CN102637874B - A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to battery material field, particularly, the present invention relates to a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery.The preparation method of this Si-C composite material is: on different material with carbon element matrix, adopts silicon-carbon organic precursor to carry out high temperature vapour deposition, by regulating reaction condition parameter, the silicon-carbon composite cathode material of excellent.This silicon-carbon composite cathode material production cost is low, technique simple, be suitable for suitability for industrialized production, and charge/discharge capacity is high, irreversible capacity is little first, cycle performance is excellent.
Description
Technical field
The present invention relates to battery material field, particularly, the present invention relates to silicon-carbon composite cathode material of lithium ion battery and preparation method thereof.
Background technology
The advantages such as lithium ion battery has compared with traditional secondary cell that open circuit voltage is high, energy density is large, long service life, memory-less effect, pollution-free and self discharge are little, apply more and more extensive.Due to fast development and the extensive use of portable electric appts and electric automobile, the demand for the lithium ion battery of high-energy-density, long circulation life, fast charging and discharging is very urgent.The lithium ion battery negative material of current commercialization is carbon class negative material, but its theoretical capacity is only 372mAh/g, and has developed close to theoretical value.The miniaturization of current various portable electric appts and electric automobile can not be adapted to the widespread demand of large-capacity high-power chemical power source.
Therefore, large quantifier elimination has turned to the Novel anode material system found and can substitute material with carbon element, wherein silicon is desirable candidate material, because it has fabulous theoretical lithium storage content (4200mAh/g) and low intercalation potential (is less than 0.5V, intercalation potential close to material with carbon element), the content simultaneously in the earth is also very abundant.But the cycle performance of the initial coulomb efficiency that silicon materials are low and extreme difference limits its practical application.Sum up, hinder silicon materials to mainly contain four reasons as lithium ion battery negative material: first, the serious bulk effect that silicon exists in charge and discharge cycles process causes the structural breakdown of electrode material and peels off; Secondly, there is the heavy damage being caused material structure by crystalline state to the irreversible transformation of unordered kenel in silicon in doff lithium process; 3rd, the poor electric conductivity of silicon, and react the uneven cycle performance reducing silicon materials with lithium; 4th, silicon particle especially nano-silicon particle is easily reunited, and causes chemical property to reduce.
In order to solve the problem, current many researchers are being devoted to modification and the optimal design of silicium cathode material, and the problems referred to above solving silicon materials have three class methods usually.
First kind method is silicon deposited film, forms carbon-coating as carbon dust mixes with adhesive to be attached on conducting base by patent CN101393980A, then forms silicon layer by the method for magnetron sputtering on carbon-coating surface, obtains lithium ion battery silicon/anode composite; US Patent No. 2008/0261116A1 discloses method silicon grain being deposited on material with carbon element (carbon fiber etc. as vapor phase growth) surface, utilizes siliceous precursor to be contacted by gas phase with material with carbon element and decompose and forms silicon grain coating at carbon material surface; US2008/0280207A1 discloses the continuous film surface deposition carbon nano-tube formed at the silicon grain of nano-scale and manufactures 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 unsuitable for large-scale production.
Equations of The Second Kind method is 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 there being high volume energy density, as patent CN101643864A by silicon and metal by a certain percentage mixing and ball milling form multielement silicon alloy, then form multielement silicon alloy/carbon composite material with graphite mixing and ball milling and be used as lithium ion battery negative; Patent CN1442916A adopts two-step sintering method, first prepares silicon-aluminum, then by organic polymer Pintsch process, after adding graphite powder, under elevated-temperature seal condition, process obtains lithium ion battery negative material alusil alloy/carbon composite.The major defect of these class methods is that silicon alloy forming process is complicated, and alloy structure difficulty controls, 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 various metals, although these alloy materials have greatly improved relative to their chemical property of pure silicon, the improvement of cycle performance is still very limited.
3rd class methods are composite materials of the siliceous/carbon of preparation, and modal is adopt carbon mode that is coated or deposition to prepare silicon/carbon composite.The specific capacity of silicon can be caused to decline to some extent although add carbon, but still be much higher than the specific capacity of carbon itself, can be used as the ideal substitute of carbon negative electrode material of lithium ion cell, as patent CN101153358A openly introduces the mixing of high molecular polymer, silica flour and graphite powder, ball milling, and a kind of lithium ion battery negative material is prepared in high temperature cabonization process in inert gas; Patent CN101210119A describes and utilizes conducting polymer coated Si particle and form lithium ion battery negative material method; Patent CN1767234A, by silica flour and carbohydrate mixing, utilizes dense sulfuric acid treatment, and forms lithium ion battery silicon/carbon/graphite cathode material; Patent CN100370959A by silica flour and graphite mixing and ball milling, then adds carbohydrate, utilizes sulfuric acid treatment, washing, dry, pulverize, sieve and form lithium ion battery silicon/carbon/graphite cathode material; Select the supporter that heat treated carbon black pellet grows as silicon ball, under low vacuum condition, adopt silane SiH4 vapour deposition process, make nano silicon particles deposit on above-mentioned carbon black, form silicon-carbon cathode material (Nature Materials 2010,9,353-358).The silicon particle that these class methods use needs special preparation, some uses a large amount of organic solvents, dispersant or binding agent, major part method at high temperature just can complete and need through 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.
These preparation method ubiquity costs of material more than reported are high, complicated process of preparation, equipment requirement are high, process condition is harsh, seriously polluted (a large amount of use HF or accessory substance), the problem such as batch production difficulty, or electrochemistry can meet business demand, cannot industrialization.
Summary of the invention
The present inventor is through carefully investigating certification, adopt containing the at high temperature vapour deposition of silicon-carbon organic precursor, prepare Si-C composite material and be used as lithium ion battery negative material, not only improve the irreversible capacity first of silicon based anode material, stable circulation performance, and solve the problems such as silicon based anode material production cost is high, complex process, suitability for industrialized production difficulty.
For the deficiencies in the prior art, an object of the present invention is to provide a kind of silicon-carbon composite cathode material of lithium ion battery, and its pattern is homogeneous, controllable.Described silicon-carbon composite cathode material of lithium ion battery comprises silicon-carbon composite bed and material with carbon element matrix.
Prior art/new technology that in described silicon-carbon composite cathode material of lithium ion battery, the content of silicon-carbon composite bed and material with carbon element matrix can be grasped according to it by one of ordinary skill in the art, determines according to specific needs.
Preferably, described silicon-carbon composite cathode material of lithium ion battery is by obtaining the vapour deposition of silicon-carbon organic matter precursor on material with carbon element matrix.
Preferably, described silicon-carbon organic matter precursor comprises organosilan, particularly preferably, also comprises hydro carbons, and described hydro carbons is for regulating the silicon-carbon mass ratio of composite material.
Preferably, described organosilan is hydrocarbyl si lanes and/or alkyl halosilanes, described alkyl and/or halogeno-group can single substituted silane and/or polysubstituted silane, more preferably alkyl silane and/or alkylchlorosilane, be more preferably C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane, be particularly preferably tetramethylsilane, tetraethyl silane, Trichloromethyl silane, dimethyldichlorosilane, 1 kind in tri-methyl-chlorosilane or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: tetramethylsilane, the combination of tetraethyl silane, dimethyldichlorosilane, the combination of tri-methyl-chlorosilane, tetraethyl silane, Trichloromethyl silane, the combination of dimethyldichlorosilane, Trichloromethyl silane, dimethyldichlorosilane, the combination of tri-methyl-chlorosilane, tetramethylsilane, tetraethyl silane, Trichloromethyl silane, the combination etc. of dimethyldichlorosilane.
Preferably, described hydro carbons is alkane, alkene, alkynes, 1 kind in aromatic hydrocarbon or the combination of at least 2 kinds, further preferably, for C1-C6 alkane, C2-C6 alkene, 1 kind in C2-C6 alkynes or the combination of at least 2 kinds, be particularly preferably methane, ethane, propane, ethene, propylene, acetylene, 1 kind in propine or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: methane, the combination of ethane, ethene, the combination of propylene, ethane, propane, the combination of ethene, propylene, acetylene, the combination of propine, propane, ethene, propylene, the combination of acetylene, propane, ethene, propylene, acetylene, the combination etc. of propine.
Preferably, described material with carbon element matrix is carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, carbon nano-tube, Graphene, 1 kind in carbon fiber or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: carbon black, the combination of native graphite, native graphite, the combination of graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, the combination of carbon nano-tube, carbon nano-tube, Graphene, the combination of carbon fiber, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, the combination of carbon nano-tube, carbon black, native graphite, graphite nodule, hollow carbon sphere, the combination etc. of carbonaceous mesophase spherules.
Preferably, described vapour deposition temperature is 300 ~ 2000 DEG C, such as: 300.1 DEG C, 301 DEG C, 302 DEG C, 303 DEG C, 350 DEG C, 500 DEG C, 1000 DEG C, 1200 DEG C, 1600 DEG C, 1800 DEG C, 1900 DEG C, 1990 DEG C, 1995 DEG C, 1998 DEG C, 1999 DEG C, 1999.9 DEG C etc., more preferably 600 ~ 1700 DEG C, be particularly preferably 700 ~ 1500 DEG C.
Preferably, described vapour deposition pressure is below 3Mpa, such as 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., more preferably below 2Mpa, is particularly preferably 0 ~ 1Mpa.
Preferably, described vapor deposition times is more than 0.2 hour, such as: 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., more preferably 0.3 ~ 48 hour, be more preferably 0.4 ~ 30 hour, be particularly preferably 1.5 ~ 24 hours.
An object of the present invention is also the preparation method providing a kind of described silicon-carbon composite cathode material of lithium ion battery, described method comprises: by by the vapour deposition of silicon-carbon organic matter precursor on material with carbon element matrix, obtain silicon-carbon composite cathode material of lithium ion battery.
Preferably, described vapour deposition is carried out under protective atmosphere.
Preferably, described material with carbon element matrix is carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, carbon nano-tube, Graphene, 1 kind in carbon fiber or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: carbon black, the combination of native graphite, native graphite, the combination of graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, the combination of carbon nano-tube, carbon nano-tube, Graphene, the combination of carbon fiber, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, the combination of carbon nano-tube, carbon black, native graphite, graphite nodule, hollow carbon sphere, the combination etc. of carbonaceous mesophase spherules.
Preferably, described silicon-carbon organic matter precursor comprises organosilan, particularly preferably, also comprises hydro carbons, and described hydro carbons is for regulating the silicon-carbon mass ratio of composite material.
Preferably, described organosilan is hydrocarbyl si lanes and/or alkyl halosilanes, described alkyl and/or halogeno-group can single substituted silane and/or polysubstituted silane, more preferably alkyl silane and/or alkylchlorosilane, be more preferably C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane, be particularly preferably tetramethylsilane, tetraethyl silane, Trichloromethyl silane, dimethyldichlorosilane, 1 kind in tri-methyl-chlorosilane or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: tetramethylsilane, the combination of tetraethyl silane, dimethyldichlorosilane, the combination of tri-methyl-chlorosilane, tetraethyl silane, Trichloromethyl silane, the combination of dimethyldichlorosilane, Trichloromethyl silane, dimethyldichlorosilane, the combination of tri-methyl-chlorosilane, tetramethylsilane, tetraethyl silane, Trichloromethyl silane, the combination etc. of dimethyldichlorosilane.
Preferably, described hydro carbons is alkane, alkene, alkynes, 1 kind in aromatic hydrocarbon or the combination of at least 2 kinds, further preferably, for C1-C6 alkane, C2-C6 alkene, 1 kind in C2-C6 alkynes or the combination of at least 2 kinds, be particularly preferably methane, ethane, propane, ethene, propylene, acetylene, 1 kind in propine or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: methane, the combination of ethane, ethene, the combination of propylene, ethane, propane, the combination of ethene, propylene, acetylene, the combination of propine, propane, ethene, propylene, the combination of acetylene, propane, ethene, propylene, acetylene, the combination etc. of propine.
Another of described protective atmosphere act as carrier gas, 1 kind preferably in nitrogen, helium, argon gas, neon or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: the combination of nitrogen, helium, the combination of helium, argon gas, the combination of helium, argon gas, neon, the combination etc. of nitrogen, helium, argon gas, neon, is particularly preferably the combination of in nitrogen, helium, argon gas a kind or at least 2 kinds; Described protection gas is preferably high-purity gas, and namely purity is equal to or higher than 99.999%.
Preferably, after described silicon-carbon organic matter precursor is dissolved in solvent, enters consersion unit and carry out vapour deposition, preferably, described solvent is ether, acetone, oxolane, benzene, toluene, dimethylbenzene, 1 kind in dimethyl formamide or the combination of at least 2 kinds, the typical but non-limiting example of described combination has: ether, the combination of acetone, benzene, the combination of toluene, oxolane, benzene, the combination of toluene, toluene, dimethylbenzene, the combination of dimethyl formamide, benzene, toluene, dimethylbenzene, the combination of dimethyl formamide, ether, acetone, oxolane, benzene, the combination etc. of toluene, be particularly preferably acetone, benzene, toluene, 1 kind in dimethylbenzene or the combination of at least 2 kinds.
Preferably, described vapour deposition temperature is 300 ~ 2000 DEG C, such as: 300.1 DEG C, 301 DEG C, 302 DEG C, 303 DEG C, 350 DEG C, 500 DEG C, 1000 DEG C, 1200 DEG C, 1600 DEG C, 1800 DEG C, 1900 DEG C, 1990 DEG C, 1995 DEG C, 1998 DEG C, 1999 DEG C, 1999.9 DEG C etc., more preferably 600 ~ 1700 DEG C, be particularly preferably 700 ~ 1500 DEG C.
Preferably, described vapour deposition pressure is below 3Mpa, such as 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., more preferably below 2Mpa, is particularly preferably 0 ~ 1Mpa.
Preferably, described vapor deposition times is more than 0.2 hour, such as: 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., more preferably 0.3 ~ 48 hour, be more preferably 0.4 ~ 30 hour, be particularly preferably 1.5 ~ 24 hours.
Preferably, described vapour deposition consersion unit used is a kind in fixed bed, agitated bed, fluid bed.
As mentioned above, the present inventor breaks through the limitation of existing Research Thinking, preparing silicon-carbon composite cathode material by employing containing the vapour deposition of silicon-carbon organic precursor high temperature is a kind of new mentality of designing, and this technique has the advantages such as production cost is low, technique is simple, suitability for industrialized production is easy.The silicon-carbon composite cathode material prepared by the method has that irreversible capacity is first low, charge/discharge capacity is high, cyclical stability is excellent, the doubly forthright advantage such as well.This composite material has excellent chemical property mainly because the amorphous carbon deposited with silicon alleviates silicon in charge and discharge process because of volumetric expansion with shrinks the mechanical stress produced, elimination bulk effect simultaneously; Amorphous carbon can increase the electric conductivity of silicon based composite material greatly; Shorten the diffusion length of lithium ion, be conducive to fast charging and discharging process, and improve specific capacity and the cyclical stability of material; Graphite type material is a kind of good lithium ion battery negative, fills again the conductivity increasing composite material.
Relative 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 of the present invention alleviates silicon because of volumetric expansion and the mechanical stress of shrinking generation in charge and discharge process, elimination bulk effect;
(3) production technology that silicon-carbon composite cathode material of lithium ion battery of the present invention is novel, has the advantages such as low production cost, technique is simple, large-scale production is easy;
(4) carbon in composite material of the present invention can increase the electric conductivity of silicon based composite material greatly;
(5) by regulating the process conditions of gas-phase reaction, the silicon-carbon quality in composite material can be realized, product morphology controllable regulates;
(6) Si-C composite material prepared of the inventive method, be conducive to fast charging and discharging process, and improve specific capacity and the cyclical stability of material, quality and the structure of solid electrolyte film can be optimized in initial charge process, realize reducing irreversible capacity first.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic 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 as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Following examples are that silicon-carbon organic matter precursor high temperature vapour deposition process prepares Si-C composite material, then carry out electrochemical property test.
Embodiment 1
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by graphite nodule 1 gram of loading fixed bed reactors, 20ml dimethyldichlorosilane is dissolved in 80ml toluene, adopt nitrogen as carrier gas, flow velocity is 100ml/min, keep pressure in reactor to be 0.3MPa, deposit 5 hours at 900 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 14.7%, and carbon content is 85.3%.
Battery makes, electrochemical property test is as follows: silicon-carbon composite cathode material, the mass ratio of acetylene black and PVDF (Kynoar) is 80: 10: 10, Si-C composite material and acetylene black are mixed, then (PVDF is the PVDF/NMP solution of the 0.02g/mL prepared to add PVDF (Kynoar), NMP is 1-METHYLPYRROLIDONE) solution, be coated on Copper Foil, in 120 DEG C of vacuumizes 24 hours in vacuum drying chamber, cut-off footpath is that the disk of 19 centimetres is as work electrode, lithium metal is to electrode, electrolyte is LiPF6/EC-DMC-EMC (volume ratio 1: 1: 1), be assembled into two electrode simulated batteries being full of in Ar glove box.Charging/discharging voltage scope is 2.0 ~ 0.01V, and charging and discharging currents density is 100mA/g (0.5C).Electrochemical property test the results are shown in Table 1.
By the JSM6700 model field emission scanning electron microscope observation surface topography that the Si-C composite material of above-mentioned preparation is produced in NEC company.Fig. 1 is the SEM figure that Si-C composite material that embodiment 1 obtains amplifies 1000 times, clearly can make out graphite nodule and silicon-carbon recombination line from figure.
By EXSTARTG/DTA 6300 thermal analyzer that the Si-C composite material of above-mentioned preparation is produced in NSK Electronics Co., Ltd..Fig. 3 is the TG figure of the Si-C composite material that obtains of embodiment 1 and pure graphite nodule, and can show that silicone content is 14.7% by figure, carbon content is 85.3%.
X ' PertPRO MPD type the Multi-functional X ray diffractometer produced Dutch Panalytical company (PANalytical) by the Si-C composite material of above-mentioned preparation carries out XRD test.Fig. 2 is the XRD spectra of the Si-C composite material that embodiment 1 obtains, and each peak is the diffraction maximum of graphite, occurs the peak bag of silicon when 2 θ are 28.8 °, is amorphous silicon.
The 2001A type charge-discharge test instrument produced in Wuhan Lan electricity company by the Si-C composite material of above-mentioned preparation carries out charge-discharge test.Fig. 4,5 is respectively the high rate performance of the first cycle charge-discharge curve of the Si-C composite material that embodiment 1 obtains, composite material and graphite nodule, known discharge capacity is first 1383mAh/g, efficiency for charge-discharge is 82.2%, and after 20 times, capability retention is 98.2%.
Embodiment 2
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by carbonaceous mesophase spherules 1 gram of loading fixed bed reactors, 30ml dimethyldichlorosilane is dissolved in 70ml benzene, adopt nitrogen as carrier gas, flow velocity is 150ml/min, keep pressure in reactor to be 0.1MPa, deposit 10 hours at 1000 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 12.8%, and carbon content is 81.2%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 3
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by native graphite 1 gram of loading fixed bed reactors, 30ml tri-methyl-chlorosilane is dissolved in 70ml toluene, adopt nitrogen as carrier gas, flow velocity is 300ml/min, keep pressure in reactor to be 0.5MPa, deposit 5 hours at 1000 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 6.3%, and carbon content is 93.7%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 4
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: 1 gram of carbonaceous mesophase spherules is loaded fixed bed reactors, 40ml Trichloromethyl silane is dissolved in 60ml dimethylbenzene, adopt argon gas as carrier gas, flow velocity is 500ml/min, keep pressure in reactor to be 0.1MPa, deposit 8 hours at 1200 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 31.5%, and carbon content is 68.5%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 5
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by native graphite 1 gram of loading fluidized-bed reactor, 40ml dimethyldichlorosilane is dissolved in 60ml dimethylbenzene, adopt helium as carrier gas, flow velocity is 800ml/min, keep pressure in reactor to be 0.1MPa, deposit 15 hours at 600 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 28.2%, and carbon content is 71.8%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 6
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by carbonaceous mesophase spherules 1 gram of loading fixed bed reactors, 20ml tri-methyl-chlorosilane is dissolved in 80ml dimethylbenzene, adopt helium as carrier gas, flow velocity is 1000ml/min, keep pressure in reactor to be 0.5MPa, deposit 10 hours at 900 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 16.2%, and carbon content is 83.8%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 7
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by carbon nano-tube 1 gram of loading fluidized-bed reactor, 20ml dimethyldichlorosilane is dissolved in 80ml dimethylbenzene, adopt argon gas as carrier gas, flow velocity is 300ml/min, keep pressure in reactor to be 0.5MPa, deposit 3 hours at 1000 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 12.5%, and carbon content is 87.5%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 8
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by carbonaceous mesophase spherules 1 gram of loading fluidized-bed reactor, 50ml dimethyldichlorosilane is dissolved in 50ml toluene, adopt nitrogen as carrier gas, flow velocity is 600ml/min, keep pressure in reactor to be 0.1MPa, deposit 5 hours at 900 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 15.6%, and carbon content is 84.4%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 9
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: by carbonaceous mesophase spherules 1 gram of loading fluidized-bed reactor, 50ml Trichloromethyl silane is dissolved in 50ml toluene, adopt nitrogen as carrier gas, flow velocity is 100ml/min, keep pressure in reactor to be 0.1MPa, deposit 12 hours at 900 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 9.2%, and agraphitic carbon content is 90.8%%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 10
Agitated bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: Graphene 0.5 gram is put into agitated bed reactor, 10mi Trichloromethyl silane is dissolved in 90ml toluene, adopt nitrogen as carrier gas, flow velocity is 100ml/min, keep pressure in reactor to be 0.1MPa, deposit 1 hour at 300 DEG C, prepare silicon silicon-carbon composite cathode material.By analysis, wherein silicone content is 19.1%, and carbon content is 80.9%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 11
Agitated bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: native graphite 0.5 gram is put into agitated bed reactor, 40ml dimethyldichlorosilane is dissolved in 60ml acetone, adopt argon gas as carrier gas, flow velocity is 400ml/min, keep pressure in reactor to be 0.4MPa, deposit 12 hours at 1000 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 35.9%, and carbon content is 64.1%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 12
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: carbonaceous mesophase spherules 1 gram is put into fixed bed reactors, 30ml tri-methyl-chlorosilane is dissolved in 70ml dimethylbenzene, adopt argon gas as carrier gas, flow velocity is 200ml/min, keep pressure in reactor to be 0.2MPa, deposit 8 hours at 1100 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 28.6%, and carbon content is 71.4%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 13
Fixed bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: Graphene 0.1 gram is put into fixed bed reactors, 15ml Trichloromethyl silane is dissolved in 85ml toluene, adopt nitrogen as carrier gas, flow velocity is 100ml/min, keep pressure in reactor to be 0.1MPa, deposit 1 hour at 800 DEG C, prepare silicon silicon-carbon composite cathode material.By analysis, wherein silicone content is 60.2%, and carbon content is 39.8%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 14
Agitated bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: 0.5 gram, carbon fiber is put into agitated bed reactor, 40ml dimethyldichlorosilane is dissolved in 60ml acetone, adopt argon gas as carrier gas, flow velocity is 400ml/min, keep pressure in reactor to be 0.4MPa, deposit 12 hours at 1000 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 30.9%, and carbon content is 69.1%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 15
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: carbonaceous mesophase spherules 1 gram is put into fluidized-bed reactor, 20ml tri-methyl-chlorosilane is dissolved in 80ml dimethylbenzene, adopt nitrogen as carrier gas, flow velocity is 300ml/min, keep pressure in reactor to be 0.3MPa, deposit 4 hours at 900 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 35.6%, and carbon content is 64.4%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 16
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: Graphene 1 gram is put into fluidized-bed reactor, 20ml tri-methyl-chlorosilane is dissolved in 80ml chloroform, adopt nitrogen as carrier gas, flow velocity is 350ml/min, keep pressure in reactor to be 0.01MPa, deposit 0.2 hour at 600 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 32.7%, and carbon content is 67.3%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Embodiment 17
Fluid bed is adopted to prepare silicon-carbon composite cathode material, method is as follows: carbonaceous mesophase spherules 1 gram is put into fluidized-bed reactor, 20ml tri-methyl-chlorosilane is dissolved in 80ml dimethylbenzene, adopt nitrogen as carrier gas, flow velocity is 400ml/min, keep pressure in reactor to be 0.3MPa, deposit 4 hours at 900 DEG C, prepare silicon-carbon composite cathode material.By analysis, wherein silicone content is 35.6%, and carbon content is 64.4%.
The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
Comparative example
The nisiloy nanowire composite prepared according to CN102263243A: by with after watery hydrochloric acid and alcohol washes nickel foam be placed in chemical vapor deposition unit, arranging silane flow rate is 80sccm, hydrogen flowing quantity is 80sccm, cavity air pressure is 600Pa, temperature is 500 DEG C, reaction time is 15min, obtains array nisiloy nano wire in cleaned nickel foam superficial growth.
Directly electrode preparation and electrochemical property test is carried out with the graphite nodule that Star City, Changsha negative material factory produces.The test of electrode preparation and property is identical with embodiment 1.Electrochemical property test the results are shown in Table 1.
The electrochemical property test result of table 1 embodiment 1-17
| Embodiment | Discharge capacity first | First charge-discharge efficiency | Circulate 20 capability retentions |
| 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 example | 583 | 80.4 | 83.4 |
| Graphite nodule | 361 | 86.9 | 96.7 |
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (32)
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;
Described silicon-carbon composite cathode material of lithium ion battery is by obtaining the vapour deposition of silicon-carbon organic matter precursor on material with carbon element matrix; Described vapour deposition is carried out under protective atmosphere;
Described material with carbon element matrix is the combination of in carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, carbon nano-tube, Graphene, carbon fiber a kind or at least 2 kinds;
Described vapour deposition temperature is 300 ~ 1700 DEG C, and vapour deposition pressure is below 3MPa, and described vapor deposition times is more than 0.2 hour;
Described silicon-carbon organic matter precursor comprises organosilan and hydro carbons;
Described organosilan is hydrocarbyl si lanes and/or alkyl halosilanes; Described hydro carbons is the combination of in alkane, alkene, alkynes, aromatic hydrocarbon a kind or at least 2 kinds.
2. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1, it is characterized in that, described organosilan is alkyl silane and/or alkylchlorosilane.
3. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 2, it is characterized in that, described organosilan is C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane.
4. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 3, it is characterized in that, described organosilan is the combination of in tetramethylsilane, tetraethyl silane, Trichloromethyl silane, dimethyldichlorosilane, tri-methyl-chlorosilane a kind or at least 2 kinds.
5. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 1, is characterized in that, described hydro carbons is the combination of in C1-C6 alkane, C2-C6 alkene, C2-C6 alkynes a kind or at least 2 kinds.
6. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 5, is characterized in that, described hydro carbons is the combination of in methane, ethane, propane, ethene, propylene, acetylene, propine a kind or at least 2 kinds.
7. the silicon-carbon composite cathode material of lithium ion battery as described in any one of claim 1-3, is characterized in that, described vapour deposition pressure is below 2MPa.
8. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 7, it is characterized in that, described vapour deposition pressure is 0 ~ 1MPa.
9. the silicon-carbon composite cathode material of lithium ion battery as described in any one of claim 1-3, is characterized in that, described vapor deposition times is 0.3 ~ 48 hour.
10. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 9, it is characterized in that, described vapor deposition times is 0.4 ~ 30 hour.
11. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 10, it is characterized in that, described vapor deposition times is 1.5 ~ 24 hours.
12. silicon-carbon composite cathode material of lithium ion battery as described in any one of claim 1-3, it is characterized in that, described vapour deposition temperature is 600 ~ 1700 DEG C.
13. silicon-carbon composite cathode material of lithium ion battery as claimed in claim 12, it is characterized in that, described vapour deposition temperature is 700 ~ 1500 DEG C.
The preparation method of 14. 1 kinds of silicon-carbon composite cathode material of lithium ion battery as described in any one of claim 1-13, comprising: by by the vapour deposition of silicon-carbon organic matter precursor on material with carbon element matrix, obtain silicon-carbon composite cathode material of lithium ion battery;
Described material with carbon element matrix is the combination of in carbon black, native graphite, graphite nodule, hollow carbon sphere, carbonaceous mesophase spherules, carbon nano-tube, Graphene, carbon fiber a kind or at least 2 kinds;
Described vapour deposition is carried out under protective atmosphere;
Described vapour deposition temperature is 300 ~ 1700 DEG C, and vapour deposition pressure is below 3MPa, and described vapor deposition times is more than 0.2 hour;
It is hydrocarbyl si lanes and/or alkyl halosilanes that described silicon-carbon organic matter precursor comprises organosilan described in organosilan and hydro carbons; Described hydro carbons is the combination of in alkane, alkene, alkynes, aromatic hydrocarbon a kind or at least 2 kinds.
15. methods as claimed in claim 14, it is characterized in that, described organosilan is alkyl silane and/or alkylchlorosilane.
16. methods as claimed in claim 15, is characterized in that, described organosilan is C1-C3 alkyl silane and/or C1-C3 alkylchlorosilane.
17. methods as claimed in claim 16, is characterized in that, described organosilan is the combination of in tetramethylsilane, tetraethyl silane, Trichloromethyl silane, dimethyldichlorosilane, tri-methyl-chlorosilane a kind or at least 2 kinds.
18. methods as claimed in claim 14, is characterized in that, described hydro carbons is the combination of in C1-C6 alkane, C2-C6 alkene, C2-C6 alkynes a kind or at least 2 kinds.
19. methods as claimed in claim 18, is characterized in that, described hydro carbons is the combination of in methane, ethane, propane, ethene, propylene, acetylene, propine a kind or at least 2 kinds.
20. methods as claimed in claim 14, is characterized in that, described protective atmosphere is the combination of in nitrogen, helium, argon gas, neon a kind or at least 2 kinds.
21. methods as claimed in claim 20, is characterized in that, described protective atmosphere is the combination of in nitrogen, helium, argon gas a kind or at least 2 kinds.
22. methods as claimed in claim 14, is characterized in that, after described silicon-carbon organic matter precursor is dissolved in solvent, carry out vapour deposition.
23. methods as claimed in claim 22, is characterized in that, described solvent is the combination of in ether, acetone, oxolane, benzene,toluene,xylene, dimethyl formamide a kind or at least 2 kinds.
24. methods as claimed in claim 23, is characterized in that, described solvent is the combination of in acetone, benzene,toluene,xylene a kind or at least 2 kinds.
25. methods as claimed in claim 14, it is characterized in that, described vapour deposition pressure is below 2MPa.
26. methods as claimed in claim 25, it is characterized in that, described vapour deposition pressure is 0 ~ 1Mpa.
27. methods as claimed in claim 14, it is characterized in that, described vapor deposition times is 0.3 ~ 48 hour.
28. methods as claimed in claim 27, it is characterized in that, described vapor deposition times is 0.4 ~ 30 hour.
29. methods as claimed in claim 28, it is characterized in that, described vapor deposition times is 1.5 ~ 24 hours.
30. methods as claimed in claim 14, is characterized in that, described vapour deposition consersion unit used is a kind in fixed bed, agitated bed, fluid bed.
31. methods as claimed in claim 14, it is characterized in that, described vapour deposition temperature is 600 ~ 1700 DEG C.
32. methods as claimed in claim 31, it is characterized in that, described vapour deposition temperature is 700 ~ 1500 DEG C.
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| CN103730658A (en) * | 2012-10-16 | 2014-04-16 | 海洋王照明科技股份有限公司 | Silicon and graphene composite material, preparing method thereof and lithium ion battery |
| CN103280581A (en) * | 2013-05-20 | 2013-09-04 | 中国科学院过程工程研究所 | Negative material of lithium-ion battery and preparation method of negative material |
| CN103311522B (en) * | 2013-05-31 | 2015-09-30 | 中国科学院过程工程研究所 | A kind of silicon/carbon composite microsphere negative electrode material and its production and use |
| CN104347858B (en) * | 2013-07-29 | 2016-12-28 | 华为技术有限公司 | Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery |
| US10914002B2 (en) * | 2015-04-12 | 2021-02-09 | Clb Americas, Inc. | Apparatus and process for semi-continuous and multi-step composite production |
| CN105206806A (en) * | 2015-08-31 | 2015-12-30 | 无锡市嘉邦电力管道厂 | Lithium ion battery negative electrode material and preparing method thereof |
| CN105406044B (en) * | 2015-12-16 | 2019-04-12 | 上海航天电源技术有限责任公司 | A kind of silicon-carbon cathode piece of anti-expansion and preparation method thereof |
| CN106252627A (en) * | 2016-08-30 | 2016-12-21 | 浙江和也健康科技有限公司 | A kind of preparation method of cathode material of lithium-ion power battery |
| CN107394176B (en) * | 2017-07-31 | 2020-07-24 | 中国地质大学（北京） | Silicon-carbon composite material, preparation method and application thereof, and lithium ion battery cathode material |
| KR102207529B1 (en) * | 2018-03-14 | 2021-01-26 | 주식회사 엘지화학 | Amorphous silicon-carbon complex, manufacturing method thereof and lithium secondary battery comprising the same |
| CN112366299B (en) * | 2020-10-28 | 2022-04-22 | 浙江大学 | Preparation method of graphite-silicon-based lithium ion battery negative electrode material and product thereof |
| CN113380998A (en) * | 2021-06-02 | 2021-09-10 | 夏秀明 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN113461016B (en) * | 2021-06-30 | 2023-05-23 | 松山湖材料实验室 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN117425975A (en) * | 2022-05-11 | 2024-01-19 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, method for producing same, secondary battery, and electricity device |
| CN116014087A (en) * | 2022-06-13 | 2023-04-25 | 浙江锂宸新材料科技有限公司 | Preparation method of long-cycle high-performance anode material for secondary battery and product thereof |
| CN116422247B (en) * | 2023-06-09 | 2023-09-01 | 中国第一汽车股份有限公司 | Fluidized bed reactor, graphite silicon composite material and preparation method |
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