beginning of inciting somebody to actionThe sample demoulding after solidifying, carries out deeply-curing processing to sample, is incubated 12h, the then every increasing of temperature in the time of 60 DEG C of initial temperaturesAdd 15 DEG C of insulation 8h, be incubated again 16h until temperature rises to 150 DEG C, at N2Under protection, carry out carbonization, rise to 600 DEG C by room temperature,Insulation 1h, heating rate is 1 DEG C/min, cools to room temperature with the furnace after completing carbonization, finally stops for N2, obtain average pore sizeBe less than the porous carbon materials of 300nm.
Prepare porous carbon/silicon composite
By above-mentioned porous silicon and porous carbon according to the ratio mechanical mixture of mass ratio 3:1, then by mixture with contain phenolic resinsFormalin mix, under inert atmosphere, carry out subsequently pyrolysis, pyrolysis temperature is 800 DEG C, pyrolysis time is 8 hours, systemFor going out porous silicon/carbon composite material.
Sintering obtains the coated lithium ferrous phosphate composite material of carbon silicon
By LiFePO4Be placed in mass concentration and be 25% the lithium metasilicate aqueous solution and soak 3h, and fully stir, solution moisture content testing is steamedSend out, by the LiFePO after soaking4Roasting 5h at 400 DEG C, at the LiFePO through roasting gained4In powder, add with respect toThe content of LiFePO4 is the above-mentioned porous silicon/carbon composite material of 3wt%, heats heating after ball milling mixes in tube furnaceTemperature is 1200 DEG C, and the heat time is 2h, obtains the coated lithium ferrous phosphate composite material of carbon silicon after cooling.
Comparative example
By common commercially available LiFePO4Be placed in mass concentration and be 20% alumina silicate and soak 3h, and fully stir, by solution moisture content testingEvaporation; By the LiFePO after soaking4Roasting 2h at 500 DEG C; (3) at the LiFePO through roasting gained4In powder, add relativelyIn LiFePO4Content be 5wt% particle diameter is the SiC of 100 μ m, the mixture obtaining is being heated in micro-wave oven, micro-Wave power is adjusted to 500W, and the control time is 25 minutes
By above-described embodiment one, two and comparative example products therefrom and conductive black and adhesive Kynoar with mass ratio 80:The ratio of 10: 10 is mixed, and is compressed on nickel screen, 150 DEG C of vacuum drying 24 hours, as working electrode. Reference electrode isLithium metal, electrolyte is 1mol/lLiPF6EC/DEC/DMC (volume ratio 1: 1: 1). Be to enter at 25 DEG C at probe temperatureRow electric performance test, after tested this embodiment mono-with two the product of material and comparative example compared with, specific capacity has improved 35-45%,Improve service life more than 1.7 times.
Claims (1)
1. a preparation method for carbon silicon coated lithium ferrous phosphate composite material for lithium ion battery, comprises the steps:
(1) prepare porous silicon
By ethyl orthosilicate pyrolysis in the ethylene glycol solution of the organic formwork that contains softex kw, preparation porousSilica, by the porous silica that contains template that obtains filter, centrifugal, clean, dry, then 500-700 in airDEG C temperature under the heat treatment carried out 3-7 hour remove template, obtain porous silica;
Be 1:5-5:1 mixed grinding by porous silica and magnesium powder according to mass ratio, then 700-900 DEG C under inert atmosphereHeat reduction 2-5 hour prepares porous silicon, and the product obtaining is cleaned through watery hydrochloric acid, remove metal oxide in product andFor the metallic reducing agent of complete reaction, dry, obtain porous silicon;
(2) prepare porous carbon materials
First by 1: 1-1: 3 weight ratio, by phenolic resins and ethylene glycol mixing and stirring, adds phenolic resins and second subsequentlyThe benzene sulfonyl chloride of glycol gross weight 8-10% mixes makes mixture, mixture is poured in mould, at 50-70 DEG CInsulation 2-5h, by the sample demoulding after just solidifying, carries out deeply-curing processing to sample, insulation in the time of initial temperature 60-80 DEG C10-12h, then 15 DEG C of insulation 6-8h of the every increase of temperature, are incubated 8～16h until temperature rises to 150-180 DEG C, again at N2ProtectionUnder carry out carbonization, rise to 600 DEG C by room temperature, insulation 1h, heating rate is 1-5 DEG C/min, cools to the furnace after completing carbonizationRoom temperature, finally stops for N2, obtain the porous carbon materials that average pore size is less than 300nm;
(3) prepare porous carbon/silicon composite
By above-mentioned porous silicon and porous carbon according to the ratio mechanical mixture of mass ratio 3:1-1:3, then by mixture with contain phenolic aldehydeThe formalin of resin is mixed, and carries out subsequently pyrolysis under inert atmosphere, and pyrolysis temperature is 800-1000 DEG C, and pyrolysis time is 5-8Hour, prepare porous silicon/carbon composite material;
(4) sintering obtains the coated lithium ferrous phosphate composite material of carbon silicon
By LiFePO4The lithium metasilicate aqueous solution that is placed in mass concentration and is 25-30% soaks 1-3h, and fully stirs, by solution waterDivide evaporation, by the LiFePO after soaking4Roasting 2-5h at 400-450 DEG C, at the LiFePO through roasting gained4In powder, addThe above-mentioned porous silicon/carbon composite material that to enter with respect to the content of LiFePO4 be 3-7wt%, after ball milling mixes in tube furnaceHeating, heating-up temperature is 1200-1500 DEG C, the heat time is 1-2h, obtains the coated LiFePO 4 of carbon silicon after cooling compoundMaterial.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946583A (en) * | 2017-12-11 | 2018-04-20 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery LiMn2O4 composite material |
| CN108039471A (en) * | 2017-12-11 | 2018-05-15 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery boron, tantalum doped iron lithium phosphate composite material |
| CN115132976A (en) * | 2021-03-26 | 2022-09-30 | 四川大学 | Method for improving capacity of lithium battery anode material and high-capacity lithium ion battery |
| CN118738337A (en) * | 2024-07-03 | 2024-10-01 | 蜂巢能源科技(上饶)有限公司 | Silicon-carbon coated lithium iron phosphate positive electrode material and preparation method thereof, positive electrode sheet, lithium ion battery and electrical equipment |
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| CN101074095A (en) * | 2007-06-26 | 2007-11-21 | 西安交通大学 | Production of porous-carbon material |
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| CN115132976A (en) * | 2021-03-26 | 2022-09-30 | 四川大学 | Method for improving capacity of lithium battery anode material and high-capacity lithium ion battery |
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| CN118738337A (en) * | 2024-07-03 | 2024-10-01 | 蜂巢能源科技(上饶)有限公司 | Silicon-carbon coated lithium iron phosphate positive electrode material and preparation method thereof, positive electrode sheet, lithium ion battery and electrical equipment |
| CN118738337B (en) * | 2024-07-03 | 2025-11-11 | 蜂巢能源科技(上饶)有限公司 | Silicon-carbon coated lithium iron phosphate positive electrode material, preparation method thereof, positive electrode plate, lithium ion battery and electric equipment |
| WO2026007934A1 (en) * | 2024-07-03 | 2026-01-08 | 蜂巢能源科技股份有限公司 | Silicon-carbon-coated lithium iron phosphate positive electrode material and preparation method therefor, positive electrode sheet, lithium-ion battery, and electric device |
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