CN105870415B - A kind of silica/nanocarbon/metal elements compounding material, preparation method and applications - Google Patents

A kind of silica/nanocarbon/metal elements compounding material, preparation method and applications Download PDF

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CN105870415B
CN105870415B CN201610262386.2A CN201610262386A CN105870415B CN 105870415 B CN105870415 B CN 105870415B CN 201610262386 A CN201610262386 A CN 201610262386A CN 105870415 B CN105870415 B CN 105870415B
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sio
composites
carbon
dispersant
slurry
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CN105870415A (en
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郭玉国
徐泉
李金熠
殷雅侠
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Beijing One Gold Amperex Technology Ltd
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Institute of Chemistry CAS
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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
    • 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
    • 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

Abstract

The present invention relates to a kind of SiOx/ C/M composites, preparation method and applications.The SiOx/ C/M composites are by SiOxMaterial, carbon material and M components are formed, and are prepared on a large scale by simple efficient, inexpensive, free of contamination production technology.The composite increases substantially SiO as lithium ion battery negative materialxThe chemical property of negative material, overcomes SiOxThe defects of electrical conductivity extreme difference of negative material, capacity play difference and coulombic efficiency are relatively low first.

Description

A kind of silica/nanocarbon/metal elements compounding material, preparation method and applications
Technical field
The present invention relates to a kind of silica/nanocarbon/metal elements compounding material, more particularly to silica/nanocarbon/metal element is answered The extensive preparation of condensation material, and the application as lithium ion battery with high energy density negative material.
Background technology：
Increasingly sharpen with a large amount of consumption and environmental pollution of non-renewable energy resources, greatly develop the renewable love knot energy Most important, there is lithium ion battery outstanding advantages of higher than energy, service life is long, green non-pollution widely should For fields such as portable electric appts and electric automobiles.Graphite is the most widely used negative pole of current commercial Li-ion battery Material, but the theoretical capacity of graphite material is only 372mAh/g, and also the graphite cathode material of current commercial applications is Close to its theoretical capacity, therefore in order to increase substantially the energy density of lithium ion battery, it is necessary to research and develop a kind of height ratio capacity Negative material replaces graphite cathode.Silicon based anode material has high theoretical capacity (4200mAh/g) and low removal lithium embedded electricity Position, the extensive concern of battery material circle is caused, but huge volume can occur during removal lithium embedded and become for silicon based anode material Change, cause electrode material coming off in cyclic process and efflorescence, cause battery performance drastically to fail.Generally use will be received at present Rice silica flour is dispersed in carbon substrate to solve the problems, such as the volumetric expansion of silicon, but the reunion of nano silica fume, oxidation and cost The problems such as high, seriously limits the application of silicon based anode material.
SiOxMaterial has high theoretical capacity (~2000mAh/g) and good bulk effect, and is followed in discharge and recharge Lithia and lithium metasilicate cushion can be formed during ring, cushion constructs stable interface in silicon face, while effectively Dispersed silicon, therefore SiOxNegative material has excellent cyclical stability, is considered as most promising high energy density lithium ion One of cell negative electrode material.But SiOxThe electrical conductivity extreme difference of material, capacity are played typically less than 1500mAh/g, and first Coulombic efficiency is relatively low, seriously limits its application.At present generally by SiOxMaterial and carbon substrate is compound improves its performance, still On the premise of not influenceing its capacity and playing, develop a kind of low cost, can prepare on a large scale, the SiO of height ratio capacityxComposite It is the technical barrier of art.
The content of the invention
It is an object of the present invention to provide a kind of silica/nanocarbon/metal element (SiOx/ C/M) composite and preparation method thereof, The composite is applied in lithium ion battery, has height ratio capacity, excellent cycling stability.Overcome SiOxThe electricity of material Conductance extreme difference, capacity play difference and the defects of coulombic efficiency are relatively low first, and provide that a kind of raw material is cheap and easy to get, production work The process route of simple, the commercially viable large-scale production of skill.
SiO provided by the inventionx/ C/M composites, wherein SiOxContent is 10%-60%, 0.5≤x≤1.5, preferably For 0.8-1.2, carbon includes agraphitic carbon and graphitized carbon, and agraphitic carbon content is 1%-20%, preferably 2%-10%, graphite Change carbon content is 30%-80%, preferably 40%-70%, M IIA, IIIA, IIB, IVB, VB, VIB, VIIB race element and its Combination, preferably aluminium, titanium, strontium, barium, manganese, vanadium, scandium, zirconium, magnesium, zinc or its combination, preferably IIIA and IIA, IVB or VB race element (combination weight is than preferred 1-5 for combination:1-5), such as Al and Mg, Ti or V combination, more preferably IIIA and Group IVB element combination, Such as Al and Ti combination, (combination weight is than preferred 1-5 for most preferably IIIA and IVB, group vib element three combination:1-5:1- 5), such as the combination of Al and Ti, V three, preferably content 0.1%-5%, 0.2%-2%, SiOx/ C/M composites are put down Equal particle diameter is 5-30 μm, preferably 8-20 μm, specific surface area 5-80m2/ g, preferably 5-20m2/ g, most preferably 5-15m2/g。
SiO of the present inventionx/ C/M composites are made in accordance with the following steps：
1) by SiOxMaterial, dispersant and M materials are crushed, mixed and sieved, and obtain dispersed slurry；
2) carbon material is added in above-mentioned slurry, is ground, disperses and mixes in ball mill, prepare viscosity it is suitable, Finely dispersed slurry；
3) slurry for obtaining step 2), dry forming；
4) precursor for obtaining step 3), sinter under an inert atmosphere, obtain SiOx/ C/M composites；
5) by SiOx/ C/M composites are sieved, except magnetic and packing.
SiO wherein described in step 1)xThe average grain diameter of material be 500nm-100 μm, preferably 1 μm -10 μm, 0.5≤x ≤ 1.5, preferably 0.8-1.2；Dispersant is selected from comprising but is not limited only to the combination of following dispersant As and dispersant B：Dispersant A is selected from polyvinylpyrrolidone, sodium alginate, preferably sodium cellulose glycolate, polyvinylpyrrolidone, and dispersant B is selected from hydroxyl Base organic matter, aldehyde radical organic matter, polymer, resin, such as sucrose, glucose, chitosan, starch, citric acid, polyacrylic acid, phenol The combination of urea formaldehyde, pitch, polyacrylonitrile, hydroxypropyl cellulose, preferably starch and hydroxypropyl cellulose, dispersant A and B's Weight is than preferred 1-3:1-3；；Broken mixing apparatus is in rolling mill, Raymond mill, airslide disintegrating mill, ball mill or sand mill The combination of one or more combination, preferably ball mill and sand mill；Screening plant is filter screen or vibratory sieve.
Wherein in step 1) in parts by weight, SiOxMaterial is 1000-6000, preferably 3000-5000, and dispersant A is 300-1000, preferably 500-800, preferably dispersant B 500-1000,800-900, metal M are 50-300, preferably 80-100.
In step 2) carbon material selected from comprising but be not limited only to the one or more in following substances：Mesocarbon is micro- Ball, hard carbon, soft carbon, crystalline flake graphite, Scaly graphite, graphene, CNT, Super P, Ketjen black, preferably crystalline flake graphite, One or more of combinations in graphene, CNT, Super P, Ketjen black；The parts by weight of carbon material are 4000- 10000, preferably 5000-7000；The rotating speed of ball mill is 300-800r/min, preferably 400-600r/min, and ball milling method is Wet ball grinding, the one or more of solution used in following solvents：Water, ethanol, acetone, ethyl acetate, Ball-milling Time For 1-9 hours, preferably 3-6 hours；Viscosity is tested in the case where temperature is 293K, and viscosity can be 10-1000mPas, be preferably 100-500mPa·s。
Drying mode is vacuum drying in step 3), open type is spray-dried, enclosed spray drying, and preferably open type spraying is dry It is dry；It can be 160~300 DEG C to be wherein spray-dried air inlet temperature, and preferably 180-250 DEG C, discharging opening temperature is 60 DEG C~120 DEG C, preferably 80-100 DEG C, solvent evaporation amount 20-60L/h, preferably 30-50L/h；Atomizer is centrifugal type atomizer, is turned Speed is 10000-30000r/min, preferably 18000-26000r/min.
Inert atmosphere described in step 4) is provided by following at least one gases：Nitrogen, argon gas, helium, the sintering temperature Spend for 400-1000 DEG C, preferably 500-800 DEG C, programming rate is 1-15 DEG C/min, preferably 5-10 DEG C/min, sintering time For 1-15h, preferably 2-5h；Agglomerating plant is atmosphere batch-type furnace, rotary furnace, roller kilns and pushed bat kiln.
SiO is removed by reciprocating sieve in step 5)xParticle diameter is more than 30 μm of particle in/C/M composites, passes through strong magnet Remove magnetic component, after composite is encapsulated in aluminium plastic bag with hot press.
The invention also discloses the SiO prepared using the above methodx/ C/M composites are as negative electrode of lithium ion battery material Material.
By SiOx/ C/M composites, conductive additive, binding agent and solvent slurrying according to a certain percentage, after slurry is passed through Cross and be coated with, be dried to obtain electrode slice.Wherein conductive additive is in carbon black, Super-P, Ketjen black, graphene, CNT One kind in one or more, preferably Super-P, graphene；The binding agent and coordinative solvent are Kynoar (with N- Methyl pyrrolidone is solvent) or polyacrylic acid, sodium carboxymethylcellulose, butadiene-styrene rubber/sodium carboxymethylcellulose, sodium alginate One or more in (using water as solvent), preferably butadiene-styrene rubber/sodium carboxymethylcellulose, sodium alginate, polyacrylic acid In one kind；Slurrying ratio is 85-95:1-5:3-10, most preferably 93:2:5, then even application dries on copper foil in vacuum Dried in case, drying temperature is 50-100 DEG C.
Any toxic solvent is not applied in the whole preparation technology of the present invention, can effectively avoid environmental pollution.
Application provided by the present invention is SiOxApplication of/C/M the composites as battery electrode material, especially as The application of lithium ion battery negative material.
Compared with prior art, SiO provided by the inventionx/ C/M composite various ingredients are well mixed, preparation method Simply, cost is low, degree of being practical is high, can prepare on a large scale, the SiO of nanosizingx(nanosizing can pass through micro-nano point to particle Dissipate grinding to realize, device therefor is mainly comprising ball mill, sand mill, between nano-scale 80-300nm, preferably 100-200) It is uniformly dispersed in carbon carrier, effectively solves SiOxThe defects of electrical conductivity difference, being applied in combination for M materials both can be SiOxSurface Creation clad, stable interface is built, caused active oxygen in calcination process can be eliminated again, given full play to SiOxCapacity, and the present invention composite in do not contain elemental silicon powder, avoid produced in deintercalation course of reaction it is huge Stress, the defects of causing efflorescence, the structural instability of material etc., be applied to lithium ion battery negative material, show Excellent cyclical stability and high coulombic efficiency.
Brief description of the drawings
Fig. 1 is the gained SiO of embodiment 1xThe electron scanning micrograph of/C/M composites.
Fig. 2 is the gained SiO of embodiment 1xThe size distribution of/C/M composites.
Fig. 3 is the gained SiO of embodiment 1x/ C/M negative materials are under 200mA/g current densities, the appearance for 100 circulations of discharging Amount change.
Embodiment
The present invention is further described with reference to specific embodiment, the present invention is not limited to following case study on implementation.
Test method described in following embodiments, it is conventional method unless otherwise specified；The reagent and material, such as Without specified otherwise, can obtain from commercial channels.
Embodiment 1
By the SiO that 3kg average grain diameters are 5 μmx, 500g sucrose, 500g polyvinylpyrrolidones, 50g aluminium powders and 40L water adds Enter into planetary ball mill, drum's speed of rotation 600r/min, after grinding 12 hours, particle diameter in slurry is removed with screen filtration Particle more than 1 μm, then add slurry into sand mill grinding pot, sand mill rotating speed is 1200r/min, is ground 12 hours Afterwards, then crystalline flake graphite, 300g graphenes and 300g SuperP that 6kg average grain diameters are 5 μm are added in above-mentioned slurry, And slurry is transferred to ball milling 4h in ball mill, drum's speed of rotation 400r/min, obtained slurry is passed through into spray dryer After dry forming, be sintered in rotary furnace in nitrogen atmosphere, sintering temperature be 700 DEG C, heating rate be 5 DEG C/ Min, sinter 2h, the SiO that will be obtainedx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 0.9, content 30%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 66% of whole composite, and amorphous carbon accounts for 3.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 14.5m2/g。
The SiO that will be prepared in embodiment 1x/ C/M composites, Super-P, CMC and SBR are with mass ratio 93:2: 2.5:2.5 mass ratio, is beaten in aqueous, the slurry being uniformly mixed, after slurry is homogeneously applied to copper foil collection On fluid, dried 8 hours in vacuum drying oven at 60 DEG C, obtain SiOx/ C/M electrode slices.Using metal lithium sheet as to electrode, Celgard2500 is as barrier film, 1mol/L LiPF6(solvent is that volume ratio is 1：1 ethylene carbonate and dimethyl carbonate mixes Close liquid) electrolyte is used as, button cell is assembled into the glove box of argon gas protection, carries out charge-discharge test, test program is 200mA/g, charging/discharging voltage section are 0.01~1.0V, and cell testing results are listed in table 1.
Embodiment 2
By the SiO that 3kg average grain diameters are 1 μmx, 500g sodium alginates, 500g polyacrylic acid, 50g magnesium powders and 40L water adds Into planetary ball mill, drum's speed of rotation 600r/min, after grinding 24 hours, by the scale that 6kg average grain diameters are 10 μm Graphite, 300g CNTs and 300g Ketjen blacks are added in above-mentioned slurry, continue the ball milling 8h in ball mill, drum's speed of rotation For 400r/min, by obtained slurry after spray dryer dry forming, it is sintered in roller kilns in argon gas atmosphere Processing, sintering temperature are 800 DEG C, and heating rate is 10 DEG C/min, sinter 3h, the SiO that will be obtainedx/ C/M composites are sieved Divide, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value is 1, and content 30%, carbon material is with nothing The two kinds of forms of carbon and graphitized carbon that shape are present, and wherein graphitized carbon accounts for the 66% of whole composite, and amorphous carbon accounts for 3.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 15.6m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Embodiment 3
By the SiO that 4kg average grain diameters are 5 μmx, 500g polyacrylic acid, 1000g polyvinylpyrrolidones, 100g zinc powders and 40L water is added in planetary ball mill, drum's speed of rotation 600r/min, after grinding 12 hours, is removed and starched with screen filtration Particle diameter is more than 1 μm of particle in material, then adds slurry into sand mill grinding pot, sand mill rotating speed is 1200r/min, is ground Mill 12 hours after, then by 5kg average grain diameters be 7 μm crystalline flake graphite, 300g graphenes be added in above-mentioned slurry, and will slurry Material is transferred to ball milling 4h in ball mill, drum's speed of rotation 400r/min, obtained slurry is dried to by spray dryer After shape, it is sintered in pushed bat kiln in nitrogen atmosphere, sintering temperature is 600 DEG C, and heating rate is 5 DEG C/min, sintering 2h, the SiO that will be obtainedx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 1.1, content 40%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 53% of whole composite, and amorphous carbon accounts for 6%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 15.8m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Embodiment 4
By the SiO that 4kg average grain diameters are 1 μmx, 400g glucose, 800g polyvinylpyrrolidones, 400g starch, 40g hydroxyls Propyl cellulose, 100g aluminium powders, 30g titanium valves, 30g vanadium powders and 40L water are added in planetary ball mill, and drum's speed of rotation is 700r/min, it is then 10 μm of crystalline flake graphite, 500g graphenes and 500g sections by 4.5kg average grain diameters after grinding 18 hours Qin is black to be added in above-mentioned slurry, and drum's speed of rotation is adjusted to 500r/min, continues ball milling 10 hours, by obtained slurry by spraying After mist drying machine dry forming, it is sintered in batch-type furnace in nitrogen atmosphere, sintering temperature is 800 DEG C, heating rate For 8 DEG C/min, 2h, the SiO that will be obtained are sinteredx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 1.2, content 40%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 55% of whole composite, and amorphous carbon accounts for 4%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 11.3m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Embodiment 5
By the SiO that 3kg average grain diameters are 5 μmx, 1000g sucrose, 1000g polyvinylpyrrolidones, 50g aluminium powders, 50g titaniums Powder and 40L water are added in planetary ball mill, drum's speed of rotation 600r/min, after grinding 12 hours, are gone with screen filtration Except particle diameter is more than 1 μm of particle in slurry, then add slurry into sand mill grinding pot, sand mill rotating speed is 1200r/ Min, it is then that 3 μm of crystalline flake graphite is added in above-mentioned slurry by 6.3kg average grain diameters after grinding 12 hours, and by slurry Ball milling 4h in ball mill, drum's speed of rotation 400r/min are transferred to, obtained slurry is passed through into spray dryer dry forming Afterwards, it is sintered in rotary furnace in nitrogen atmosphere, sintering temperature is 700 DEG C, and heating rate is 5 DEG C/min, sinters 2h, The SiO that will be obtainedx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 0.9, content 30%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 63% of whole composite, and amorphous carbon accounts for 6.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 12.5m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Embodiment 6
By the SiO that 3kg average grain diameters are 10 μmxMaterial after Raymond mill is broken, with 1000g glucose, 500g phenol Urea formaldehyde, 25g sodium carboxymethylcelluloses, 50g titanium valves, crystalline flake graphite, 500g carbon blacks and the 40L water that 6kg average grain diameters are 3 μm add Enter in ball mill, grind 12 hours, drum's speed of rotation 600r/min, obtained slurry is passed through into spray dryer dry forming Afterwards, it is sintered in rotary furnace in nitrogen atmosphere, sintering temperature is 600 DEG C, and heating rate is 5 DEG C/min, sinters 4h, The SiO that will be obtainedx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 1.0, content 30%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 65% of whole composite, and amorphous carbon accounts for 4.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 13.7m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Embodiment 7
By the SiO that 3.8kg average grain diameters are 5 μmx, 500g polyacrylic acid, 500g polyvinylpyrrolidones, 50g aluminium powders, 40g titanium valves and 40L water are added in planetary ball mill, drum's speed of rotation 600r/min, after grinding 12 hours, with screen cloth mistake Filter off and remove the particle that particle diameter in slurry is more than 1 μm, then add slurry into sand mill grinding pot, sand mill rotating speed is 1200r/min, after grinding 12 hours, the crystalline flake graphite, 600g graphenes, 700g that are then 5 μm by 4kg average grain diameters SuperP and 2kg pitches are added in above-mentioned slurry, and slurry is transferred into ball milling 6h in ball mill, and drum's speed of rotation is 500r/min, by obtained slurry after spray dryer dry forming, place is sintered in nitrogen atmosphere in pushed bat kiln Reason, sintering temperature are 800 DEG C, and heating rate is 5 DEG C/min, sinter 3h, the SiO that will be obtainedx/ C/M composites are sieved, Except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 0.9, content 38%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 53% of whole composite, and amorphous carbon accounts for 8.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 12.9m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Embodiment 8
By the SiO that 2kg average grain diameters are 5 μmx, 1000g polyvinylpyrrolidones, 500g starch, 50g aluminium powders, 20g titanium valves It is added in planetary ball mill with 40L water, drum's speed of rotation 800r/min, after grinding 24 hours, then 6kg is averaged grain Footpath is that 10 μm of crystalline flake graphite, 300g CNTs, 600g carbon blacks and 1kg pitches are added in above-mentioned slurry, in ball mill Continue ball milling 12h, drum's speed of rotation 600r/min, by obtained slurry after spray dryer dry forming, box It is sintered in stove in argon atmospher, sintering temperature is 700 DEG C, and heating rate is 5 DEG C/min, 3h is sintered, by what is obtained SiOx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 0.9, content 20%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 67% of whole composite, and amorphous carbon accounts for 8.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 12.1m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Comparative example 1
By the SiO that 3kg average grain diameters are 5 μmxIt is added to 40L water in planetary ball mill, drum's speed of rotation 600r/ Min, after grinding 12 hours, particle of the particle diameter more than 1 μm in slurry is removed with screen filtration, then adds slurry into sand mill In grinding pot, sand mill rotating speed is 1200r/min, and after grinding 12 hours, obtained slurry is dried to by spray dryer After shape, it is sintered in rotary furnace in nitrogen atmosphere, sintering temperature is 700 DEG C, and heating rate is 5 DEG C/min, sintering 2h, obtain SiOxMaterial.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value is 0.9, content 100%；Nitrogen is inhaled Desorption test obtains SiOxThe specific surface area of/C/M composites is 214.8m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Comparative example 2
By the SiO that 3kg average grain diameters are 5 μmxIt is added to 40L water in planetary ball mill, drum's speed of rotation 600r/ Min, after grinding 12 hours, particle of the particle diameter more than 1 μm in slurry is removed with screen filtration, then adds slurry into sand mill In grinding pot, sand mill rotating speed is 1200r/min, is then 5 μm of crystalline flake graphite by 7kg average grain diameters after grinding 12 hours It is added in above-mentioned slurry, and slurry is transferred to ball milling 4h in ball mill, drum's speed of rotation 400r/min, the slurry that will be obtained Material is sintered after spray dryer dry forming in rotary furnace in nitrogen atmosphere, and sintering temperature is 700 DEG C, Heating rate is 5 DEG C/min, sinters 2h, the SiO that will be obtainedx/ C/M composites are sieved, except magnetic and packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 0.9, content 30%, carbon material with Graphitized carbon form is present, and graphitized carbon accounts for the 70% of whole composite；Nitrogen adsorption desorption is tested to obtain SiOx/ C/M is compound The specific surface area of material is 48.2m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Comparative example 3
By the SiO that 3kg average grain diameters are 1 μmx, 500g sucrose, 500g phenolic resin, 50g aluminium powders and 40L water be added to row Drum's speed of rotation 600r/min, it is then 5 μm of scale stone by 6kg average grain diameters after grinding 24 hours in planetary ball mill Ink, 600g SuperP are added in above-mentioned slurry, and slurry are transferred into ball milling 4h in ball mill, drum's speed of rotation 400r/ Min, after the vacuum dried unit dry forming of obtained slurry, it is sintered, burns in nitrogen atmosphere in rotary furnace Junction temperature is 700 DEG C, and heating rate is 5 DEG C/min, sinters 2h, the SiO that will be obtainedx/ C/M composites are sieved, except magnetic And packing.
SiO is obtained under SEM (JEOL-6700F) test above-mentioned conditionxThe pattern of/C/M composites, use Laser particle analyzer tests its size distribution, and test result is shown in Table 1；SiOxMiddle x numerical value be 0.9, content 30%, carbon material with Two kinds of forms of amorphous carbon and graphitized carbon are present, and wherein graphitized carbon accounts for the 66% of whole composite, and amorphous carbon accounts for 3.5%；Nitrogen adsorption desorption is tested to obtain SiOxThe specific surface area of/C/M composites is 50.2m2/g。
Battery testing method is same as Example 1, and test result is listed in table 1.
Table 1, SiOxThe performance test results of/C/M composites

Claims (11)

  1. A kind of 1. SiOx/ C/M composites, wherein SiOxContent is 10%-60%, 0.5≤x≤1.5, and carbon includes agraphitic carbon And graphitized carbon, agraphitic carbon content are 4%-10%, graphitized carbon content is 40%-70%, and M is selected from IIIA and IVB, VIB The combination of race element three, combination weight ratio are 1-5:1-5:1-5, M content are 0.2%-2%, SiOx/ C/M composites Average grain diameter be 5-30 μm, specific surface area 5-15m2/ g, and the content sum of all components is 100%.
  2. 2. the SiO described in claim 1x/ C/M composites, wherein combinations of the M selected from Al with Ti, V three, and three Combination weight ratio is 1-5:1-5:1-5.
  3. 3. the SiO described in claim any one of 1-2xThe preparation method of/C/M composites, its preparation method are as follows：
    1) by SiOxMaterial, dispersant and M materials are crushed, mixed and sieved, and obtain dispersed slurry；
    2) carbon material is added in above-mentioned slurry, is ground, disperses and mixes in ball mill, it is suitable, scattered to prepare viscosity Uniform slurry；
    3) slurry for obtaining step 2), dry forming；
    4) precursor for obtaining step 3), sinter under an inert atmosphere, obtain SiOx/ C/M composites；
    5) by SiOx/ C/M composites are sieved, except magnetic and packing.
  4. 4. according to the method for claim 3, it is characterised in that SiO described in step 1)xThe average grain diameter of material is 1 μm -10 μm, 0.8≤x≤1.2；Dispersant is selected from the combination of following dispersant As and dispersant B：Dispersant A is selected from polyvinylpyrrolidine Ketone, sodium alginate, sodium cellulose glycolate, dispersant B are selected from sucrose, glucose, chitosan, starch, citric acid, polypropylene Acid, phenolic resin, pitch, polyacrylonitrile, hydroxypropyl cellulose, and dispersant A and B weight ratio are 1-3:1-3；Broken mixing Equipment is the one or more combination in rolling mill, Raymond mill, airslide disintegrating mill, ball mill or sand mill；Screening plant is filter Net or vibratory sieve.
  5. 5. according to the method for claim 4, it is characterised in that dispersant A is polyvinylpyrrolidone, and dispersant B is starch With the combination of hydroxypropyl cellulose.
  6. 6. according to the method described in claim any one of 3-4, it is characterised in that carbon material is in following substances in step 2) One or more：Carbonaceous mesophase spherules, hard carbon, soft carbon, crystalline flake graphite, Scaly graphite, graphene, CNT, Super P, Ketjen black, the rotating speed of ball mill is 300-800r/min, and ball milling method is wet ball grinding, and solution used is selected from following solvents In one or more：Water, ethanol, acetone, ethyl acetate, Ball-milling Time are 1-9 hours；Viscosity is surveyed in the case where temperature is 293K Examination, is 10-1000mPas.
  7. 7. according to the method described in claim any one of 3-4, it is characterised in that in step 3) drying mode for vacuum drying, Open type is spray-dried or enclosed spray drying；It is 160~300 DEG C to be wherein spray-dried air inlet temperature, and discharging opening temperature is 60 DEG C~120 DEG C, solvent evaporation amount 20-60L/h；Atomizer is centrifugal type atomizer, rotating speed 10000-30000r/min.
  8. 8. according to the method described in claim any one of 3-4, it is characterised in that inert atmosphere described in step 4) by it is following extremely A kind of few gas provides：Nitrogen, argon gas, helium, the sintering temperature are 400-1000 DEG C, and programming rate is 1-15 DEG C/min, Sintering time is 1-15h；Agglomerating plant is atmosphere batch-type furnace, rotary furnace, roller kilns or pushed bat kiln.
  9. A kind of 9. SiOx/ C/M negative materials, it is characterised in that comprising any one of the claim 1-2 composites or comprising The composite that preparation method according to claim any one of 3-8 obtains, and conductive additive, binding agent and corresponding Solvent, through slurrying, smear, dry the obtained negative material.
  10. 10. a kind of lithium ion battery, including barrier film, organic electrolyte and SiOx/ C/M composites, wherein the SiOx/ C/M is multiple Condensation material is answered for what any one of claim 1-2 any one of the composite or claim the 3-8 preparation method obtained Condensation material, the organic electrolyte are carbonic ester electrolyte, concentration 0.1-2M；In the carbonic ester electrolyte, solvent is selected from At least one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and propene carbonate, solute six Lithium fluophosphate；Barrier film is the barrier films of Celgard 2500.
  11. 11. the SiO described in claim any one of 1-2x/ C/M composites as lithium ion battery negative material application or Application of the composite that any one of person's claim 3-8 preparation method obtains as lithium ion battery negative material.
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CN106654194B (en) * 2016-11-07 2018-05-15 北京壹金新能源科技有限公司 A kind of SiO of element dopingxAnode material and its preparation method and application
CN108584907A (en) * 2018-06-12 2018-09-28 广东电网有限责任公司电力科学研究院 A kind of hard carbon material and its preparation method and application
CN108933259B (en) * 2018-08-21 2020-07-28 大同新成新材料股份有限公司 Preparation process of lithium ion battery negative electrode material
CN109659514A (en) * 2018-11-21 2019-04-19 郑州中科新兴产业技术研究院 A kind of silicon-carbon cathode material and preparation method thereof based on mesocarbon microspheres
CN110635129B (en) * 2019-08-21 2022-08-09 合肥国轩高科动力能源有限公司 Preparation method and application of silicon-based composite material
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TWI724981B (en) * 2020-10-16 2021-04-11 國立清華大學 Manufacturing method of carbide

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