CN108987689A - A kind of preparation method of silicon-carbon cathode material - Google Patents
A kind of preparation method of silicon-carbon cathode material Download PDFInfo
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- CN108987689A CN108987689A CN201810654489.2A CN201810654489A CN108987689A CN 108987689 A CN108987689 A CN 108987689A CN 201810654489 A CN201810654489 A CN 201810654489A CN 108987689 A CN108987689 A CN 108987689A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 35
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 238000009818 secondary granulation Methods 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002341 toxic gas Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910004668 SiO0.6 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
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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
- H01M4/364—Composites as mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
-
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
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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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- Silicon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of silicon-carbon cathode material.This method comprises the following steps: 1) under conditions of oxygen content is lower than 1000ppm, by metal oxide powder and SiOxPowder is uniformly mixed, and obtains mixture；2) under conditions of oxygen content is lower than 1000ppm, mixture is subjected to secondary granulation, obtains secondary granulation mixture；3) under conditions of oxygen content is lower than 1000ppm, secondary granulation mixture is calcined, compound is obtained；4) unreacted metal oxide is removed, presoma is obtained；5) carbon material is added, is uniformly mixed, calcining obtains silicon-carbon cathode material；Wherein, 0.5≤x≤1.8.The preparation method is simple, easily controllable, discharges in reaction without toxic gas, preparation process is safer, and cost of material is low, and coulombic efficiency can reach 80% or more for the first time.
Description
Technical field
The present invention relates to lithium ion Material Fields, and in particular to a kind of preparation method of silicon-carbon cathode material.
Background technique
With the fast development of portable electronic equipment, the lithium ion battery excellent for specific energy height, cycle performance
Demand is very urgent.Past lithium metal is used for negative electrode material, but will form Li dendrite in charge and discharge process using lithium metal, easily
Battery short circuit occurs, there are the risk of explosion.Thus lithium ion battery commercial at present is using graphite cathode material, though
Right graphite can show good performance as lithium ion battery negative material, but due to the low (372mAh/ of its theoretical specific capacity
G), to limit further increasing for lithium ion battery specific energy.
Silicon materials receive much attention because having high theoretical capacity (4200mAh/g), but its bad cycle performance makes
It is difficult to industrialization.The theoretical capacity that sub- silicon has 2200mAh/g is aoxidized, equally can satisfy at present to negative electrode material performance
Demand, and due to the presence of wherein oxygen atom, the Volumetric expansion of silicon is effectively inhibited, cycle life is relatively long.
But the coulombic efficiency for the first time for aoxidizing sub- silicon is too low to limit its application in negative electrode of lithium ion battery.
The method for solving the cyclical stability of silicon materials at present mainly prepares nano silicon material, but nano-silicon scale is wanted
Ask too small, it is difficult to accomplish scale production.CN103618070A discloses a kind of method for preparing nano-silicon negative electrode material, adopts
With the silicon of ceramic powders and the available 60~20nm of silicon powder mixing and ball milling, in battery performance, nanometer silicium cathode is shown
Relatively outstanding cyclical stability illustrates that this method largely successfully alleviates the huge volume expansion effect of silicon
It answers, but in order to alleviate Volumetric expansion, the theoretical capacity of silicon has only played about 25%, and the capacity reported in patent is 800
~1400mAh/g.Therefore, because the addition of a large amount of inert matters, largely improves the cost of material, and it is followed
Ring stability is also not very ideal, due to reuniting effect of the nano particle in cyclic process so that capacity attenuation still compared with
Fastly.
For improving the method for aoxidizing sub- silicon coulombic efficiency for the first time at present mainly by prelithiation and carbon coating, pass through pre- lithium
After change processing, the coulombic efficiency for the first time and cyclical stability for aoxidizing sub- silicon are all significantly improved, but currently used sub- for oxidation
The prelithiation method of silicon is less and process is complicated, operation difficulty is big；In addition, material table can be improved in carbon coating to a certain extent
Face electric conductivity improves material surface chemical property, but its effect is limited, cannot fundamentally solve asking for coulombic efficiency for the first time
Topic, CN104577086A disclose the oxidation Asia silicium cathode of a kind of prelithiation and graphene coated, make electrode material capacity for the first time
Reach 1500mAh/g, first charge-discharge efficiency reaches 91% or more, but the method higher cost and has certain risk, uncomfortable
Close large-scale production；CN103915609A mixes progress chemical vapour deposition reaction with organic carbon source by will aoxidize sub- silicon and obtains
The primary particle of first indefiniteness carbon-coating cladding, then primary particle and thermoplastic resin are subjected to solidification polymerization reaction, then low temperature
Pyrolysis, simultaneously disproportionated reaction occurs for preroast, and then classification obtains hard carbon particle, although carbon-coating equably coats the sub- silicon of oxidation,
So that the capacity and stability of material are all improved, but its carbon content is relatively high, and technique is relative complex and first circle coulomb
Efficiency, which has no, to be significantly improved；CN107611415A discloses a kind of preparation side of spherical porous silicium cathode material of lithium ion battery
Method, the first discharge specific capacity of the porous silicon negative electrode material are 2322mAh/g, charge specific capacity 1230mAh/g, but its library for the first time
Human relations efficiency is only 53%；CN105789577A then discloses the preparation method and the silicon of a kind of lithium ion battery silicium cathode material
Negative electrode material, coulombic efficiency is 75~79% for the first time, and its preparation step is cumbersome.
How using the method synthesis of silica-base negative electrode material being simple and efficient, so as to improve the coulomb for the first time of silicon based anode material
Efficiency has important practical significance for the further development and realization large-scale industrial production of silicon based anode material.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of silicon-carbon cathode material.
The technical solution used in the present invention is:
A kind of preparation method of silicon-carbon cathode material, includes the following steps:
1) under conditions of oxygen content is lower than 1000ppm, by metal oxide powder and SiOxPowder is uniformly mixed, and is obtained
Mixture；
2) under conditions of oxygen content is lower than 1000ppm, mixture is subjected to secondary granulation, obtains secondary granulation mixing
Object；
3) under conditions of oxygen content is lower than 1000ppm, secondary granulation mixture is calcined, compound is obtained；
4) unreacted metal oxide is removed, presoma is obtained；
5) carbon material is added, is uniformly mixed, calcining obtains silicon-carbon cathode material；
Wherein, 0.5≤x≤1.8.Preferably, 0.8≤x≤1.2.
Preferably, metal oxide powder and SiO in step 1)xThe mass ratio of powder is (0.1~10): 1.
Preferably, metal oxide powder and SiO in step 1)xThe mass ratio of powder is (0.5~3): 1.
It is highly preferred that metal oxide powder and SiO in step 1)xThe mass ratio of powder is (0.5~2.5): 1.
The addition of suitable metal oxide simultaneously passes through later period high-temperature process, may consequently contribute to the effect of coulomb for the first time for improving product
Rate；Excessive metal oxide will reduce the volumetric properties of material；Very few metal oxide is to product coulombic efficiency for the first time
Raising it is unobvious.
Preferably, metal oxide powder and SiO in step 1)xThe partial size D50 of powder stands alone as 0.1~1000 μm.
Preferably, the partial size D50 of metal oxide powder is 2~10 μm in step 1).
Preferably, SiO in step 1)xThe partial size D50 of powder is 3~10 μm.
Wherein, too small metal oxide and SiOxThe partial size of powder can improve cost of material, and will increase SiOxIt is exposed to
The risk being oxidized in air, and partial size is excessive, improves the subsequent energy consumption that technique is sanded.
Preferably, in step 1) metal oxide in magnesia, calcium oxide, lithia, iron oxide, aluminium oxide extremely
Few one kind.
Preferably, the partial size of mixture is D50 < 500nm, D90 < 1000nm in step 1).
It is highly preferred that the partial size of mixture is D50 < 200nm, D90 < 600nm in step 1).
Uniformity coefficient when mixture small particle helps to improve mixing and the contact area for improving mixing material.
Preferably, the partial size D50 of secondary granulation mixture is 1~30 μm in step 2).
Preferably, the partial size D50 of secondary granulation mixture is 3~20 μm in step 2).
It is highly preferred that the partial size D50 of secondary granulation mixture is 10~15 μm in step 2).
The partial size of too small secondary granulation mixture can reduce the coulombic efficiency for the first time of product, and can improve subsequent screening
The technology difficulty of partial size, and partial size is excessive, can reduce the electric conductivity and capacity of material entirety.
Preferably, step 3) is fired to the clad that outer silicon forms crystal structure, and silicon therein is also crystal structure.
Preferably, step 3) is fired to the silicate clad that outer silicon forms crystal structure.
In addition, to reach the calcining effect of step 3), calcination condition can be with are as follows: 700~1500 DEG C of calcination temperature, calcining
Time 0.1~for 24 hours, it is highly preferred that calcination condition can be with are as follows: 900~1300 DEG C of calcination temperature, 1~6h of calcination time.
Preferably, step 3) is calcined under conditions of inert gas shielding, when calcination temperature is lower than 800 DEG C, is adopted
Argon gas, nitrogen protection with purity higher than 90%；When calcination temperature is at 800 DEG C~900 DEG C, using the argon of purity 99.999%
Gas, nitrogen protection；When calcination temperature is more than or equal to 900 DEG C, protected using the argon gas of purity 99.999%.
Preferably, the mass ratio of carbon material and presoma is (0.1~30): 100.
It is highly preferred that the mass ratio of carbon material and presoma is (1~5): 100.
Preferably, unreacted metal oxide is removed using acid solution or alkaline solution.
Preferably, acid solution is selected from least one of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid.
Preferably, alkaline solution is selected from sodium hydroxide or potassium hydroxide.
Preferably, the partial size D50 of gained silicon-carbon cathode material is 1~30 μm in step 5).
Preferably, the partial size D50 of silicon-carbon cathode material is 3~20 μm.
It is highly preferred that the partial size D50 of silicon-carbon cathode material is 10~18 μm.
Wherein, the partial size of too small silicon-carbon cathode material can reduce the coulombic efficiency for the first time of product, and partial size is excessive then can
Reduce the electric conductivity and capacity of material entirety.
Wherein, D50 is indicated: the particle that partial size is greater than it accounts for 50%, and the particle less than it also accounts for 50%, is expressed as average grain
Diameter；D90 is expressed as partial size and accounts for 90% less than its particle.
Preferably, carbon material is selected from thickness≤500nm carbon material.
Preferably, carbon material in thickness≤500nm graphene, carbon nanotube, expanded graphite, thin layer graphite extremely
Few one kind.
Preferably, calcination temperature is 400 DEG C~1500 DEG C in step 5), and calcination time is 0.2~20h.
It is highly preferred that the calcination temperature in step 5) is 700 DEG C~1300 DEG C, calcination time is 1~6h.
Preferably, step 5) is calcined under conditions of inert gas, when temperature is lower than 800 DEG C, using purity is high
Argon gas, nitrogen protection in 90%；When temperature is at 800 DEG C~900 DEG C, using the argon gas of purity 99.999%, nitrogen protection；
When temperature is more than or equal to 900 DEG C, protected using the argon gas of purity 99.999%.
The beneficial effects of the present invention are:
1, the coulombic efficiency for the first time of silicon-carbon cathode material prepared by the present invention reaches 80%, thus has in lithium ion battery
There is very big application potential, also lays a good foundation for the further development of silicon based anode material.
2, the present invention is compound using first nanoscale mixing granulation, then the silicon substrate of secondary granulation fabricated in situ silicate cladding
Material, by being mixed to form silicon-carbon cathode material with carbon material, the preparation method is simple, and the macro-size of material is easily controllable,
It is discharged in reaction without toxic gas, preparation process is safer, and cost of material is low, it is easy to accomplish large-scale industrial production.
Detailed description of the invention
Fig. 1 is the electron scanning electron microscope (SEM) for the silicon-carbon cathode material that embodiment 2 obtains；
Fig. 2 is the silicon-carbon cathode material first charge-discharge curve graph that comparative example 1 obtains；
Fig. 3 is the silicon-carbon cathode material first charge-discharge curve graph that comparative example 2 obtains；
Fig. 4 is the silicon-carbon cathode material first charge-discharge curve graph that embodiment 2 obtains.
Specific embodiment
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art are according to the present invention
Some nonessential modifications and adaptations that the principle of elaboration is made all belong to the scope of protection of the present invention.Following specific works of example
Skill parameter etc. is also only an example in OK range, i.e. those skilled in the art can do suitable model by the explanation of this paper
Interior selection is enclosed, and does not really want to be defined in hereafter exemplary specific data.
Embodiment 1
A kind of preparation method of silicon-carbon cathode material, includes the following steps:
1) under conditions of oxygen content is lower than 1000ppm, by the partial size D50 magnesium oxide powder for being about 2 μm and partial size D50
About 3 μm oxidation Asia silicon (SiO) powder weighs in mass ratio for 3:2, and it is equal that dehydrated alcohol mixing of the purity greater than 99% is added
It is even, after with nanometer sand mill be sanded 7h, obtain the mixture of partial size D50 < 200nm；
2) under nitrogen gas protection, the mixture in step 1) is subjected to secondary granulation using spray drying, wherein into
Tower temperature degree is 180 DEG C, and tower exit temperature is 80 DEG C, obtains the secondary granulation mixture for the spherical particle that partial size D50 is about 15 μm；
3) under argon gas protection, secondary granulation mixture is calcined into 2h in 900 DEG C, obtains compound；
4) compound in step 3) is placed in the hydrofluoric acid that mass fraction is 10% and handles 0.5h, removed unreacted
Magnesium oxide powder obtains presoma；
5) expanded graphite that 1wt% thickness is less than 500nm is added in the resulting presoma of step 4), is uniformly mixed,
800 DEG C of calcining 2h, obtain the silicon-carbon cathode material that partial size D50 is about 15 μm in nitrogen atmosphere.
Embodiment 2~7
For operating procedure with embodiment 1, raw material and reaction condition setting see the table below 1, table 1 it is unmentioned then with embodiment 1 one
It causes:
Table 1
Comparative example 1
A kind of preparation method of silicon-carbon cathode material, includes the following steps:
1) under conditions of oxygen content is lower than 1000ppm, the SiO that 10kg partial size D50 is 10 μm is weighed0.6, purity is added
Dehydrated alcohol greater than 99% is uniformly mixed, after with nanometer sand mill 7h is sanded, obtain the Nano-meter SiO_2 of partial size D50 < 200nm0.6；
2) under argon gas protection, by Nano-meter SiO_20.6In 1000 DEG C of calcining 2h；
3) by Nano-meter SiO_2 calcined in step 2)0.6It is placed in the hydrofluoric acid that mass fraction is 10% and handles 0.5h, obtain
Presoma；
4) thin layer graphite (thickness is less than 500nm) of 3wt% is added in the resulting presoma of step 3), is uniformly mixed,
In 800 DEG C of calcining 2h in nitrogen atmosphere, the silicon-carbon cathode material that partial size is 10 μm is obtained.
Comparative example 2
A kind of preparation method of silicon-carbon cathode material, includes the following steps:
1) under conditions of oxygen content is lower than 1000ppm, the SiO that 10kg partial size D50 is 10 μm is weighed0.6, purity is added
For 99% dehydrated alcohol be uniformly mixed, after with nanometer sand mill be sanded 7h, obtain partial size D50 be 141nm Nano-meter SiO_20.6；
2) under argon gas protection, by the Nano-meter SiO_2 in step 1)0.6Secondary granulation is carried out using spray drying,
In, inlet temperature of stabilizer is 180 DEG C, and tower exit temperature is 80 DEG C, obtains the secondary granulation SiO for the spherical particle that partial size D50 is 12 μm0.6；
3) under argon gas protection, by secondary granulation SiO0.62h is calcined in 1000 DEG C；
4) gains calcined in step 3) are placed in the hydrofluoric acid that mass fraction is 10% and handle 0.5h, obtain forerunner
Body；
5) thin layer graphite (thickness is less than 500nm) of 3wt% is added in the resulting presoma of step 4), is uniformly mixed,
800 DEG C of calcining 2h in nitrogen atmosphere obtain the silicon-carbon cathode material that partial size D50 is 12 μm.
1, morphology characterization:
As seen from Figure 1, the spherical particle that the partial size of the silicon-carbon cathode material of the application preparation is about 8~25 μm.
2, electric performance test:
It is respectively anode with Examples 1 to 3 and comparative example 1~2, using lithium metal as cathode, makes half-cell test material
Performance, PVDF are binder, and active carbon is conductive agent, and the mass percent of three is that 50:30:20 passes through using NMP as solvent
Stirring is made into slurry, and slurry is uniformly coated on aluminium foil using coating machine, positive plate, electrolyte 1M are made after drying
LiPF6It is dissolved in EC/DMC (1:1, v/v), it is assembled into CR2016 battery respectively in the glove box full of argon gas, in 0.01~3V
Voltage range in, constant current charge-discharge test is carried out to battery with the current density of 150mA/g, test result is shown in Table 2, comparison
The discharge curve for the first time of example 1 and 2 is shown in that Fig. 2 and Fig. 3, Fig. 4 are the first charge-discharge curve of embodiment 2.
Table 2
It was found from table 1, Fig. 2~4: the first discharge specific capacity of embodiment is apparently higher than comparative example, highest electric discharge specific volume
Measure up to 2312mAh/g, meanwhile, when comparative example 1 and comparative example 2 charge to 2V, specific capacity be respectively 815mAh/g,
950mAh/g, and the specific capacity of embodiment 2 is then 1465mAh/g, thus the head of silicon-carbon cathode material that embodiment is prepared
Secondary coulombic efficiency is apparently higher than comparative example, up to 80% or more, this illustrates that silicon-carbon cathode material prepared by the present invention can have
Effect improves the chemical property of silicium cathode material, especially coulombic efficiency for the first time.
The coulombic efficiency for the first time of comparative example 1 is 55%, and the coulombic efficiency for the first time of comparative example 2 is 65%, it can thus be appreciated that: it is secondary
It is granulated the coulombic efficiency for the first time that can improve silicon-carbon cathode material to a certain extent.
Claims (10)
1. a kind of preparation method of silicon-carbon cathode material, characterized by the following steps:
1) under conditions of oxygen content is lower than 1000ppm, by metal oxide powder and SiOxPowder is uniformly mixed, and must be mixed
Object；
2) under conditions of oxygen content is lower than 1000ppm, mixture is subjected to secondary granulation, obtains secondary granulation mixture；
3) under conditions of oxygen content is lower than 1000ppm, secondary granulation mixture is calcined, compound is obtained；
4) unreacted metal oxide is removed, presoma is obtained；
5) carbon material is added, is uniformly mixed, calcining obtains silicon-carbon cathode material；
Wherein, 0.5≤x≤1.8.
2. preparation method according to claim 1, it is characterised in that: metal oxide powder and SiO in step 1)xPowder
Mass ratio be (0.1~10): 1.
3. preparation method according to claim 2, it is characterised in that: metal oxide powder and SiO in step 1)xPowder
Mass ratio be (0.5~3): 1.
4. preparation method according to claim 1, it is characterised in that: metal oxide powder and SiO in step 1)xPowder
Partial size D50 stand alone as 0.1~1000 μm.
5. preparation method according to any one of claims 1 to 4, it is characterised in that: metal oxide is selected from step 1)
At least one of magnesia, calcium oxide, lithia, iron oxide, aluminium oxide.
6. preparation method according to claim 1, it is characterised in that: the partial size of mixture is D50 < 500nm in step 1),
D90<1000nm。
7. preparation method according to claim 1, it is characterised in that: the partial size D50 of secondary granulation mixture in step 2)
It is 1~30 μm.
8. preparation method according to claim 1, it is characterised in that: step 3) is fired to outer silicon and forms crystal structure
Clad.
9. preparation method according to claim 1, it is characterised in that: the mass ratio of carbon material and presoma be (0.1~
30): 100.
10. preparation method according to claim 1, it is characterised in that: the partial size of gained silicon-carbon cathode material in step 5)
D50 is 1~30 μm.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1989637A (en) * | 2004-07-20 | 2007-06-27 | 三菱化学株式会社 | Anode material for lithium secondary battery, manufacturing method of the same, lithium secondary battery anode using the same, and lithium secondary battery |
| JP2009070825A (en) * | 2007-09-17 | 2009-04-02 | Samsung Sdi Co Ltd | Negative active material for lithium secondary battery, its manufacturing method, negative electrode for lithium secondary battery and lithium secondary battery |
| CN102593426A (en) * | 2011-05-07 | 2012-07-18 | 天津锦美碳材科技发展有限公司 | Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery |
| CN103608952A (en) * | 2011-06-24 | 2014-02-26 | 丰田自动车株式会社 | Negative-electrode active material, and method for production of negative-electrode active material |
| CN105655564A (en) * | 2016-03-30 | 2016-06-08 | 深圳市国创新能源研究院 | SiO<x>/C composite cathode material, method for preparing same and application of SiO<x>/C composite cathode material |
| JP2017224600A (en) * | 2016-06-09 | 2017-12-21 | 株式会社大阪チタニウムテクノロジーズ | Silicon oxide based negative electrode material |
| CN107579227A (en) * | 2017-08-31 | 2018-01-12 | 北方奥钛纳米技术有限公司 | Preparation method, silicon-carbon cathode piece and the lithium ion battery of silicon-carbon cathode piece |
| CN107768626A (en) * | 2017-09-30 | 2018-03-06 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of high power capacity rate C-base composte material, its preparation method and the purposes in lithium ion battery |
| CN107863512A (en) * | 2017-10-26 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | Silicon-carbon anode material with core-shell structure and preparation method thereof |
| EP3312916A1 (en) * | 2015-06-17 | 2018-04-25 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material for nonaqueous electrolyte secondary batteries, nonaqueous electrolyte secondary battery, and method for producing negative electrode material for nonaqueous electrolyte secondary batteries |
| CN108183217A (en) * | 2017-12-28 | 2018-06-19 | 中南大学 | Composite cathode material for lithium ion cell and preparation method thereof |
-
2018
- 2018-06-22 CN CN201810654489.2A patent/CN108987689B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1989637A (en) * | 2004-07-20 | 2007-06-27 | 三菱化学株式会社 | Anode material for lithium secondary battery, manufacturing method of the same, lithium secondary battery anode using the same, and lithium secondary battery |
| JP2009070825A (en) * | 2007-09-17 | 2009-04-02 | Samsung Sdi Co Ltd | Negative active material for lithium secondary battery, its manufacturing method, negative electrode for lithium secondary battery and lithium secondary battery |
| CN102593426A (en) * | 2011-05-07 | 2012-07-18 | 天津锦美碳材科技发展有限公司 | Method for preparing silicon oxide (SiOx) / carbon (C) composite materials and prepared silicon carbon cathode materials for lithium ion battery |
| CN103608952A (en) * | 2011-06-24 | 2014-02-26 | 丰田自动车株式会社 | Negative-electrode active material, and method for production of negative-electrode active material |
| EP3312916A1 (en) * | 2015-06-17 | 2018-04-25 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material for nonaqueous electrolyte secondary batteries, nonaqueous electrolyte secondary battery, and method for producing negative electrode material for nonaqueous electrolyte secondary batteries |
| CN105655564A (en) * | 2016-03-30 | 2016-06-08 | 深圳市国创新能源研究院 | SiO<x>/C composite cathode material, method for preparing same and application of SiO<x>/C composite cathode material |
| JP2017224600A (en) * | 2016-06-09 | 2017-12-21 | 株式会社大阪チタニウムテクノロジーズ | Silicon oxide based negative electrode material |
| CN107579227A (en) * | 2017-08-31 | 2018-01-12 | 北方奥钛纳米技术有限公司 | Preparation method, silicon-carbon cathode piece and the lithium ion battery of silicon-carbon cathode piece |
| CN107768626A (en) * | 2017-09-30 | 2018-03-06 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of high power capacity rate C-base composte material, its preparation method and the purposes in lithium ion battery |
| CN107863512A (en) * | 2017-10-26 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | Silicon-carbon anode material with core-shell structure and preparation method thereof |
| CN108183217A (en) * | 2017-12-28 | 2018-06-19 | 中南大学 | Composite cathode material for lithium ion cell and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHIL-HOON DOH 等: "A new SiO/C anode composition for lithium-ion battery", 《JOURNAL OF POWER SOURCES》 * |
| 王福庆等: "锂离子电池聚阴离子型正极材料 ", 《化学进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403741A (en) * | 2020-03-24 | 2020-07-10 | 华鼎国联四川动力电池有限公司 | Nano SiO-C composite material and application thereof in preparation of lithium ion battery cathode material |
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