CN106848264A - A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof - Google Patents
A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN106848264A CN106848264A CN201710213023.4A CN201710213023A CN106848264A CN 106848264 A CN106848264 A CN 106848264A CN 201710213023 A CN201710213023 A CN 201710213023A CN 106848264 A CN106848264 A CN 106848264A
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a kind of porous silicon oxide lithium ion battery negative material and preparation method thereof, porous silicon oxide lithium ion battery negative material is with (Si+SiOX)/C is the porous core shell structure of matrix, and the porous core shell structure is made up of internal layer and clad, and the internal layer is mixed for the porous silicon and Si oxide and small particle graphite material of nano-pore structure with conductive agent, and the clad is organic pyrolytic carbon.The present invention is using pitch as carbon source elder generation SiOXMaterial surface coats one layer of carbon, and is disproportionated into nano Si by high-temperature process and is dispersed in SiOXIn, it is to avoid SiO when ultimately forming loose structureXExposure in the electrolytic solution, improves the stability and efficiency first of the material of preparation；(Si+SiOXSmall particle graphite and cracking carbon around)/C further buffer volumes can change, and increase the electric conductivity of material together with the conductive agent for adding, further the cycle performance of the porous material of lifting preparation.
Description
Technical field
The present invention relates to cathode material of lithium-ion power battery field, and in particular to a kind of porous silicon oxide lithium-ion electric
Pond negative material and preparation method thereof.
Background technology
It is raw material that current commercialized lithium ion battery negative material uses graphite mostly, but the theoretical capacity of graphite is
372mAh/g, it is impossible to meet the current market demand growing to lithium ion battery with high energy density, in the urgent need to exploitation one
New energy-density lithium ion battery negative material is planted, and the theoretical specific capacity of silicon is up to 4200mAh/g, and de- lithium current potential is put down
Platform is relatively low, meanwhile, its rich reserves, cost are relatively low, safety and environmental protection, therefore as the most lithium ion battery of potentiality to be exploited at present
One of negative material.Huge Volume Changes can be produced in charge and discharge process yet with silicon, material structure is suffered rapidly
Efflorescence, destruction, cause electrode material to be come off with collector, and capacity is greatly lowered, thus want by silicon use business lithium from
In sub- battery material, it is necessary to solve the problems, such as the volumetric expansion that silicon is produced in charge and discharge process.
Application No. CN102263245A discloses a kind of preparation side of spherical porous composite cathode material for lithium ion cell
Method, mist projection granulating is carried out by mixing with graphite after Si oxide high-energy ball milling, and the globular material that then will be obtained is in inert atmosphere
Middle sintering obtains spherical porous composite cathode material for lithium ion cell.The particle obtained after invention spray drying is surface only
The porous material of layer amorphous carbon, in lithium battery, the silicon in material is easy to exposure in the electrolytic solution, it is difficult to form stabilization
SEI films, and then cause that efficiency for charge-discharge is low, cycle performance of battery is poor.
Application No. CN103474667A discloses a kind of Si-C composite material and preparation method thereof, using nano-silicon plus stone
Ink is mixed, and then CVD coats one layer of carbon, then one layer of carbon of liquid phase coating, is finally crushed and is obtained final material.Party's legal system
Standby Si-C composite material by including nano-silicon/graphite particle, the first carbon coating layer and organic cracking carbon-coating, tool outside interior successively
There is excellent cycle performance and rate charge-discharge performance.But the method complex operation, and CVD is employed, it is relatively costly, no
It is adapted to industrialization.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, a kind of preparation method process is simple, automation are now provided
Degree is higher, low cost, the porous silicon oxide lithium ion battery negative material and preparation method thereof that is suitable for industrialized production.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of porous silicon oxide lithium ion battery
Negative material, its innovative point is：The porous silicon oxide lithium ion battery negative material is with (Si+SiOX)/C is matrix
Porous core shell structure, the porous core shell structure is made up of internal layer and clad, and the internal layer is porous for nano-pore structure
Silicon and Si oxide and small particle graphite material are mixed with conductive agent, and the clad is organic pyrolytic carbon.
Further, described (Si+SiOX)/C matrix is by acid and alkali corrosion and by the (Si+SiO of carbon coatingX) matrix,
The span of the X is 0<X≤2, (Si+SiOX) matrix average grain diameter be 1-3 μm.
Another object of the present invention is to disclose a kind of preparation method of porous silicon oxide lithium ion battery negative material,
Its innovative point is：Comprise the following steps that：
（1）Silicon and its oxide are uniformly mixed, then porous material is obtained for a period of time by acid and alkali corrosion；
（2）By step（1）The porous material for obtaining is uniformly mixed after drying a period of time at a certain temperature with binding agent
And according to 1:The ratio of 50-200 is added in deionized water, obtains the slurry of appropriate particle size for a period of time through wet ball grinding；
（3）By step（2）The slurry for obtaining be added to according to a certain percentage mixed in proportion by binding agent, conductive agent, graphite and
Into slurry in, certain hour is stirred in mixer, obtain precursor pulp；
（4）By step（3）Precursor pulp obtain (Si+SiO through mist projection granulatingX)/C matrix particle；
（5）By step（4）Particle stirred according to a certain percentage with graphite, pitch particle and mix, then under protective atmosphere
Uniform temperature is warming up to, after insulation a period of time, cooling eventually passes sieve classification, completes porous silicon oxide lithium ion
The preparation of cell negative electrode material.
Further, the step（1）In silicon and its oxide average grain diameter be 1-200 μm, the stir speed (S.S.) 50-
100rpm, the mixing time is 1-5h, and the mixed proportion is 1:1-20, further preferred mixed proportion is 1:1-15, institute
Caustic acid alkali lye body is stated for sulfuric acid, nitric acid, carbonic acid, citric acid, hydrofluoric acid, phosphoric acid, oxalic acid, hydrochloric acid, potassium hydroxide, hydroxide
1 kind or at least 2 kinds of combination in sodium, calcium hydroxide, magnesium hydroxide, the etching time are 0.5-8h, the corrosion gained
Porous material average grain diameter is 1-150 μm.
Further, the step（2）Middle drying temperature is 100-500 DEG C, and the heating rate is 2-15 DEG C/min, institute
The heating-up time is stated for 1-5h, the binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, poly- second
1 kind or at least 2 kinds of combination in alkene pyrrolidone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, the quality of the binding agent
Fraction is 5-25%, and the mixing time is 1-5h, and the stir speed (S.S.) is 50-100rpm, and the ball milling is using horizontal thick/thin
Sand mill, the Ball-milling Time is 1-5h, and the final gained slurry particle diameter is 1-100 μm.
Further, the step（3）Middle binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl alcohol contracting
1 kind or at least 2 kinds of combination in butyraldehyde, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, the conduction
Agent is cathode of lithium battery often with the combination of a kind or 2 kinds in conductive agent acetylene black, Super P, carbon fiber and CNT, matter
Amount fraction is 0.1-10%, the graphite behave make spherical graphite, natural spherical plumbago, natural flaky graphite, micro crystal graphite,
The combination of a kind or at least 2 kinds in veiny graphite and carbonaceous mesophase spherules is crystallized, the average grain diameter of the graphite matrix is 1-20
μm, the conductive agent, binding agent, the ratio of graphite are 10:1-3:20-60, the ratio of described two slurries is 1:1.5-5, institute
Stir speed (S.S.) is stated for 50-100rpm, the mixing time is 1-5h, the precursor pulp solid content is 10-40%.
Further, the step（4）In spray drying granulation use centrifugal spraying granulator, inlet temperature is 220-
270 DEG C, outlet temperature is 80-120 DEG C；The sponging granulator feed pump frequency is 10-50Hz, and atomizing disk frequency is 200-
300Hz。
Further, the step（5）In graphite behave make spherical graphite, natural spherical plumbago, natural flakey stone
1 kind or at least 2 kinds of combination in ink, micro crystal graphite, crystallization veiny graphite and carbonaceous mesophase spherules, the graphite matrix it is flat
Equal particle diameter is 1-10 μm, and the pitch particle is asphalt or coal tar pitch, and pitch particle average grain diameter is 1-15 μm；It is described
(Si+SiOXThe mass percent 60-90 of)/C matrix particle and pitch particle：10-40；The speed of agitator is 50-100rpm,
Mixing time 1-4h, the protective gas is a kind or at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon
Combination, 1-5 DEG C of the heating rate/min, final temperature is 200-800 DEG C, and soaking time is 1-5h.
Beneficial effects of the present invention are as follows：
（1）The present invention can form loose structure when carbon source binding agent sintering is cracked into carbon, can accommodate SiOXIn discharge and recharge
During Volume Changes, while fully and electrolyte contacts, final silicon carbon material is possessed specific capacity higher and good
Cycle performance；
（2）The present invention is using pitch as carbon source first in SiOXMaterial surface coats one layer of carbon, and is disproportionated by high-temperature process
For nano Si is dispersed in SiOXIn, it is to avoid SiO when ultimately forming loose structureXExposure in the electrolytic solution, improves the material of preparation
Stability and efficiency first；(Si+SiOXSmall particle graphite and cracking carbon around)/C further buffer volumes can change,
And the same conductive agent for adding increases the electric conductivity of material together, further lifts the cycle performance of the porous material for preparing；
（3）Porous silicon oxide cathode material preparation method of the invention is simple, cost is relatively low, high degree of automation, easily put
Greatly, it is especially suitable for industrialization.
Brief description of the drawings
Fig. 1 is material surface scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1；
Fig. 2 is the (Si+SiO before and after the high-temperature heat treatment of the embodiment of the present invention 1X)/C-material X ray diffracting spectrum；
Fig. 3 is porous (Si+SiO in the embodiment of the present invention 1XThe forming process sketch of)/C-material；
Fig. 4 for the embodiment of the present invention 1 porous silicon oxide material as negative pole when button cell test loop performance map.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages of the invention and effect easily.
A kind of porous silicon oxide lithium ion battery negative material is with (Si+SiOX)/C is the porous nucleocapsid knot of matrix
Structure, porous core shell structure is made up of internal layer and clad, and internal layer is the porous silicon and Si oxide and granule of nano-pore structure
Footpath graphite material is mixed with conductive agent, and clad is organic pyrolytic carbon.
Feasible, (Si+SiOX)/C matrix is by acid and alkali corrosion and by the (Si+SiO of carbon coatingX) matrix, X's takes
Value scope is 0<X≤2, (Si+SiOX) matrix average grain diameter be 1-3 μm.
A kind of preparation method of porous silicon oxide lithium ion battery negative material, comprises the following steps that：
（1）Silicon and its oxide are uniformly mixed, then porous material is obtained for a period of time by acid and alkali corrosion；
（2）By step（1）The porous material for obtaining is uniformly mixed after drying a period of time at a certain temperature with binding agent
And according to 1:The ratio of 50-200 is added in deionized water, obtains the slurry of appropriate particle size for a period of time through wet ball grinding；
（3）By step（2）The slurry for obtaining be added to according to a certain percentage mixed in proportion by binding agent, conductive agent, graphite and
Into slurry in, certain hour is stirred in mixer, obtain precursor pulp；
（4）By step（3）Precursor pulp obtain (Si+SiO through mist projection granulatingX)/C matrix particle；
（5）By step（4）Particle stirred according to a certain percentage with graphite, pitch particle and mix, then under protective atmosphere
Uniform temperature is warming up to, after insulation a period of time, cooling eventually passes sieve classification, completes porous silicon oxide lithium ion
The preparation of cell negative electrode material.
Feasible, step（1）In silicon and its oxide average grain diameter be 1-200 μm, stir speed (S.S.) 50-100rpm is stirred
The time is mixed for 1-5h, mixed proportion is 1:1-15, further preferred mixed proportion is 1:1-20, caustic acid alkali lye body is sulphur
Acid, nitric acid, carbonic acid, citric acid, hydrofluoric acid, phosphoric acid, oxalic acid, hydrochloric acid, potassium hydroxide, NaOH, calcium hydroxide, magnesium hydroxide
In a kind or at least 2 kinds of combination, etching time is 0.5-8h, and corrosion gained porous material average grain diameter is 1-150 μm.
Feasible, step（2）Middle drying temperature is 100-500 DEG C, and heating rate is 2-15 DEG C/min, and the heating-up time is 1-
5h, binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, polyvinylpyrrolidone, polyethylene
1 kind or at least 2 kinds of combination in alcohol, polyacrylonitrile, polyacrylic acid, the mass fraction of binding agent is 5-25%, and mixing time is
1-5h, stir speed (S.S.) is 50-100rpm, and using horizontal thick/fine sand grinding machine, Ball-milling Time is 1-5h to ball milling, final gained slurry
Particle diameter is 1-100 μm.
Feasible, step（3）Middle binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, poly-
1 kind or at least 2 kinds of combination in vinylpyrrolidone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, conductive agent is lithium battery
Negative pole often uses the combination of a kind or 2 kinds in conductive agent acetylene black, Super P, carbon fiber and CNT, and mass fraction is
0.1-10%, graphite is behaved and makes spherical graphite, natural spherical plumbago, natural flaky graphite, micro crystal graphite, crystallization veiny graphite
With a kind or at least 2 kinds of combination in carbonaceous mesophase spherules, the average grain diameter of graphite matrix is 1-20 μm, conductive agent, bonding
Agent, the ratio of graphite are 10:1-3:20-60, two kinds of ratios of slurry are 1:1.5-5, stir speed (S.S.) is 50-100rpm, stirring
Time is 1-5h, and precursor pulp solid content is 10-40%.
Feasible, step（4）In spray drying granulation use centrifugal spraying granulator, inlet temperature is 220-270 DEG C,
Outlet temperature is 80-120 DEG C；Sponging granulator feed pump frequency is 10-50Hz, and atomizing disk frequency is 200-300Hz.
Feasible, step（5）In graphite behave make spherical graphite, natural spherical plumbago, natural flaky graphite, crystallite
The combination of graphite, a kind or at least 2 kinds crystallized in veiny graphite and carbonaceous mesophase spherules, the average grain diameter of graphite matrix is 1-
10 μm, pitch particle is asphalt or coal tar pitch, and pitch particle average grain diameter is 1-15 μm；(Si+SiOX)/C matrix particle
With the mass percent 60-90 of pitch particle：10-40；Speed of agitator is 50-100rpm, mixing time 1-4h, protective gas
It is a kind or at least 2 kinds of combination in nitrogen, helium, neon, argon gas, Krypton, xenon, 1-5 DEG C of heating rate/min, finally
Temperature is 200-800 DEG C, and soaking time is 1-5h.
Embodiment 1
A kind of preparation method of porous silicon oxide negative material：
（1）After 2kg silica flours and the sub- silica flour of 4kg oxidations are well mixed, it is added in the 12kg aqueous solution containing 100gPVP, enters
Row wet ball grinding to D50 particle diameters are 200nm, obtain slurry；
（2）By 5kg (Si+SiOX)/C slurries and meso-phase graphite, 50gCMC, 100gSP and 4kg that 2kg D50 particle diameters are 10 μm
The slurry agitation of water mixing is well mixed, and is spray-dried, and controls the inlet temperature of spray dryer for 250 DEG C, outlet temperature
It is 100 DEG C to spend, and atomizing disk frequency is 250Hz, obtains near-spherical porous particle；
（3）Near-spherical porous particle is sufficiently mixed with the asphalt that 1kg particle diameters are 10 μm in VC heating mixers, in nitrogen
Cladding treatment 6h, material after must coating are carried out under gas atmosphere in 600 DEG C；
（4）By material after cladding in charing process 8h is carried out under nitrogen atmosphere at 1200 DEG C in chamber type electric resistance furnace, obtain final product porous
Si oxide negative material, by screening process, is obtaining the homogeneous negative material of different-grain diameter size again.
Embodiment 2
" 1kg particle diameters are 10 μm of asphalt " in embodiment 1 is changed to " 1.5kg particle diameters are 10 μm of coal tar pitch ", other
It is constant.
Embodiment 3
" 2kg D50 particle diameters are 10 μm of meso-phase graphite " in embodiment 1 be changed to " 1.5kg D50 particle diameters are 8 μm artificial
Graphite ", other are constant.
Comparative example
The preparation of porous silicon oxide negative material：Remove " by material after cladding under nitrogen atmosphere 1200 DEG C in retort
Under carry out charing process 8h " this step, directly using VC heating mixer be warming up to 1100 DEG C and be incubated 8h sieving, obtain hot place
(Si+SiO after reasonX)/C-material, other steps are consistent with embodiment 1.
Directly taking above-described embodiment 1-3 and the porous silicon oxide of comparative example carries out button cell preparation：
It is prepared by negative plate：Electrode slice is prepared slurry and then is coated on Copper Foil using automatic spray dryer and formed by stirring,
Slurry solvent is deionized water, and conductive agent is Super-p, and binding agent adds SBR emulsion, active matter for carboxymethylcellulose calcium
Matter, conductive agent and binding agent ratio are 8:1:1.
It is prepared by battery：Button half-cell using lithium piece as to electrode, in glove box according to anode cover, electrode slice, every
The order assembling CR2025 button cells of film, lithium piece, stainless steel gasket, nickel foam and negative electrode casing, electrolyte is using 1mol/L's
LiPF6Used as electrolyte, solvent is 1:1:1 EC/EMC/DMC, adds 10%FEC.
Battery testing：Using the charging and discharging curve of blue electrical testing button cell, 0.1C rate charge-discharges, blanking voltage
0.005-1.5V。
The Si-C composite material scanning electron microscope (SEM) photograph of preparation is as shown in Figure 1, it can be seen that the material for obtaining is spherical porous
Structure, preferably, there is the cotton-shaped carbon of cracking on surface to spheroidization degree.Accompanying drawing 2 is hot SiOXSiOx/C material X-rays after before processing
Diffracting spectrum, it can be seen that material is non crystalline structure before heat treatment, and the peak of Si is occurred in that after heat treatment, shows that SiOx there occurs discrimination
Change.
The charging and discharging curve test knot of the button cell prepared as negative material using Si-C composite material of the invention
Really as shown in fig. 4, it can be seen that the specific capacity of material is 617.5mAh/g or so, efficiency 90.04% or so, circulate 20 times first
Capability retention is 97.0%.
Porous silicon oxide material button electricity relevant parameter prepared by embodiment 1-3 and comparative example is as shown in table 1：
Table 1
| Parameter | Reversible capacity first | Efficiency first | 20 circulation volume conservation rates |
| Embodiment 1 | 617.5mAh/g | 90.1% | 97.0% |
| Embodiment 2 | 634.2mAh/g | 89.9% | 95.8% |
| Embodiment 3 | 641.8mAh/g | 85.7% | 91.2% |
| Comparative example | 646.7mAh/g | 82.5% | 88.9% |
The present invention can form loose structure when carbon source binding agent sintering is cracked into carbon, can accommodate SiOXIn charge and discharge process
Middle Volume Changes, while fully and electrolyte contacts, making final silicon carbon material possess specific capacity and good circulation higher
Performance；The present invention is using pitch as carbon source elder generation SiOXMaterial surface coats one layer of carbon, and is disproportionated into nanometer by high-temperature process
Si is dispersed in SiOXIn, it is to avoid SiO when ultimately forming loose structureXExposure in the electrolytic solution, improves the stabilization of the material of preparation
Property and first efficiency；(Si+SiOXSmall particle graphite around)/C and cracking carbon can further buffer volumes change, and with adding
The conductive agent for entering increases the electric conductivity of material together, further the cycle performance of porous material prepared by lifting；It is of the invention many
Hole Si oxide cathode material preparation method is simple, cost is relatively low, high degree of automation, easily amplification, is especially suitable for industrialization.
Above-described embodiment is presently preferred embodiments of the present invention, is not the limitation to technical solution of the present invention, as long as
Without the technical scheme that creative work can be realized on the basis of above-described embodiment, it is regarded as falling into patent of the present invention
Rights protection scope in.
Claims (8)
1. a kind of porous silicon oxide lithium ion battery negative material, it is characterised in that：The porous silicon oxide lithium-ion electric
Pond negative material is with (Si+SiOX)/C is the porous core shell structure of matrix, and the porous core shell structure is by internal layer and clad
Composition, the internal layer is for the porous silicon and Si oxide and small particle graphite material of nano-pore structure mix with conductive agent
Into the clad is organic pyrolytic carbon.
2. a kind of porous silicon oxide lithium ion battery negative material according to claim 1, it is characterised in that：It is described
(Si+SiOX)/C matrix is by acid and alkali corrosion and by the (Si+SiO of carbon coatingX) matrix, the span of the X is 0<X
≤ the 2, (Si+SiOX) matrix average grain diameter be 1-3 μm.
3. a kind of preparation method of porous silicon oxide lithium ion battery negative material as claimed in claim 1, its feature exists
In：Comprise the following steps that：
（1）Silicon and its oxide are uniformly mixed, then porous material is obtained for a period of time by acid and alkali corrosion；
（2）By step（1）The porous material for obtaining is uniformly mixed after drying a period of time at a certain temperature with binding agent
And according to 1:The ratio of 50-200 is added in deionized water, obtains the slurry of appropriate particle size for a period of time through wet ball grinding；
（3）By step（2）The slurry for obtaining be added to according to a certain percentage mixed in proportion by binding agent, conductive agent, graphite and
Into slurry in, certain hour is stirred in mixer, obtain precursor pulp；
（4）By step（3）Precursor pulp obtain (Si+SiO through mist projection granulatingX)/C matrix particle；
（5）By step（4）Particle stirred according to a certain percentage with graphite, pitch particle and mix, then under protective atmosphere
Uniform temperature is warming up to, after insulation a period of time, cooling eventually passes sieve classification, completes porous silicon oxide lithium ion
The preparation of cell negative electrode material.
4. a kind of preparation method of porous silicon oxide lithium ion battery negative material according to claim 3, its feature
It is：The step（1）In silicon and its oxide average grain diameter be 1-200 μm, the stir speed (S.S.) 50-100rpm is described
Mixing time is 1-5h, and the mixed proportion is 1:1-20, further preferred mixed proportion is 1:1-15, the corrosivity soda acid
Liquid be sulfuric acid, nitric acid, carbonic acid, citric acid, hydrofluoric acid, phosphoric acid, oxalic acid, hydrochloric acid, potassium hydroxide, NaOH, calcium hydroxide,
1 kind or at least 2 kinds of combination in magnesium hydroxide, the etching time are 0.5-8h, and the corrosion gained porous material is average
Particle diameter is 1-150 μm.
5. a kind of preparation method of porous silicon oxide lithium ion battery negative material according to claim 3, its feature
It is：The step（2）Middle drying temperature is 100-500 DEG C, and the heating rate is 2-15 DEG C/min, and the heating-up time is
1-5h, the binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, polyvinylpyrrolidone, poly-
1 kind or at least 2 kinds of combination in vinyl alcohol, polyacrylonitrile, polyacrylic acid, the mass fraction of the binding agent is 5-25%, institute
Mixing time is stated for 1-5h, the stir speed (S.S.) is 50-100rpm, and the ball milling is using horizontal thick/fine sand grinding machine, the ball milling
Time is 1-5h, and the final gained slurry particle diameter is 1-100 μm.
6. a kind of preparation method of porous silicon oxide lithium ion battery negative material according to claim 3, its feature
It is：The step（3）Middle binding agent is glucose, sucrose, citric acid, polyethylene glycol, polyvinyl butyral resin, polyethylene pyrrole
1 kind or at least 2 kinds of combination in pyrrolidone, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, the conductive agent are negative for lithium battery
The combination of a kind or 2 kinds in conductive agent acetylene black, Super P, carbon fiber and CNT is extremely commonly used, mass fraction is 0.1-
10%, the graphite is behaved and makes spherical graphite, natural spherical plumbago, natural flaky graphite, micro crystal graphite, crystallization veiny graphite
With a kind or at least 2 kinds of combination in carbonaceous mesophase spherules, the average grain diameter of the graphite matrix is 1-20 μm, the conduction
Agent, binding agent, the ratio of graphite are 10:1-3:20-60, the ratio of described two slurries is 1:1.5-5, the stir speed (S.S.) is
50-100rpm, the mixing time is 1-5h, and the precursor pulp solid content is 10-40%.
7. a kind of preparation method of porous silicon oxide lithium ion battery negative material according to claim 3, its feature
It is：The step（4）In spray drying granulation use centrifugal spraying granulator, inlet temperature is 220-270 DEG C, outlet temperature
Spend is 80-120 DEG C；The sponging granulator feed pump frequency is 10-50Hz, and atomizing disk frequency is 200-300Hz.
8. a kind of preparation method of porous silicon oxide lithium ion battery negative material according to claim 3, its feature
It is：The step（5）In graphite behave make spherical graphite, natural spherical plumbago, natural flaky graphite, micro crystal graphite,
The combination of a kind or at least 2 kinds in veiny graphite and carbonaceous mesophase spherules is crystallized, the average grain diameter of the graphite matrix is 1-10
μm, the pitch particle is asphalt or coal tar pitch, and pitch particle average grain diameter is 1-15 μm；(the Si+SiOX)/C bases
The mass percent 60-90 of body particle and pitch particle：10-40；The speed of agitator be 50-100rpm, mixing time 1-4h,
The protective gas is the combination of a kind or at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton, xenon, the intensification
1-5 DEG C of speed/min, final temperature is 200-800 DEG C, and soaking time is 1-5h.
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