CN102637874A - Lithium ion battery silicon-carbon composite negative-electrode material and preparation method thereof - Google Patents
Lithium ion battery silicon-carbon composite negative-electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of battery materials, in particular to a preparation method of the lithium ion battery silicon-carbon composite negative-electrode material. The preparation method of the silicon-carbon composite material comprises the following steps of: on different carbon material matrixes, carrying out high-temperature gas-phase deposition by using a silicon-carbon organic precursor and regulating parameters of reaction conditions to prepare the silicon-carbon composite negative-electrode material with excellent performances. The silicon-carbon composite negative-electrode material has the advantages of low production cost, simple process, high charge/ discharge capacity, small first irreversible capacity and excellent cycle performance, and is suitable for industrial production.
Description
Technical field
The present invention relates to the battery material field, particularly, the present invention relates to silicon-carbon composite cathode material of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is compared advantage such as have the open circuit voltage height, energy density is big, long service life, memory-less effect, pollution-free and self discharge are little with the traditional secondary battery, use more and more widely.Because the fast development and the extensive use of portable electric appts and electric automobile, very urgently for the demand of the lithium ion battery of high-energy-density, long circulation life, fast charging and discharging.Commercial at present lithium ion battery negative material is a carbon class negative material, but its theoretical capacity is merely 372mAh/g, and develops near theoretical value.Can not adapt to miniaturization development and the electric automobile of present various portable electric appts widespread demand to the large-capacity high-power chemical power source.
Therefore; A large amount of research has turned to searching can substitute the novel negative material system of material with carbon element; Wherein silicon is desirable candidate material; Because it has fabulous theoretical lithium storage content (4200mAh/g) and low embedding lithium current potential (less than 0.5V, near the embedding lithium current potential of material with carbon element), the content in the earth is also very abundant simultaneously.Yet the coulombic efficiency first that silicon materials are low and the cycle performance of extreme difference have limited its practical application.Summary is got up, and hinders silicon materials to mainly contain four reasons as lithium ion battery negative material: at first, the serious bulk effect that silicon exists in the charge and discharge cycles process causes the structural breakdown of electrode material and peels off; Secondly, the heavy damage of material structure takes place to be caused to the irreversible transformation of unordered kenel by crystalline state in silicon in the doff lithium process; The 3rd, the poor electric conductivity of silicon, and with the inhomogeneous cycle performance that reduces silicon materials of lithium reaction; The 4th, silicon particle especially nano-silicon particle is reunited easily, causes chemical property to reduce.
In order to address the above problem, present many researchers are in the modification of being devoted to the silicium cathode material and optimal design, and the problems referred to above that solve silicon materials have three class methods usually.
First kind method is a silicon deposited film, like patent CN101393980A carbon dust is mixed with adhesive attached to forming carbon-coating on the conducting base, and the method through magnetron sputtering forms silicon layer on the carbon-coating surface then, obtains lithium ion battery silicon/carbon anode material; U.S. Pat 2008/0261116A1 discloses the method that silicon grain is deposited on material with carbon element (like the carbon fiber of vapor phase growth etc.) surface, utilizes siliceous precursor to contact with material with carbon element through gas phase and decomposes in carbon material surface formation silicon grain coating; US2008/0280207A1 discloses the continuous film surface deposition CNT of forming at the silicon grain of nano-scale and has made lithium ion battery negative material.The shortcoming of the method for this formation silicon thin film is that process is complicated, and manufacturing cost is high, is inappropriate for large-scale production.
Second class methods are that silicon and other metal reactions generate silicon alloy or add other metal components; Silicon alloy becomes a focus of silicon based composite material research because of high volume energy density is arranged; With silicon and metal mixing and ball milling formation by a certain percentage multielement silicon alloy, form multielement silicon alloy/carbon composite as lithium ion battery negative with the graphite mixing and ball milling like patent CN101643864A again; Patent CN1442916A adopts two-step sintering method, and the preparation silicon-aluminum again with the organic polymer Pintsch process, is handled under the elevated-temperature seal condition behind the adding graphite powder and obtained lithium ion battery negative material alusil alloy/carbon composite earlier.The major defect of these class methods is that the silicon alloy forming process is complicated, the difficult control of alloy structure, and production cost is high, and the electrochemical properties of material is unstable.Because these silicon alloys do not make full use of the cooperative effect of multiple metal, though these alloy materials have greatly improved with respect to their chemical property of pure silicon, the improvement of cycle performance is still very limited.
The 3rd class methods are composite materials of the siliceous/carbon of preparation, and modal is to adopt the mode of carbon coating or deposition to prepare silicon/carbon composite.Can cause the specific capacity of silicon to descend to some extent though add carbon; But still be much higher than the specific capacity of carbon itself; Can be used as the desirable substitute of carbon negative electrode material of lithium ion cell; As patent CN101153358A openly introduce with high molecular polymer, silica flour and graphite powder mix, ball milling, and in inert gas a kind of lithium ion battery negative material of high temperature cabonization Processing of Preparation; Patent CN101210119A has introduced and has utilized conducting polymer coating silicon particle and form the lithium ion battery negative material method; Patent CN1767234A mixes silica flour and carbohydrate, utilizes the concentrated sulfuric acid to handle, and forms lithium ion battery silicon/carbon/graphite cathode material; Patent CN100370959A adds carbohydrate again with silica flour and graphite mixing and ball milling, utilizes sulfuric acid treatment, washing, dry, pulverize, sieve and form lithium ion battery silicon/carbon/graphite cathode material; Select the supporter of heat treated carbon black pellet as the growth of silicon ball; Under the low vacuum condition, adopt silane SiH4 vapour deposition process, nano silicon particles is deposited on the above-mentioned carbon black, form silicon-carbon cathode material (Nature Materials 2010; 9,353-358).The employed silicon particle of these class methods needs special preparation; Some uses a large amount of organic solvent, dispersant or binding agent; Major part method is at high temperature could accomplish and needs process break process; Destroy the clad structure of product, these all increase production cost and bring great inconvenience to suitability for industrialized production simultaneously, are unfavorable for the industrialization of lithium ion silicon-based anode material.
Problems such as these preparation method ubiquity cost of material height of more than reporting, complicated process of preparation, equipment requirements height, process condition harsh, seriously polluted (using HF or accessory substance in a large number), batch process difficulty; Or electrochemistry can satisfy business demand, can't industrialization.
Summary of the invention
Inventor of the present invention is through careful investigation authentication; Employing contains the vapour deposition at high temperature of silicon-carbon organic precursor; The preparation Si-C composite material is as lithium ion battery negative material; Not only improve irreversible capacity first, the stable circulation performance of silicon-based anode material, and solved problems such as silicon-based anode manufacture of materials cost height, complex process, suitability for industrialized production difficulty.
To the deficiency of prior art, one of the object of the invention is to provide a kind of silicon-carbon composite cathode material of lithium ion battery, its pattern homogeneous, controllable.Said silicon-carbon composite cathode material of lithium ion battery comprises silicon-carbon composite bed and material with carbon element matrix.
The content of silicon-carbon composite bed and material with carbon element matrix can be confirmed according to concrete needs by the prior art/new technology of one of ordinary skill in the art according to its grasp in the said silicon-carbon composite cathode material of lithium ion battery.
Preferably, said silicon-carbon composite cathode material of lithium ion battery obtains through silicon-carbon organic substance presoma gas phase is deposited on the material with carbon element matrix.
Preferably, said silicon-carbon organic substance presoma comprises organosilan, and is preferred especially, also comprises hydro carbons, and said hydro carbons is used to regulate the silicon-carbon mass ratio of composite material.
Preferably; Said organosilan is hydrocarbyl si lanes and/or alkyl halosilanes; Said alkyl and/or halogeno-group can single substituted silane and/or polysubstituted silane; Further be preferably alkyl silane and/or alkylchlorosilane; More preferably C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane are preferably a kind or at least 2 kinds combination in tetramethylsilane, tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane, the tri-methyl-chlorosilane especially, and said combination typical case but non-limiting instance have: the combination of tetramethylsilane, tetraethyl silane; The combination of dimethyldichlorosilane, tri-methyl-chlorosilane; The combination of tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane, the combination of monomethyl trichlorosilane, dimethyldichlorosilane, tri-methyl-chlorosilane, the combination of tetramethylsilane, tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane etc.
Preferably, said hydro carbons is a kind or at least 2 kinds combination in alkane, alkene, alkynes, the aromatic hydrocarbon, and is further preferred; Be a kind in C1-C6 alkane, C2-C6 alkene, the C2-C6 alkynes or at least 2 kinds combination; Be preferably a kind or at least 2 kinds combination in methane, ethane, propane, ethene, propylene, acetylene, the propine especially, said combination typical case but non-limiting instance have: the combination of methane, ethane, the combination of ethene, propylene; The combination of ethane, propane, ethene; The combination of propylene, acetylene, propine, the combination of propane, ethene, propylene, acetylene, the combination of propane, ethene, propylene, acetylene, propine etc.
Preferably; Said material with carbon element matrix is a kind or at least 2 kinds combination in carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, CNT, Graphene, the carbon fiber; Said combination typical case but non-limiting instance have: the combination of carbon black, native graphite; The combination of native graphite, graphite nodule, the combination of hollow carbon sphere, carbonaceous mesophase spherules, CNT, the combination of CNT, Graphene, carbon fiber; The combination of graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, CNT, the combination of carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules etc.
Preferably; Said vapour deposition temperature is 300～2000 ℃; For example: 300.1 ℃, 301 ℃, 302 ℃, 303 ℃, 350 ℃, 500 ℃, 1000 ℃, 1200 ℃, 1600 ℃, 1800 ℃, 1900 ℃, 1990 ℃, 1995 ℃, 1998 ℃, 1999 ℃, 1999.9 ℃ etc.; Further be preferably 600～1700 ℃, be preferably 700～1500 ℃ especially.
Preferably; Said vapour deposition pressure is below the 3Mpa; For example 0.001Mpa, 0.002Mpa, 0.003Mpa, 0.005,0.1Mpa, 0.5Mpa, 0.9Mpa, 0.99Mpa, 1.5Mpa, 2.5Mpa, 2.9Mpa, 2.95Mpa, 2.99Mpa etc.; Further be preferably below the 2Mpa, be preferably 0～1Mpa especially.
Preferably; The said vapour deposition time is more than 0.2 hour; For example: 0.21 hour, 0.22 hour, 0.23 hour, 0.25 hour, 0.35 hour, 0.45 hour, 1 hour, 5 hours, 10 hours, 15 hours, 30 hours, 40 hours, 45 hours, 47.9 hours, 47.99 hours, 50 hours etc.; Further be preferably 0.3～48 hour, more preferably 0.4～30 hour, be preferably 1.5～24 hours especially.
One of the object of the invention also is to provide a kind of preparation method of said silicon-carbon composite cathode material of lithium ion battery; Said method comprises: through silicon-carbon organic substance presoma gas phase is deposited on the material with carbon element matrix, obtain silicon-carbon composite cathode material of lithium ion battery.
Preferably, said vapour deposition is carried out under protective atmosphere.
Preferably; Said material with carbon element matrix is a kind or at least 2 kinds combination in carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, CNT, Graphene, the carbon fiber; Said combination typical case but non-limiting instance have: the combination of carbon black, native graphite; The combination of native graphite, graphite nodule, the combination of hollow carbon sphere, carbonaceous mesophase spherules, CNT, the combination of CNT, Graphene, carbon fiber; The combination of graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, CNT, the combination of carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules etc.
Preferably, said silicon-carbon organic substance presoma comprises organosilan, and is preferred especially, also comprises hydro carbons, and said hydro carbons is used to regulate the silicon-carbon mass ratio of composite material.
Preferably; Said organosilan is hydrocarbyl si lanes and/or alkyl halosilanes; Said alkyl and/or halogeno-group can single substituted silane and/or polysubstituted silane; Further be preferably alkyl silane and/or alkylchlorosilane; More preferably C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane are preferably a kind or at least 2 kinds combination in tetramethylsilane, tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane, the tri-methyl-chlorosilane especially, and said combination typical case but non-limiting instance have: the combination of tetramethylsilane, tetraethyl silane; The combination of dimethyldichlorosilane, tri-methyl-chlorosilane; The combination of tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane, the combination of monomethyl trichlorosilane, dimethyldichlorosilane, tri-methyl-chlorosilane, the combination of tetramethylsilane, tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane etc.
Preferably, said hydro carbons is a kind or at least 2 kinds combination in alkane, alkene, alkynes, the aromatic hydrocarbon, and is further preferred; Be a kind in C1-C6 alkane, C2-C6 alkene, the C2-C6 alkynes or at least 2 kinds combination; Be preferably a kind or at least 2 kinds combination in methane, ethane, propane, ethene, propylene, acetylene, the propine especially, said combination typical case but non-limiting instance have: the combination of methane, ethane, the combination of ethene, propylene; The combination of ethane, propane, ethene; The combination of propylene, acetylene, propine, the combination of propane, ethene, propylene, acetylene, the combination of propane, ethene, propylene, acetylene, propine etc.
Another of said protective atmosphere act as carrier gas; Be preferably a kind or at least 2 kinds combination in nitrogen, helium, argon gas, the neon; Said combination typical case but non-limiting instance have: the combination of nitrogen, helium, the combination of helium, argon gas, the combination of helium, argon gas, neon; The combinations of nitrogen, helium, argon gas, neon etc. are preferably a kind or at least 2 kinds combination in nitrogen, helium, the argon gas especially; Said protection gas is preferably high-purity gas, and promptly purity is equal to or higher than 99.999%.
Preferably, after said silicon-carbon organic substance presoma is dissolved in solvent, gets into consersion unit and carry out vapour deposition; Preferably; Said solvent is a kind or at least 2 kinds combination in ether, acetone, oxolane, benzene,toluene,xylene, the dimethyl formamide; Said combination typical case but non-limiting instance have: the combination of ether, acetone, the combination of benzene, toluene, the combination of oxolane, benzene, toluene; The combination of toluene, xylenes, dimethyl formamide; The combination of benzene,toluene,xylene, dimethyl formamide, the combination of ether, acetone, oxolane, benzene, toluene etc. are preferably a kind or at least 2 kinds combination in acetone, the benzene,toluene,xylene especially.
Preferably; Said vapour deposition temperature is 300～2000 ℃; For example: 300.1 ℃, 301 ℃, 302 ℃, 303 ℃, 350 ℃, 500 ℃, 1000 ℃, 1200 ℃, 1600 ℃, 1800 ℃, 1900 ℃, 1990 ℃, 1995 ℃, 1998 ℃, 1999 ℃, 1999.9 ℃ etc.; Further be preferably 600～1700 ℃, be preferably 700～1500 ℃ especially.
Preferably; Said vapour deposition pressure is below the 3Mpa; For example 0.001Mpa, 0.002Mpa, 0.003Mpa, 0.005,0.1Mpa, 0.5Mpa, 0.9Mpa, 0.99Mpa, 1.5Mpa, 2.5Mpa, 2.9Mpa, 2.95Mpa, 2.99Mpa etc.; Further be preferably below the 2Mpa, be preferably 0～1Mpa especially.
Preferably; The said vapour deposition time is more than 0.2 hour; For example: 0.21 hour, 0.22 hour, 0.23 hour, 0.25 hour, 0.35 hour, 0.45 hour, 1 hour, 5 hours, 10 hours, 15 hours, 30 hours, 40 hours, 45 hours, 47.9 hours, 47.99 hours, 50 hours etc.; Further be preferably 0.3～48 hour, more preferably 0.4～30 hour, be preferably 1.5～24 hours especially.
Preferably, the used consersion unit of said vapour deposition is a kind in fixed bed, agitated bed, the fluid bed.
As stated; Inventor of the present invention breaks through the limitation of existing research thinking; Containing the vapour deposition of silicon-carbon organic precursor high temperature through employing, to prepare silicon-carbon composite cathode material be a kind of new mentality of designing, and this technology has advantages such as production cost is low, technology is simple, suitability for industrialized production is easy.Silicon-carbon composite cathode material through this method preparation has advantages such as irreversible capacity is low first, charge/discharge capacity is high, cyclical stability is good, multiplying power property is good.This composite material have excellent electrochemical properties mainly be because the amorphous carbon that deposits simultaneously with silicon alleviated silicon in charge and discharge process because of volumetric expansion with shrink the mechanical stress that produces, eliminate bulk effect; Amorphous carbon can increase the electric conductivity of silicon based composite material greatly; Shorten the diffusion length of lithium ion, helped the fast charging and discharging process, and improved the specific capacity and the cyclical stability of material; Graphite type material is a kind of good lithium ion battery negative, fills the conductivity that increases composite material again.
With respect to prior art, the invention has the advantages that:
(1) a kind of new preparation method of silicon-carbon composite cathode material of lithium ion battery is provided;
(2) silicon-carbon composite cathode material structure according to the invention has been alleviated the mechanical stress that silicon produces because of volumetric expansion and contraction in charge and discharge process, eliminates bulk effect;
(3) the novel production technology of silicon-carbon composite cathode material of lithium ion battery according to the invention has advantages such as low production cost, technology is simple, large-scale production is easy;
(4) carbon in the composite material according to the invention can increase the electric conductivity of silicon based composite material greatly;
(5) through regulating the process conditions of gas-phase reaction, can realize silicon-carbon quality, product pattern controllable adjustment in the composite material;
(6) Si-C composite material of the inventive method preparation helps the fast charging and discharging process, and improves the specific capacity and the cyclical stability of material, in the initial charge process, can optimize the quality and the structure of solid electrolyte film, realizes reducing irreversible capacity first.
Description of drawings
Fig. 1 is the ESEM picture of embodiment 1 silicon-carbon composite cathode material.
Fig. 2 is the X-ray diffractogram of embodiment 1 silicon-carbon composite cathode material.
Fig. 3 is the thermal analysis curue of embodiment 1 silicon-carbon composite cathode material.
Fig. 4 is the first cycle charge discharge electrograph of embodiment 1 silicon-carbon composite cathode material.
Fig. 5 is the cycle performance figure of embodiment 1 silicon-carbon composite cathode material.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Following examples are that silicon-carbon organic substance presoma high temperature vapour deposition process prepares Si-C composite material, carry out electrochemical property test then.
Embodiment 1
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: graphite nodule 1 is restrained the fixed bed reactors of packing into, the 20ml dimethyldichlorosilane is dissolved in the 80ml toluene, adopt nitrogen as carrier gas; Flow velocity is 100ml/min; Pressure is 0.3MPa in the maintenance reactor, deposits 5 hours at 900 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 14.7%, and carbon content is 85.3%.
Battery is made, electrochemical property test is following: the mass ratio of silicon-carbon composite cathode material, acetylene black and PVDF (Kynoar) is 80: 10: 10; Si-C composite material and acetylene black are mixed, add PVDF (Kynoar) (PVDF is the PVDF/NMP solution of the 0.02g/mL for preparing, and NMP is the N-methyl pyrrolidone) solution then; Be coated on the Copper Foil; In vacuum drying chamber in 120 ℃ of vacuumizes 24 hours, cut-off directly be 19 centimetres disk as work electrode, lithium metal is to electrode; Electrolyte is LiPF6/EC-DMC-EMC (volume ratio 1: 1: 1), in being full of the Ar glove box, is assembled into two electrode simulated batteries.The charging/discharging voltage scope is 2.0～0.01V, and charging and discharging currents density is 100mA/g (0.5C).The electrochemical property test result sees table 1.
The Si-C composite material of above-mentioned preparation is observed surface topography at the JSM6700 model field emission scanning electron microscope that company of NEC produces.The Si-C composite material that Fig. 1 obtains for embodiment 1 amplifies 1000 times SEM figure, can clearly make out graphite nodule and silicon-carbon recombination line from figure.
EXSTARTG/DTA 6300 thermal analyzers that the Si-C composite material of above-mentioned preparation is produced in NSK Electronics Co., Ltd..Si-C composite material that Fig. 3 obtains for embodiment 1 and the TG of pure graphite nodule figure, can draw silicone content by figure is 14.7%, carbon content is 85.3%.
The Si-C composite material of above-mentioned preparation is carried out the XRD test on the X ' PertPRO MPD type multi-functional X-ray diffractometer that Dutch Panalytical company (PANalytical) produces.The XRD spectra of the Si-C composite material that Fig. 2 obtains for embodiment 1, each peak are the diffraction maximum of graphite, the peak bag of silicon when 2 θ are 28.8 °, occurs, are amorphous silicon.
The Si-C composite material of above-mentioned preparation is carried out charge-discharge test on the 2001A type charge-discharge test appearance that the blue electric company in Wuhan produces.Fig. 4,5 is respectively the high rate performance of the first cycle charge-discharge curve, composite material and the graphite nodule of the Si-C composite material that embodiment 1 obtains; Can know that discharge capacity is 1383mAh/g first; Efficiency for charge-discharge is 82.2%, is 98.2% through capability retention after 20 times.
Embodiment 2
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 is restrained the fixed bed reactors of packing into, the 30ml dimethyldichlorosilane is dissolved in the 70ml benzene, adopt nitrogen as carrier gas; Flow velocity is 150ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 10 hours at 1000 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 12.8%, and carbon content is 81.2%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 3
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: native graphite 1 is restrained the fixed bed reactors of packing into, the 30ml tri-methyl-chlorosilane is dissolved in the 70ml toluene, adopt nitrogen as carrier gas; Flow velocity is 300ml/min; Pressure is 0.5MPa in the maintenance reactor, deposits 5 hours at 1000 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 6.3%, and carbon content is 93.7%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 4
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: with the 1 gram carbonaceous mesophase spherules fixed bed reactors of packing into, 40ml monomethyl trichlorosilane is dissolved in the 60ml xylenes, adopts argon gas as carrier gas; Flow velocity is 500ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 8 hours at 1200 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 31.5%, and carbon content is 68.5%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 5
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: native graphite 1 is restrained the fluidized-bed reactor of packing into, the 40ml dimethyldichlorosilane is dissolved in the 60ml xylenes, adopt helium as carrier gas; Flow velocity is 800ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 15 hours at 600 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 28.2%, and carbon content is 71.8%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 6
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 is restrained the fixed bed reactors of packing into, the 20ml tri-methyl-chlorosilane is dissolved in the 80ml xylenes, adopt helium as carrier gas; Flow velocity is 1000ml/min; Pressure is 0.5MPa in the maintenance reactor, deposits 10 hours at 900 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 16.2%, and carbon content is 83.8%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 7
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: CNT 1 is restrained the fluidized-bed reactor of packing into, the 20ml dimethyldichlorosilane is dissolved in the 80ml xylenes, adopt argon gas as carrier gas; Flow velocity is 300ml/min; Pressure is 0.5MPa in the maintenance reactor, deposits 3 hours at 1000 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 12.5%, and carbon content is 87.5%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 8
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 is restrained the fluidized-bed reactor of packing into, the 50ml dimethyldichlorosilane is dissolved in the 50ml toluene, adopt nitrogen as carrier gas; Flow velocity is 600ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 5 hours at 900 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 15.6%, and carbon content is 84.4%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 9
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 is restrained the fluidized-bed reactor of packing into, 50ml monomethyl trichlorosilane is dissolved in the 50ml toluene, adopt nitrogen as carrier gas; Flow velocity is 100ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 12 hours at 900 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 9.2%, and agraphitic carbon content is 90.8%%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Adopt agitated bed to prepare silicon-carbon composite cathode material; Method is following: Graphene 0.5 gram is put into agitated bed reactor, 10mi monomethyl trichlorosilane is dissolved in the 90ml toluene, adopt nitrogen as carrier gas; Flow velocity is 100ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 1 hour at 300 ℃, prepares the silicon silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 19.1%, and carbon content is 80.9%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 11
Adopt agitated bed to prepare silicon-carbon composite cathode material; Method is following: native graphite 0.5 gram is put into agitated bed reactor, the 40ml dimethyldichlorosilane is dissolved in the 60ml acetone, adopt argon gas as carrier gas; Flow velocity is 400ml/min; Pressure is 0.4MPa in the maintenance reactor, deposits 12 hours at 1000 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 35.9%, and carbon content is 64.1%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 12
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 gram is put into fixed bed reactors, the 30ml tri-methyl-chlorosilane is dissolved in the 70ml xylenes, adopt argon gas as carrier gas; Flow velocity is 200ml/min; Pressure is 0.2MPa in the maintenance reactor, deposits 8 hours at 1100 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 28.6%, and carbon content is 71.4%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 13
Adopt fixed bed to prepare silicon-carbon composite cathode material; Method is following: Graphene 0.1 gram is put into fixed bed reactors, 15ml monomethyl trichlorosilane is dissolved in the 85ml toluene, adopt nitrogen as carrier gas; Flow velocity is 100ml/min; Pressure is 0.1MPa in the maintenance reactor, deposits 1 hour at 800 ℃, prepares the silicon silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 60.2%, and carbon content is 39.8%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 14
Adopt agitated bed to prepare silicon-carbon composite cathode material; Method is following: carbon fiber 0.5 gram is put into agitated bed reactor, the 40ml dimethyldichlorosilane is dissolved in the 60ml acetone, adopt argon gas as carrier gas; Flow velocity is 400ml/min; Pressure is 0.4MPa in the maintenance reactor, deposits 12 hours at 1000 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 30.9%, and carbon content is 69.1%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 15
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 gram is put into fluidized-bed reactor, the 20ml tri-methyl-chlorosilane is dissolved in the 80ml xylenes, adopt nitrogen as carrier gas; Flow velocity is 300ml/min; Pressure is 0.3MPa in the maintenance reactor, deposits 4 hours at 900 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 35.6%, and carbon content is 64.4%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 16
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: Graphene 1 gram is put into fluidized-bed reactor, the 20ml tri-methyl-chlorosilane is dissolved in the 80ml chloroform, adopt nitrogen as carrier gas; Flow velocity is 350ml/min; Pressure is 0.01MPa in the maintenance reactor, deposits 0.2 hour at 600 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 32.7%, and carbon content is 67.3%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Embodiment 17
Adopt fluid bed to prepare silicon-carbon composite cathode material; Method is following: carbonaceous mesophase spherules 1 gram is put into fluidized-bed reactor, the 20ml tri-methyl-chlorosilane is dissolved in the 80ml xylenes, adopt nitrogen as carrier gas; Flow velocity is 400ml/min; Pressure is 0.3MPa in the maintenance reactor, deposits 4 hours at 900 ℃, prepares silicon-carbon composite cathode material.Through analyzing, wherein silicone content is 35.6%, and carbon content is 64.4%.
Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
Comparative Examples
Nisiloy nano wire composite material according to CN102263243A preparation: will with after watery hydrochloric acid and the alcohol wash nickel foam be placed in the chemical vapor deposition unit; It is 80sccm that silane flow rate is set; Hydrogen flowing quantity is 80sccm, and cavity air pressure is 600Pa, and temperature is 500 ℃; Reaction time is 15min, obtains array nisiloy nano wire in the nickel foam superficial growth of cleaning.
The graphite nodule of producing with Changsha Xing Cheng negative material factory directly carries out electrode preparation and electrochemical property test.Electrode preparation and performance test are identical with embodiment 1.The electrochemical property test result sees table 1.
The electrochemical property test result of table 1 embodiment 1-17
| Embodiment | Discharge capacity first | First charge-discharge efficiency | Capability retention circulates 20 times |
| mAh/g | ％ | ％ | |
| 1 | 1383 | 82.2 | 98.2 |
| 2 | 1818 | 89.1 | 99.5 |
| 3 | 1253 | 68.6 | 79.3 |
| 4 | 2009 | 85.1 | 86.3 |
| 5 | 1034 | 61.5 | 50.3 |
| 6 | 1424 | 83.2 | 80.7 |
| 7 | 2135 | 88.9 | 99.4 |
| 8 | 1612 | 86.3 | 91.6 |
| 9 | 1399 | 78.4 | 92.9 |
| 10 | 907 | 52.5 | 46.1 |
| 11 | 2584 | 89.7 | 98.4 |
| 12 | 2393 | 87.2 | 97.8 |
| 13 | 1298 | 80.4 | 91.9 |
| 14 | 988 | 54.6 | 50.4 |
| 15 | 2145 | 88.7 | 96.5 |
| 16 | 925 | 51.6 | 61.2 |
| 17 | 1053 | 64.3 | 67.4 |
| Comparative Examples | 583 | 80.4 | 83.4 |
| Graphite nodule | 361 | 86.9 | 96.7 |
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a silicon-carbon composite cathode material of lithium ion battery is characterized in that, comprises silicon-carbon composite bed and material with carbon element matrix.
2. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1 is characterized in that, said silicon-carbon composite cathode material of lithium ion battery obtains through silicon-carbon organic substance presoma gas phase is deposited on the material with carbon element matrix;
Preferably, said silicon-carbon organic substance presoma comprises organosilan, and is preferred especially, comprises organosilan and hydro carbons;
Preferably; Said organosilan is hydrocarbyl si lanes and/or alkyl halosilanes; Further be preferably alkyl silane and/or alkylchlorosilane; More preferably C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane are preferably a kind or at least 2 kinds combination in tetramethylsilane, tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane, the tri-methyl-chlorosilane especially.
3. according to claim 1 or claim 2 silicon-carbon composite cathode material of lithium ion battery; It is characterized in that; Said hydro carbons is preferably a kind or at least 2 kinds combination in alkane, alkene, alkynes, the aromatic hydrocarbon; Further be preferably a kind or at least 2 kinds combination in C1-C6 alkane, C2-C6 alkene, the C2-C6 alkynes, be preferably a kind or at least 2 kinds combination in methane, ethane, propane, ethene, propylene, acetylene, the propine especially;
Preferably, said material with carbon element matrix is a kind or at least 2 kinds combination in carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, CNT, Graphene, the carbon fiber.
4. like each described silicon-carbon composite cathode material of lithium ion battery of claim 1-3, it is characterized in that said vapour deposition temperature is preferably 300～2000 ℃, further be preferably 600～1700 ℃, be preferably 700～1500 ℃ especially;
Preferably, said vapour deposition pressure is below the 3Mpa, further is preferably below the 2Mpa, is preferably 0～1Mpa especially;
Preferably, the said vapour deposition time is more than 0.2 hour, further is preferably 0.3～48 hour, more preferably 0.4～30 hour, is preferably 1.5～24 hours especially.
5. the preparation method like each said silicon-carbon composite cathode material of lithium ion battery of claim 1-4 comprises: through silicon-carbon organic substance presoma gas phase is deposited on the material with carbon element matrix, obtain silicon-carbon composite cathode material of lithium ion battery.
6. method as claimed in claim 5 is characterized in that, said material with carbon element matrix is preferably a kind or at least 2 kinds combination in carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, CNT, Graphene, the carbon fiber;
Preferably, said vapour deposition is carried out under protective atmosphere;
Preferably, said silicon-carbon organic substance presoma comprises organosilan, and is preferred especially, also comprises hydro carbons.
7. like claim 5 or 6 described methods; It is characterized in that; Said organosilan is hydrocarbyl si lanes and/or alkyl halosilanes; Further be preferably alkyl silane and/or alkylchlorosilane, more preferably C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane are preferably a kind or at least 2 kinds combination in tetramethylsilane, tetraethyl silane, monomethyl trichlorosilane, dimethyldichlorosilane, the tri-methyl-chlorosilane especially;
Preferably; Said hydro carbons is a kind or at least 2 kinds combination in alkane, alkene, alkynes, the aromatic hydrocarbon; Further preferred; Be a kind in C1-C6 alkane, C2-C6 alkene, the C2-C6 alkynes or at least 2 kinds combination, be preferably a kind or at least 2 kinds combination in methane, ethane, propane, ethene, propylene, acetylene, the propine especially.
8. like each described method of claim 5-7, it is characterized in that said protective atmosphere is preferably a kind or at least 2 kinds combination in nitrogen, helium, argon gas, the neon, be preferably a kind or at least 2 kinds combination in nitrogen, helium, the argon gas especially;
Preferably, after said silicon-carbon organic substance presoma is dissolved in solvent, carry out vapour deposition; Preferably, said solvent is a kind or at least 2 kinds combination in ether, acetone, oxolane, benzene,toluene,xylene, the dimethyl formamide, is preferably a kind or at least 2 kinds combination in acetone, the benzene,toluene,xylene especially.
9. like each described method of claim 5-8, it is characterized in that said vapour deposition temperature is 300～2000 ℃, further be preferably 600～1700 ℃, be preferably 700～1500 ℃ especially;
Preferably, said vapour deposition pressure is below the 3Mpa, further is preferably below the 2Mpa, is preferably 0～1Mpa especially.
10. like each described method of claim 5-9, it is characterized in that the said vapour deposition time is more than 0.2 hour, further is preferably 0.3～48 hour, more preferably 0.4～30 hour, be preferably 1.5～24 hours especially;
Preferably, the used consersion unit of said vapour deposition is a kind in fixed bed, agitated bed, the fluid bed.
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