CN103326023A - High-performance lithium ion battery silicon-carbon cathode material and preparation method thereof - Google Patents
High-performance lithium ion battery silicon-carbon cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lithium ion battery high specific capacity silicon-carbon composite cathode material. The high-performance lithium ion battery silicon-carbon cathode material comprises a Si-SiOx/C/DC composite system with a specific surface area of 1-30 square meters per gram, wherein the composite system comprises C matrix, Si-SiOx compound stuck in the C matrix, carbon nanotube distributed in C matrix and Si-SiOx-C, and an organic pyrolytic carbon coating on the outermost layer. The high-performance lithium ion battery cathode material has high quality specific capacity, good cycle stability and long service life, and can be used as high energy density cell cathode material for portable mobile terminals and digital products.
Description
Technical field
The invention belongs to the materialogy field, be specifically related to a kind of lithium ion battery high-specific-capacity silicon carbon composite negative pole material.
Background technology
Lithium ion battery from the nineties in last century begin practical since, because have that voltage is high, the outstanding advantages such as energy density is large, good cycle, self discharge amount are little, memory-less effect, be widely used in the fields such as portable terminal, digital product and portable mobile apparatus, electric automobile and energy-accumulating power station.But along with the birth of intelligent mobile terminal electronic equipment, lithium ion battery is difficult to satisfy its long-time instructions for use at present, and because the finite volume of portable terminal, so the exploitation of high-specific energy battery product is extremely urgent.
Used commercial lithium battery adopts cobalt acid lithium/graphite, nickel-cobalt-manganese ternary/graphite system mostly at present, but the theoretical lithium storage content of graphite itself is lower, has been difficult to the breakthrough of the capacity of obtaining by the improvement of battery process.Elemental silicon has ten theoretical specific capacity (4200mAh/g) that are multiple times than native graphite as negative material, is subject to the general concern of material circle and research.Yet there is following problem in elemental silicon as battery cathode active substance: (1) forms Li under the full power state in embedding lithium process
22Si
5Alloy phase, the change in volume of material reaches more than 300%.The mechanical internal stress that so huge bulk effect produces can make electrode active material and collector peel off gradually, and the silicon activity mutually itself also can efflorescence in addition, thereby has lost and the electrically contacting of collector, and causes cycle performance of battery to descend rapidly; (2) conductivity is low.Silicon itself is semi-conducting material, and conductivity is low only 6.7 * 10
-4Scm-1 needs to add conductive agent to improve the electronic conductivity of silicon active matter; (3) be difficult to form stable SEI film.In the charge and discharge process, huge bulk effect can cause constantly having silicon exposed in electrolyte, is difficult to form stable SEI film, causes electroactive material cycle performance fast-descending.
In the patent application of many Si-C composite negative pole materials, it mostly is the lithium storage content that improves negative material by methods such as the mixing of silicon and graphite, coating, doping, but the scattering problem of nanoscale silica flour thoroughly is not resolved always, causes electrode part subregion inactivation.The present invention adopts high-energy ball milling method to prepare the Si-SiOx presoma, in mechanical milling process, introduce submicron metal reduction SILICA FUME, obtain having with Si the SiOx of certain compatibility, when having realized good dispersion, the porousness feature of presoma has reduced the internal stress that silicon produces to a certain extent when bulk effect occurs.The present invention adopts organic RESEARCH OF PYROCARBON to coat, and not only makes the Si-SiOx of porous and carbon matrix material that better bonding is arranged, and has also eliminated the dangling bonds on the carbon base body, has also avoided activated silica to contact with the direct of electrolyte, has improved the cyclical stability of battery.
Summary of the invention
The technical problem that exists in order to solve above-mentioned carbon lithium ion cell negative electrode material an object of the present invention is to disclose a kind of specific discharge capacity high, and cyclical stability is better, the high performance carbon carbon negative electrode material of lithium ion cell that can increase the service life.Another object of the present invention is the preparation method who discloses above-mentioned high performance carbon lithium ion battery silicon-carbon cathode material.
In order to realize the foregoing invention purpose, the present invention has adopted following technical scheme:
A kind of high performance lithium ion battery silicon-carbon cathode material comprises that specific area is 1~30m
2The Si-SiOx/C/DC compound system of/g, described compound system comprises the C matrix, be bonded in Si-SiOx compound in the C matrix, be distributed in carbon nano-tube and outermost organic RESEARCH OF PYROCARBON coating layer among C matrix and the Si-SiOx-C, and described C matrix is one or more in the native graphite, Delanium, carbonaceous mesophase spherules MCMB, hard carbon through oxidation processes; Described Si-SiOx is to be that 0.01~10 μ silica flour, particle diameter are that 0.1~10 μ SILICA FUME and super-fine metal powder are removed a kind of porous compound that metal forms behind the high energy mechanical chemical reaction by particle diameter; The average diameter of described carbon nano-tube is that 5~100nm, draw ratio are the nanofiber of 2~25:1; The organic RESEARCH OF PYROCARBON coating layer of described outermost layer is the carbon coating layer that organic substance forms after polycondensation, carbonization.
As preferably, the Si-SiOx compound is the Si-SiOx of submicron order, be bonded in uniformly in the C matrix, the Si-SiOx of submicron order is scattered in the constitutionally stable material with carbon element uniformly, utilize carbon base body the cushioning effect of volumetric expansion to be improved the cycle life of silicium cathode, better prolonged useful life.
As preferably, described super-fine metal powder is one or more in aluminium powder, glass putty, zinc powder, magnesium powder, calcium powder and the titanium valve, and described super-fine metal powder particle diameter is for being 0.1~10 μ m; Described organic RESEARCH OF PYROCARBON raw material is selected from one or more in glucose, sucrose, polyvinyl chloride, phenolic resins, furfural resin, poly furfuryl alcohol, polyacrylonitrile, coal tar pitch and the petroleum asphalt.
As preferably, the mass ratio of described Si-SiOx compound and C matrix is 1:100~100:10, the mass ratio of described SILICA FUME and silica flour is 1:100~100:100, the ratio of described super-fine metal powder and SILICA FUME is 1:100~100:100, and the mass ratio of described carbon nano-tube and Si-SiOx-C is 0.1:100~20:100; The mass ratio of described organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1:100~50:100.
A kind of preparation method of high performance lithium ion battery silicon-carbon cathode material comprises the steps:
(1) with silica flour, SILICA FUME, submicron metal and dispersant, in ball grinder, carries out ball milling;
(2) with step (1) product with 50~150 ℃ of vacuumize 1~24h; Product is sintering in nitrogen and/or argon gas;
(3) step (2) product is carried out pickling, filtration, vacuum drying;
(4) the C matrix is carried out high temperature oxidation process in air atmosphere;
(5) step (3) product and step (4) product are mixed, join in the RESEARCH OF PYROCARBON solution that is added with carbon nano-tube, the low speed secondary ball milling disperses;
(6) with the heating of step (5) product, stir the evaporation desolventizing;
(7) with step (6) product sintering in non-oxidizing atmosphere, organic RESEARCH OF PYROCARBON carbonization treatment, and naturally cool to room temperature, realize that organic RESEARCH OF PYROCARBON coats;
(8) step (7) product is sieved with 200~500 eye mesh screens, obtain the Si-O-C composite negative pole material.
As preferably, the mass ratio of described Si-SiOx compound and C matrix is 1:100~100:10, the mass ratio of described SILICA FUME and silica flour is 1:100~100:100, the ratio of described super-fine metal powder and SILICA FUME is 1:100~100:100, and the mass ratio of described carbon nano-tube and Si-SiOx-C is 0.1:100~20:100; The mass ratio of described organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1:100~50:100.
As preferably, described step (1) dispersant is one or more in ethanol, the deionized water; Described ball milling is planetary milling, and abrading-ball is that diameter is the zirconia ball of 0.1~50mm, and Ball-milling Time is 1~30 hour, described drum's speed of rotation 150~500r/min.
As preferably, used acid is that mass fraction is one or more in hydrochloric acid, sulfuric acid and the nitric acid of 3%-15% in described step (3) acid cleaning process, and pickling time is 30~300 minutes; The high-temperature oxydation temperature of described step (4) C matrix is 200~500 ℃, and oxidization time is 0.5~10h; The solvent of described step (5) RESEARCH OF PYROCARBON solution be water, ethanol, benzene, toluene, how, in anthracene, cyclohexane, trichloroethylene, acetone, ethyl acetate, pyridine and the oxolane one or more; The temperature that described step (6) stirs desolventizing is 80~250 ℃, and mixing time is 1~10 hour.
As preferably, the mixed proportion of step (3) product and step (4) product is 1:100~100:100 in the described step (5).
As preferably, non-oxidizing atmosphere is one or both in nitrogen, the argon gas in the described step (7), 600~1400 ℃ of described sintering temperatures, described sintering time 1~24 hour.
Adopted a kind of high performance lithium ion battery silicon-carbon cathode material of technique scheme, negative material is the Si-SiOx/C/DC compound system, can satisfy the requirement to cell high-capacity and high circulation, Si-SiOx is bonded in the constitutionally stable material with carbon element, utilize the C matrix cushioning effect of volumetric expansion to be improved the cycle life of silicium cathode, its advantage is that specific discharge capacity is high, cyclical stability is better, long service life is fit to do the high energy density cells negative material of portable mobile termianl and digital products.The preparation method's of high performance lithium ionic cell cathode material advantage is simple, goes for technical scale production.
Description of drawings
Fig. 1 is the crystallogram (adopting Cuk α target emanation) of the prepared high power capacity silico-carbo composite material of embodiment 1;
Fig. 2 is the SEM figure of the prepared Si-C composite material of embodiment 1.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
A kind of high performance carbon carbon negative electrode material of lithium ion cell comprises the C matrix, is bonded in Si-SiOx-C in the matrix, is distributed in carbon nano-tube and outermost organic RESEARCH OF PYROCARBON coating layer among matrix and the Si-SiOx-C.
The used C matrix of this programme is native graphite, and the average grain diameter of native graphite is 6~30 μ m.Si-SiOx-C is a kind of compound that is formed with the oxide of rare HCl removal aluminium or aluminium behind the high energy mechanical chemical reaction by silica flour, SILICA FUME, ultra-fine aluminium, carbon nano-tube.Carbon nano-tube is that average diameter is that 10~100nm, draw ratio are (8~24): 1 finely disseminated nanofiber.The RESEARCH OF PYROCARBON coating layer is the RESEARCH OF PYROCARBON coating layer that organic substance forms after high temperature pyrolysis, carbonization, and the coating thickness of described organic RESEARCH OF PYROCARBON coating layer is 50~300nm.Submicron order cavernous Si-SiOx composite particles Uniform Dispersion also is bonded in the surface of native graphite matrix, and utilize organic RESEARCH OF PYROCARBON that it is coated, and forms the RESEARCH OF PYROCARBON coating layer of complete densification.Be dispersed with the carbon nanotube conducting network between composite particles and the coating layer and between the composite particles, forming height ratio capacity silico-carbo composite material of the present invention.The specific area of nucleocapsid structure composite particles is 0.8~30 ㎡/g, more preferably 0.9~10 ㎡/g.The coating thickness of matrix coating layer is 50~300nm, more preferably 80~200nm.Organic RESEARCH OF PYROCARBON quality account for whole composite negative pole material quality 1%~50%, more preferably 5%~30%.The mass ratio of Si-SiOx compound and C matrix is 1:100~100:10, the mass ratio of SILICA FUME and silica flour is 1:100~100:100, the ratio of super-fine metal powder and SILICA FUME is 1:100~100:100, and the mass ratio of carbon nano-tube and Si-SiOx-C is 0.1:100~20:100; The mass ratio of organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1:100~50:100.Among the present invention the specific capacity size of composite material accounted for by Si-SiOx compound quality whole composite negative pole material quality mark determine, the present invention is preferred 1%~50%, more preferably 10%~30%; The preferred SILICA FUME quality of the present invention account for whole composite negative pole material quality 0.01%~25%, more preferably 0.1%~15%; The preferred aluminium powder quality of the present invention account for whole composite negative pole material quality 0.0001%~10%, more preferably 0.001%5%; The preferred carbon nano-tube quality of the present invention account for whole composite negative pole material quality 0.1%~20%, more preferably 0.5%~5%;
A kind of preparation method of high performance lithium ion battery silicon-carbon cathode material comprises the steps:
(1) just high-purity silicon powder, SILICA FUME, aluminium powder mix by a certain percentage, and add alcohol as dispersant, ultrasonic dispersion 30-120 minute, change over to and carry out ball milling in the stainless steel jar mill, and add the zirconia ball of 0.2~20mm, ratio of grinding media to material example 10:1~20:1, behind the deaeration at 350~450r/min ball milling, 12~24h;
(2) with step (1) product with 60~100 ℃ of vacuum drying drying 1~24h, mechanical crushing; Product is sintering in nitrogen and/or argon gas, under the protection of industrial nitrogen, and 400~900 ℃ of sintering 1~10 hour;
(3) step (2) product is carried out pickling, filtration, vacuum drying, specifically add among rare HCl, stirring at normal temperature 10min~6h filters and washs to neutral;
(4) the C matrix is carried out high temperature oxidation process in air atmosphere, specifically with 200~600 ℃ of oxidations 2~4 hours in air atmosphere of native graphite raw material;
(5) step (3) product and step (4) product are mixed, join in the RESEARCH OF PYROCARBON solution that is added with carbon nano-tube, the low speed secondary ball milling disperses, specifically step (3) and step (4) product are added after the proportioning by a certain percentage and be dispersed with in organic RESEARCH OF PYROCARBON dispersion liquid of carbon nano-tube, 150~200r/min ball milling is 2~4 hours in the stainless steel jar mill; Ratio of grinding media to material example 10:1~15:1; Zirconia sphere diameter 10~20mm;
(6) with step (5) product heating, stir the evaporation desolventizing, specifically consider deoxidation zirconium ball after, dry out solvent under dynamic condition, temperature are 80~120 ℃;
(7) with step (6) product sintering in non-oxidizing atmosphere, organic RESEARCH OF PYROCARBON carbonization treatment, and naturally cool to room temperature, specifically 600~900 ℃ of lower sintering 4~8h under the industrial nitrogen atmosphere protection, then naturally cool to room temperature, realize that organic RESEARCH OF PYROCARBON coats;
(8) step (7) product is sieved with 200~500 eye mesh screens, obtain the Si-O-C composite negative pole material.
Above-mentioned organic RESEARCH OF PYROCARBON coating layer raw material is known in those skilled in the art, and organic RESEARCH OF PYROCARBON commonly used has glucose, sucrose, polyvinyl chloride, phenolic resins, furfural resin, poly furfuryl alcohol, polyacrylonitrile, coal tar pitch, petroleum asphalt etc.Solvent is selected from one or more of deionized water, ethanol, hexane, octane, cyclohexane, benzene, toluene, biphenyl, naphthalene, anthracene, pyridine, oxolane, and the present embodiment is selected deionized water.The average diameter of carbon nano-tube is that 20nm, average length are draw ratio 8:1~12:1.Non-oxidizing atmosphere is one or both of nitrogen and argon gas.The dispersant quality accounts for 20%~95% of whole dispersion.
Embodiment 1
Each component is as follows:
The high pure metal silica flour: 11.0g(99.9%), average grain diameter is 1.0~2.5 μ m;
SILICA FUME: 4.8g(99%), average grain diameter 3~10 μ m;
The superfine metal aluminium powder: 2.2g(99%), average grain diameter 5~10 μ m;
Rare HCl:120g(10% mass concentration);
Carbon nano tube paste: 40g(LITHIUM BATTERY, water system 5% concentration), average diameter is 20~30nm, average aspect ratio 8~12;
Native graphite: 89g(spherical graphite, LITHIUM BATTERY) average grain diameter is 6~12 μ m, and interlamellar spacing d002 is 0.3353~0.3354nm;
Sucrose: the 25g(food grade).
The preparation method is as follows:
(1) get high pure metal silica flour, SILICA FUME, superfine aluminium power, and with 100ml alcohol as the ultrasonic dispersion of dispersant 1h;
(2) above-mentioned dispersion is changed in the stainless steel jar mill, and to add the 300g diameter be 0.2~10mm zirconia ball, use the argon gas deaeration, 400r/min batch (-type) ball milling 16h on planetary ball mill after the preservative film sealing;
(3) with step (2) product elimination zirconia ball, vacuum drying, pulverizing, the lower 670 ℃ of sintering 4h of industrial nitrogen protective condition, and naturally cool to room temperature;
(4) step (3) product is added among rare HCl, stir 2h, filter and wash to neutral;
(5) with native graphite 400 ℃ of sintering 2h in air atmosphere, naturally cool to room temperature;
(6) with sucrose dissolved in 200ml distilled water, add carbon nano tube paste and step (4), (5) product, add ball grinder behind the ultrasonic dispersion 30min, and to add the 400g diameter be the zirconia ball of 5~20mm, 200r/min ball milling 2h on planetary ball mill;
(7) with behind step (6) the product filtering zirconia ball, solvent evaporated under the stirring;
(8) step (7) product is warming up to 750 and constant temperature 6h with 3~5 ℃ programming rate under industrial nitrogen protection, 900 ℃ of constant temperature 2h naturally cool to room temperature, cross 300 mesh sieves.
Make at last the composite silica carbon negative pole material, be denoted as A1.
Embodiment 2
With embodiment 1 difference be: " native graphite " changes " MCMB (MCMB) " in the component;
Other are as embodiment 1.The silicon-carbon cathode material that makes at last is denoted as A2.
Embodiment 3
With embodiment 1 difference be: " superfine metal aluminium powder " changes " superfine magnesium powder " in the component;
Other are as embodiment 1.The silicon-carbon cathode material that makes at last is denoted as A3.
Comparative Examples 1
With embodiment 1 difference be: without " the rare HCl washing of step (4) ";
Other are as embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B1.
Comparative Examples 2
With embodiment 1 difference be: (1) step did not have " adding superfine aluminium power ", without " the rare HCl washing of step (4) ";
Other are with embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B2.
Comparative Examples 3:
With embodiment 1 difference be: (1) step did not have " adding SILICA FUME ";
Other are with embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B3.
Comparative Examples 4
With embodiment 1 difference be: " step (1) does not add aluminium powder and SILICA FUME ", without " the rare HCl washing of (3) 670 ℃ of sintering of step and step (4) " process;
Other are with embodiment 1.The silicon-carbon cathode material that makes at last is denoted as B4.
Electrochemical property test
The preparation of simulated battery: water is as dispersion; 1.5 part sodium carboxymethylcellulose (CMC) and 2.5 parts of butadiene-styrene rubber (SBR) are as binding agent; 2 parts super-P is as conductive agent; 94 parts active material A1; A2; A3 and B; stirring is polished into uniform sizing material and is coated on the Copper Foil behind the drying moisture; 80 ℃ of vacuum baking 12h and compressing tablet are as electrode to be measured; metal lithium sheet is to electrode; electrolyte is that the LiPF6(EC+DMC of 1mol/L mixes with the volume ratio of 1:1); barrier film adopts the cellgard2400 film, is assembled into the button cell of CR2025 in the argon shield glove box.
Reversible specific capacity test: at LAND CT2001A battery testing cashier's office in a shop with the electric current of 0.1C with above-mentioned button cell from the 0.02V initial charge to 1.2V, calculate specific capacity by the charging capacity that records, computing formula is: specific capacity=take off first lithium capacity/active material quality.The results are shown in Table 1.
First charge-discharge efficiency test: with the constant current of 0.1C~0.002C above-mentioned button cell is discharged to 0.02V cashier's office in a shop at LAND CT2001A battery testing, then the constant current with 0.1C charges to 1.2V with battery, record first discharge capacity and initial charge capacity, thereby the calculating first charge-discharge efficiency, computing formula is: discharge capacity * 100% of first charge-discharge efficiency=initial charge capacity/first.The results are shown in Table 1.
Loop test:, under 25 ℃ of constant temperatures, button cell is carried out charge-discharge test with the 0.1C electric current between 0.02-1.2V at LAND CT2001A battery testing cashier's office in a shop.Circulate 50 weeks or volume lowering to initial capacity below 70%, stop test.The results are shown in Table 1.
As can be seen from Table 1, embodiment A 2, A3 and A1 compare, first reversible specific capacity A2<A1, A3, first charge-discharge efficiency and cyclical stability A2 are better than A1, A3 a little, and this phenomenon is because, Stability Analysis of Structures little than native graphite as the specific capacity of skeleton carbon MCMB own causes.B3 compares with embodiment A 1 with B4 in the Comparative Examples, and reversible specific capacity, first charge-discharge efficiency all present B4>B3>A1 first, illustrates that the introducing of SiOx has increased its first irreversible specific capacity; B1, B2 compare with embodiment A 1 with B3 in the Comparative Examples, and pilot process is introduced the raising that reactive metal is conducive to cyclical stability, and reactive metal or its compound cause capacity that very fast decay is arranged without removal.The comprehensive above data of analyzing illustrate that the cycle performance of high-specific-capacity silicon carbon negative pole of the present invention is greatly improved.
Below only be that feature of the present invention is implemented example, protection range of the present invention is not constituted any limitation.The equal exchange of all employings or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (10)
1. high performance lithium ion battery silicon-carbon cathode material, it is characterized in that comprising that specific area is the Si-SiOx/C/DC compound system of 1~30 ㎡/g, described compound system comprises the C matrix, be bonded in Si-SiOx compound in the C matrix, be distributed in carbon nano-tube and outermost organic RESEARCH OF PYROCARBON coating layer among C matrix and the Si-SiOx-C;
Described C matrix is one or more in the native graphite, Delanium, carbonaceous mesophase spherules MCMB, hard carbon through oxidation processes;
Described Si-SiOx is to be that 0.01~10 μ silica flour, particle diameter are that 0.1~10 μ SILICA FUME and super-fine metal powder are removed a kind of porous compound that metal forms behind the high energy mechanical chemical reaction by particle diameter;
The average diameter of described carbon nano-tube is that 5~100nm, draw ratio are the nanofiber of 2~25:1;
The organic RESEARCH OF PYROCARBON coating layer of described outermost layer is the carbon coating layer that organic substance forms after polycondensation, carbonization.
2. a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 1, it is characterized in that: the Si-SiOx compound is the Si-SiOx of submicron order, is bonded in uniformly in the C matrix.
3. a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 1, it is characterized in that: described super-fine metal powder is one or more in aluminium powder, glass putty, zinc powder, magnesium powder, calcium powder and the titanium valve,
Described super-fine metal powder particle diameter is for being 0.1~10 μ m; Described organic RESEARCH OF PYROCARBON raw material is selected from one or more in glucose, sucrose, polyvinyl chloride, phenolic resins, furfural resin, poly furfuryl alcohol, polyacrylonitrile, coal tar pitch and the petroleum asphalt.
4. a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 1, it is characterized in that: the mass ratio of described Si-SiOx compound and C matrix is 1:100~100:10, the mass ratio of described SILICA FUME and silica flour is 1:100~100:100, the ratio of described super-fine metal powder and SILICA FUME is 1:100~100:100, and the mass ratio of described carbon nano-tube and Si-SiOx-C is 0.1:100~20:100; The mass ratio of described organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1:100~50:100.
5. the preparation method of a high performance lithium ion battery silicon-carbon cathode material is characterized in that comprising the steps:
(1) with silica flour, SILICA FUME, submicron metal and dispersant, in ball grinder, carries out ball milling;
(2) with step (1) product with 50~150 ℃ of vacuumize 1~24h; Product is sintering in nitrogen and/or argon gas;
(3) step (2) product is carried out pickling, filtration, vacuum drying;
(4) the C matrix is carried out high temperature oxidation process in air atmosphere;
(5) step (3) product and step (4) product are mixed, join in the RESEARCH OF PYROCARBON solution that is added with carbon nano-tube, the low speed secondary ball milling disperses;
(6) with the heating of step (5) product, stir the evaporation desolventizing;
(7) with step (6) product sintering in non-oxidizing atmosphere, organic RESEARCH OF PYROCARBON carbonization treatment, and naturally cool to room temperature, realize that organic RESEARCH OF PYROCARBON coats;
(8) step (7) product is sieved with 200~500 eye mesh screens, obtain the Si-O-C composite negative pole material.
6. the preparation method of a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 5, it is characterized in that: the mass ratio of described Si-SiOx compound and C matrix is 1:100~100:10, the mass ratio of described SILICA FUME and silica flour is 1:100~100:100, the ratio of described super-fine metal powder and SILICA FUME is 1:100~100:100, and the mass ratio of described carbon nano-tube and Si-SiOx-C is 0.1:100~20:100; The mass ratio of described organic RESEARCH OF PYROCARBON and Si-SiOx-C is 1:100~50:100.
7. the preparation method of a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 5, it is characterized in that: described step (1) dispersant is one or more in ethanol, the deionized water; Described ball milling is planetary milling, and abrading-ball is that diameter is the zirconia ball of 0.1~50mm, and Ball-milling Time is 1~30 hour, described drum's speed of rotation 150~500r/min.
8. the preparation method of a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 5, it is characterized in that: used acid is that mass fraction is one or more in hydrochloric acid, sulfuric acid and the nitric acid of 3%-15% in described step (3) acid cleaning process, and pickling time is 30~300 minutes; The high-temperature oxydation temperature of described step (4) C matrix is 200~500 ℃, and oxidization time is 0.5~10h; The solvent of described step (5) RESEARCH OF PYROCARBON solution be water, ethanol, benzene, toluene, how, in anthracene, cyclohexane, trichloroethylene, acetone, ethyl acetate, pyridine and the oxolane one or more; The temperature that described step (6) stirs desolventizing is 80~250 ℃, and mixing time is 1~10 hour.
9. the preparation method of a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 5 is characterized in that: the mixed proportion of step (3) product and step (4) product is 1:100~100:100 in the described step (5).
10. the preparation method of a kind of high performance lithium ion battery silicon-carbon cathode material according to claim 5, it is characterized in that: non-oxidizing atmosphere is one or both in nitrogen, the argon gas in the described step (7), 600~1400 ℃ of described sintering temperatures, described sintering time 1~24 hour.
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CN103779601A (en) * | 2013-12-19 | 2014-05-07 | 宁波维科电池股份有限公司 | Silicon cathode lithium ion battery and manufacturing method thereof |
CN103956496A (en) * | 2014-04-29 | 2014-07-30 | 长沙格翎电池材料有限公司 | Lithium ion battery negative active material and preparation method thereof |
CN104393262A (en) * | 2014-10-22 | 2015-03-04 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon composite anode material and preparation method thereof, as well as lithium ion battery containing same |
CN107221654A (en) * | 2017-05-25 | 2017-09-29 | 济南大学 | A kind of three-dimensional porous nest like silicon-carbon composite cathode material and preparation method thereof |
CN108336342A (en) * | 2018-02-28 | 2018-07-27 | 宁波富理电池材料科技有限公司 | Si/SiOx/C composite negative pole materials, preparation method and lithium ion battery |
CN108598454A (en) * | 2018-05-29 | 2018-09-28 | 宁波大学 | A kind of silicon-carbon cathode material, preparation method and lithium ion battery |
CN108933232A (en) * | 2018-07-17 | 2018-12-04 | 大同新成新材料股份有限公司 | A kind of preparation process of lithium battery silicon-carbon cathode |
CN109921020A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material |
CN110178251A (en) * | 2017-02-07 | 2019-08-27 | 瓦克化学股份公司 | The nucleocapsid composite particles of anode material for lithium ion battery |
CN111082005A (en) * | 2019-12-06 | 2020-04-28 | 欣旺达电动汽车电池有限公司 | Negative electrode material, composite material and preparation method thereof |
CN111640919A (en) * | 2020-05-14 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-first-efficiency silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
CN111668463A (en) * | 2020-05-07 | 2020-09-15 | 东莞市鸿德电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
EP3653576A3 (en) * | 2018-11-16 | 2020-09-30 | National Chung-Shan Institute of Science and Technology | Anode material of nano-silicon having multilayer-graphene as carrier and coated with silicon suboxide and with amorphous carbon layer and method for fabricating the same |
US10879530B2 (en) | 2018-12-13 | 2020-12-29 | National Chung-Shan Institute Of Science And Technology | Anode material of nano-silicon having multilayer-graphene as carrier and coated with silicon suboxide and with amorphous carbon layer and method for fabricating the same |
CN112374482A (en) * | 2020-10-08 | 2021-02-19 | 孚林(常州)新材料科技有限公司 | Lithium ion battery silicon-oxygen-fluorine-carbon negative electrode material prepared by mechanochemical method |
CN112713273A (en) * | 2020-12-18 | 2021-04-27 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of battery zinc cathode material |
US11069885B2 (en) | 2017-09-13 | 2021-07-20 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
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CN114824237A (en) * | 2022-04-15 | 2022-07-29 | 晖阳(贵州)新能源材料有限公司 | Silicon-carbon composite material coated with fast ion conductor and preparation method thereof |
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CN1794494A (en) * | 2004-09-24 | 2006-06-28 | 株式会社东芝 | Negative electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
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CN103779601B (en) * | 2013-12-19 | 2016-08-31 | 宁波维科电池股份有限公司 | A kind of silicon cathode lithium ion battery and manufacture method |
CN103779601A (en) * | 2013-12-19 | 2014-05-07 | 宁波维科电池股份有限公司 | Silicon cathode lithium ion battery and manufacturing method thereof |
CN103956496A (en) * | 2014-04-29 | 2014-07-30 | 长沙格翎电池材料有限公司 | Lithium ion battery negative active material and preparation method thereof |
CN104393262B (en) * | 2014-10-22 | 2018-05-15 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of carbon compound cathode materials and preparation method thereof and the lithium ion battery for including it |
CN104393262A (en) * | 2014-10-22 | 2015-03-04 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon composite anode material and preparation method thereof, as well as lithium ion battery containing same |
CN110178251A (en) * | 2017-02-07 | 2019-08-27 | 瓦克化学股份公司 | The nucleocapsid composite particles of anode material for lithium ion battery |
CN110178251B (en) * | 2017-02-07 | 2022-09-16 | 瓦克化学股份公司 | Core-shell composite particles for anode materials of lithium ion batteries |
CN107221654A (en) * | 2017-05-25 | 2017-09-29 | 济南大学 | A kind of three-dimensional porous nest like silicon-carbon composite cathode material and preparation method thereof |
US11069885B2 (en) | 2017-09-13 | 2021-07-20 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
US11652201B2 (en) | 2017-09-13 | 2023-05-16 | Unifrax I Llc | Silicon-based anode material for lithium ion battery |
CN109921020A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material |
CN108336342A (en) * | 2018-02-28 | 2018-07-27 | 宁波富理电池材料科技有限公司 | Si/SiOx/C composite negative pole materials, preparation method and lithium ion battery |
CN108336342B (en) * | 2018-02-28 | 2020-10-13 | 宁波富理电池材料科技有限公司 | Si/SiOx/C composite negative electrode material, preparation method thereof and lithium ion battery |
CN108598454A (en) * | 2018-05-29 | 2018-09-28 | 宁波大学 | A kind of silicon-carbon cathode material, preparation method and lithium ion battery |
CN108933232A (en) * | 2018-07-17 | 2018-12-04 | 大同新成新材料股份有限公司 | A kind of preparation process of lithium battery silicon-carbon cathode |
EP3653576A3 (en) * | 2018-11-16 | 2020-09-30 | National Chung-Shan Institute of Science and Technology | Anode material of nano-silicon having multilayer-graphene as carrier and coated with silicon suboxide and with amorphous carbon layer and method for fabricating the same |
US10879530B2 (en) | 2018-12-13 | 2020-12-29 | National Chung-Shan Institute Of Science And Technology | Anode material of nano-silicon having multilayer-graphene as carrier and coated with silicon suboxide and with amorphous carbon layer and method for fabricating the same |
CN111082005A (en) * | 2019-12-06 | 2020-04-28 | 欣旺达电动汽车电池有限公司 | Negative electrode material, composite material and preparation method thereof |
CN111668463A (en) * | 2020-05-07 | 2020-09-15 | 东莞市鸿德电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
CN111668463B (en) * | 2020-05-07 | 2022-11-08 | 东莞市鸿德电池有限公司 | Lithium ion battery cathode material and preparation method thereof |
CN111640919A (en) * | 2020-05-14 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-first-efficiency silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
CN111640919B (en) * | 2020-05-14 | 2021-10-22 | 浙江金鹰新能源技术开发有限公司 | High-first-efficiency silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
CN112374482A (en) * | 2020-10-08 | 2021-02-19 | 孚林(常州)新材料科技有限公司 | Lithium ion battery silicon-oxygen-fluorine-carbon negative electrode material prepared by mechanochemical method |
CN112713273B (en) * | 2020-12-18 | 2022-04-26 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of battery zinc cathode material |
CN112713273A (en) * | 2020-12-18 | 2021-04-27 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of battery zinc cathode material |
CN113644243A (en) * | 2021-07-30 | 2021-11-12 | 清华大学 | Nitrogen-doped hollow-structure graphite microsphere, composite negative electrode material and preparation method of composite negative electrode material |
CN114824237A (en) * | 2022-04-15 | 2022-07-29 | 晖阳(贵州)新能源材料有限公司 | Silicon-carbon composite material coated with fast ion conductor and preparation method thereof |
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