CN109728289A - A kind of preparation method of lithium electronics composite negative pole material - Google Patents
A kind of preparation method of lithium electronics composite negative pole material Download PDFInfo
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- CN109728289A CN109728289A CN201910025659.5A CN201910025659A CN109728289A CN 109728289 A CN109728289 A CN 109728289A CN 201910025659 A CN201910025659 A CN 201910025659A CN 109728289 A CN109728289 A CN 109728289A
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Abstract
The present invention discloses a kind of preparation method of lithium electronics composite negative pole material, includes: that natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination pitch coke and carbon black are combined ingredient resulting mixture by weight percentage;The mixture of combined ingredient is dry-mixed uniformly, coal tar pitch is added and carries out heating kneading, forms silicon covered composite yarn plastic body；Carbon material is made in the roasting of compound plastic body at 800~1150 DEG C using roaster；High-temperature process, charcoal/graphite/silicon clad composite material of system are carried out to carbon material under the conditions of 2100 DEG C~3100 DEG C using graphitizing furnace;Charcoal/graphite/silicon clad composite material is crushed into simultaneously nodularization, spherical or oval charcoal/graphite/silicon that partial size is 5-26um is obtained and coats cathode powder, up to lithium electronics composite negative pole material.The negative electrode material of the method for the present invention preparation has height ratio capacity, low charge and discharge potential and stable charge and discharge platform, high-pressure solid performance, highly conductive and high rate capability and long circulating performance.
Description
Technical field
The present invention relates to lithium battery material technical fields, more particularly to a kind of preparation side of lithium electronics composite negative pole material
Method.
Background technique
With the warming of global climate, oil price it is surging, people come to realise the importance and energy of environmental protection
The seriousness of source crisis.In order to reduce the use of fossil fuels, the discharge of carbon dioxide is reduced, the speed of slowing global warming,
On the one hand countries in the world government and enterprise are sought for new alternative energy source (such as solar energy, fuel cell), on the other hand with lithium
Ion battery replaces plumbic acid, nickel-metal hydride battery to improve the transfer efficiency of secondary cell.It is developed so far, secondary cell industry has been sent out
Structural transformation is given birth to, lithium ion battery will gradually replace lead-acid battery and nickel-metal hydride battery.Since especially into the new century,
The new-energy automobiles such as hybrid vehicle/pure electric automobile are fast-developing, started the research and development of power-type lithium ion battery newly
Climax, and be expected to gradually to replace nickel-metal hydride battery to become the preferred energy of electric car.2010, lithium ion battery 90% with
The upper market share concentrates on the small-sized energy storage field that electric energy is provided for electronic device.And arrive the year two thousand twenty, this-application only account for total city
The 18.4% of market share;Lithium ion battery main application fields translate into the power battery for electric car and are applied to electricity
The extensive energy storage field of net.This undoubtedly proposes update, higher requirement to performance of lithium ion battery.Currently, how to improve
Energy density, power density, safety and the service life of lithium ion battery, and cost is reduced, it is the hot spot of current research,
Key is the research and development of high-performance negative electrode material.
Carbon Materials are inexpensive with its, nontoxic and its superior chemical property has obtained widely answering in clang ion battery
With at present, the clang ion battery carbon negative pole material of commercialization can be divided into graphite, hard carbon and soft carbon, and wherein graphite type material is still
It is the mainstream of clang ion battery cathode material.Various graphite and graphited carbon material have lower embedding lithium/deintercalation current potential, put down
Steady charge and discharge platform and excellent electric conductivity, and be easy to batch and make and use, it is outstanding lithium ion battery negative material.
Its shortcoming is that intercalation potential is too low, it is easy to appear analysis lithium when polarizing, leads to safety problem.Meanwhile theoretical capacity mistake
Low (372 mAhg-1), high rate performance is poor and is difficult to meet the requirement to lithium ion battery such as electric car and high capacity storage.
Si is a kind of very promising negative electrode material, it has highest theoretical capacity, low (~370 mV of discharge voltage
Vs.Li/Li+), the advantages that abundance is high, nontoxic in the earth's crust, while Si has stable charge and discharge platform and without as graphite-like
Solvent is total to imbedding problem, at present, restrict Si as negative electrode material application mainly following problem: first is that, Si with lithium alloy
Change during have nearly 400% volume expansion, make electrode material in charge and discharge process repeatedly because repeatedly expansion and contraction make
At electrode material dusting and it is detached from collector, the capacity of electrode material is caused to be decayed rapidly；Second is that because of " bulk effect ",
SEI film is highly unstable, in charge and discharge process repeatedly the surface Si be formed by SEI film experience it is continuous " formed ---
Fragmentation --- re-formed in fresh surfaces " process, SEI film, which is constantly grown up, to be thickened, when thickness increases to-fixed value when, lithium
Ion cannot by and seriously consume lithium ion in electrolyte, make lithium battery cyclical stability degradation；Third is that Si
Electric conductivity it is poor.
It is directed to three above problem, current main resolving ideas is nanosizing, Si/C is compound and microstructure design.
It is numerous it is demonstrated experimentally that the nanosizing of Si is the effective way solved the problems, such as.Nanostructure can quickly mitigate stress, make electrode material
Material resists the ability enhancing of dusting failure.Meanwhile nanosizing can enhance the high rate performance of electrode material again.This is because with
The transmission range of the reduction of scantling, lithium ion tails off.Also, the electronics and ion caused by the poorly conductive because of Si pass
The problem of Movement Capabilities difference will be greatly enhanced with the increase of material specific surface area area along the mass transfer of surface and crystal boundary.
It is compound by Si/C, the shortcomings that capable of effectively making up Si poorly conductive, the electric conductivity of electrode is improved, and buffer Si in charge and discharge cycles
Volume change in the process improves electrochemical stability.The expansion preset buffering of Si when microstructure design then can be charge and discharge
The expansion of material entirety is reduced, to improve cycle performance in space.Be generally basede in practical operation the above thinking be prepared into it is various
Si nano material.
Summary of the invention
The technical issues of solution of the invention, is to provide a kind of preparation method of lithium electronics composite negative pole material, the preparation side
The negative electrode material of method preparation has height ratio capacity, low charge and discharge potential and stable charge and discharge platform, high-pressure solid performance, highly conductive
With high rate capability and long circulating performance.
In order to solve the above technical problems, to provide a kind of technical solution as follows by the present invention: a kind of lithium electronics composite negative pole material
Preparation method, include the following steps:
Step I ingredient, kneading include:
A. by weight percentage by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination pitch coke and carbon black
It is combined ingredient resulting mixture;
B. the mixture of combined ingredient is dry-mixed uniformly, and coal tar pitch is added and carries out heating kneading, form silicon covered composite yarn plasticity
Body；
Using roaster carbon material is made at 800~1150 DEG C in the roasting of compound plastic body by step II roasting；
Step III graphitization carries out high-temperature process to carbon material under the conditions of 2100 DEG C~3100 DEG C using graphitizing furnace,
Charcoal/graphite/silicon clad composite material of system
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
It is further described as to above-mentioned technical proposal:
In the above-mentioned technical solutions, ingredient and kneading are carried out in step I as following weight percent:
Natural graphite 4~9%；
Nano-silicon 1~5%；
It is calcined petroleum coke powder 25~29%
It is calcined petroleum coke 14~22%；
It is calcined pitch coke 10~16%；
Coal tar pitch 16~22%；
Carbon black 1~5%；
Wherein, the granularity of the natural graphite is 0.9~1mm, and the granularity of the nano-silicon is 40nm~300nm, the calcination
The granularity of petroleum coke powder is 0.06~0.08mm, and the granularity of the calcination petroleum coke is 1~4.5mm, the calcination pitch coke
Granularity is 8~15mm.
3. a kind of preparation method of lithium electronics composite negative pole material according to claim 2, which is characterized in that step
The mixture by combined ingredient in I is dry-mixed uniformly, and coal tar pitch is added carries out heating kneading and include:
Natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination pitch coke and carbon black are preset in kneading machine by I
In, preset time is 6~8min;
II sets the temperature of kneading machine as 110~150 DEG C, by preset natural graphite, nano-silicon, calcination petroleum coke powder, calcination
Petroleum coke, calcination pitch coke and the dry-mixed 30~50min of carbon black;
III sets the temperature of kneading machine as 155~165 DEG C, and it is wet that 174 DEG C~185 DEG C of coal tar pitch progress is added in kneading machine
Mixed and kneading is thickener, and the wet mixing time is 40~55min；
After the cool material of thickener to temperature is 120~150 DEG C by IV, thickener is injected into die for molding silicon covered composite yarn plastic body；.
In the above-mentioned technical solutions, the natural graphite is the amorphous graphite of crystalline flake graphite or low ash.
In the above-mentioned technical solutions, the carbon black is conductive black or acetylene carbon black or semi-reinforcing hydrocarbon black.
In the above-mentioned technical solutions, the coal tar pitch is medium temperature coal pitch or modified coal asphalt.
In the above-mentioned technical solutions, the calcination petroleum coke powder and calcination petroleum coke are forged under the conditions of 1250 DEG C by petroleum coke
It fires standby.
In the above-mentioned technical solutions, the calcination pitch coke is calcined preparation by pitch coke under the conditions of 1250 DEG C.
Compared with prior art, included the beneficial effects of the present invention are the lithium battery of: this preparation method preparation first is that,
With height ratio capacity, low charge and discharge potential and stable charge and discharge platform, make battery that there is high capacity, relatively high and stable work
Voltage;Second is that there is no structure change in lithium ion intercalation/deintercalation, make material that there is good cycle performance;Third is that larger
Lithium ion diffusion coefficient, it is ensured that battery has preferable fast charging and discharging performance；Fourth is that macroscopically have preferable powder and at
Membrane property, it is easy to use;Fifth is that abundance, cheap, it is environmentally protective.
Detailed description of the invention
Fig. 1 is a kind of effect picture of lithium electronics composite negative pole material electric performance test of the embodiment of the present invention.
Specific embodiment
The present invention is described in further detail below.
Embodiment 1
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 9%, the grain of 1mm
Spend the nano-silicon 1% for being 40nm~300nm, the calcination petroleum coke powder 25% that granularity is 0.08mm, granularity is the calcination of 1~4.5mm
Petroleum coke 22%, granularity are the calcination pitch coke 16% and acetylene carbon black 5% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 2
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 9%, the grain of 1mm
Spend the nano-silicon 2% for being 40nm~300nm, the calcination petroleum coke powder 25% that granularity is 0.08mm, granularity is the calcination of 1~4.5mm
Petroleum coke 22%, granularity are the calcination pitch coke 16% and acetylene carbon black 5% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
21% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 3
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 7%, the grain of 1mm
Spend the nano-silicon 3% for being 40nm~300nm, the calcination petroleum coke powder 25% that granularity is 0.08mm, granularity is the calcination of 1~4.5mm
Petroleum coke 22%, granularity are the calcination pitch coke 16% and acetylene carbon black 5% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 4
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 8%, the grain of 1mm
Spend the nano-silicon 4% for being 40nm~300nm, the calcination petroleum coke powder 24% that granularity is 0.08mm, granularity is the calcination of 1~4.5mm
Petroleum coke 21%, granularity are the calcination pitch coke 16% and acetylene carbon black 5% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 5
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 9%, the grain of 1mm
Spend the nano-silicon 5% for being 40nm~300nm, the calcination petroleum coke powder 25% that granularity is 0.08mm, granularity is the calcination of 1~4.5mm
Petroleum coke 22%, granularity are the calcination pitch coke 16% and acetylene carbon black 1% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
For the performance examination for the negative electrode material for examining 1-5 of the embodiment of the present invention to prepare, tested with half-cell test method,
With the negative electrode material of above embodiments: acetylene black: PVDF (Kynoar)=93:3:4 (weight ratio) adds appropriate NMP (N- first
Base pyrrolidones) it is tuned into pulpous state, it is coated on copper foil, negative electrode tab is made within 8 hours through 110 DEG C of dryings of vacuum;It is with metal lithium sheet
To electrode, electrolyte is l mol/L LiPF6/EC+DEC+DMC=1:1:1, and microporous polypropylene membrane is diaphragm, is assembled into battery.
Charging/discharging voltage is 0-2.0V, and charge-discharge velocity is 0.2 C, carries out energy test to battery performance, test result refers to attached drawing 1.
Embodiment 6
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. ingredient resulting mixture is combined by following raw material granularity and weight percent: scale graphite 4% that granularity is 0.9mm,
The calcination petroleum coke powder 29% that nano-silicon 5% that granularity is 40nm~300nm, granularity are 0.08mm, granularity are the forging of 1~4.5mm
Scoria oil coke 22%, granularity are the calcination pitch coke 16% and acetylene carbon black 2% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 7
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is the scale graphite of 0.9~1mm
4%, the calcination petroleum coke powder 29% that granularity is 300nm nano-silicon 5%, granularity are 0.06mm, granularity are the calcination stone of 1~4.5mm
Oil coke 20%, granularity are the calcination pitch coke 16% and acetylene carbon black 5% of 8~15mm, and are added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
21% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 8
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is the scale graphite of 0.9~1mm
9%, the calcination petroleum coke powder 29% that granularity is 40nm~300nm nano-silicon 5%, granularity are 0.06~0.08mm, granularity 1mm
Calcination petroleum coke 14%, the calcination pitch coke 16% and acetylene carbon black 5% that granularity is 15mm, and be added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 9
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is the scale graphite of 0.9~1mm
9%, the calcination petroleum coke powder 29% that granularity is 40nm~300nm nano-silicon 5%, granularity are 0.06~0.08mm, granularity 3mm
Calcination petroleum coke 22%, the calcination pitch coke 10% and acetylene carbon black 5% that granularity is 10mm, and be added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
20% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 10
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. ingredient resulting mixture is combined by following raw material granularity and weight percent: scale graphite 9% that granularity is 0.9mm,
The calcination petroleum coke powder 29% that nano-silicon 5% that granularity is 40nm, granularity are 0.06mm, granularity are the calcination petroleum coke of 4.5mm
22%, granularity is the calcination pitch coke 10% and acetylene carbon black 5% of 8mm, and is added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
20% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 11
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is the scale graphite of 0.9~1mm
9%, the calcination petroleum coke powder 29% that granularity is 40nm~300nm nano-silicon 5%, granularity are 0.06~0.08mm, granularity 2mm
Calcination petroleum coke 22%, the calcination pitch coke 16% and acetylene carbon black 3% that granularity is 15mm, and be added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
16% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 12
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 6%, the grain of 1mm
Spend the nano-silicon 4% for being 200nm, the calcination petroleum coke powder 28% that granularity is 0.07mm, granularity is calcination petroleum coke 20%, the grain of 3mm
Degree is the calcination pitch coke 15% and acetylene carbon black 5% of 10mm, and is added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
Embodiment 13
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. ingredient resulting mixture is combined by following raw material granularity and weight percent: scale graphite 9% that granularity is 0.9mm,
The calcination petroleum coke powder 29% that nano-silicon 5% that granularity is 100nm, granularity are 0.07mm, calcination petroleum coke 22% that granularity is 3mm,
Granularity is the calcination pitch coke 16% and acetylene carbon black 3% of 9mm, and is added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
16% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization crushes charcoal/graphite/silicon clad composite material and nodularization, obtain spherical shape that partial size is 5um or
Oval charcoal/graphite/silicon coats cathode powder, up to lithium electronics composite negative pole material.
Embodiment 14
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 5%, the grain of 1mm
Spend the nano-silicon 5% for being 150nm, the calcination petroleum coke powder 27% that granularity is 0.06~0.08mm, granularity is the calcination petroleum coke of 2mm
20%, granularity is the calcination pitch coke 16% and acetylene carbon black 1% of 15mm, and is added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
16% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the spherical shape that partial size is 26um
Or oval charcoal/graphite/silicon coats cathode powder, up to lithium electronics composite negative pole material.
Embodiment 15
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 9%, the grain of 1mm
Spend the nano-silicon 5% for being 150nm, the calcination petroleum coke powder 27% that granularity is 0.06~0.08mm, granularity is the calcination petroleum coke of 2mm
20%, granularity is the calcination pitch coke 16% and acetylene carbon black 5% of 15mm, and is added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
18% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the spherical shape that partial size is 10um
Or oval charcoal/graphite/silicon coats cathode powder, up to lithium electronics composite negative pole material.
Embodiment 16
A kind of preparation method of lithium battery composite negative pole material, includes the following steps:
Step I ingredient, kneading include:
A. be combined ingredient resulting mixture by following raw material granularity and weight percent: granularity is scale graphite 6%, the grain of 1mm
Spend the nano-silicon 5% for being 150nm, the calcination petroleum coke powder 26% that granularity is 0.06~0.08mm, granularity is the calcination petroleum coke of 2mm
20%, granularity is the calcination pitch coke 16% and acetylene carbon black 5% of 15mm, and is added in kneading machine;
B. the temperature of kneading machine is set as 120 DEG C, by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination
Pitch coke and the dry-mixed 35min of carbon black;
C. set the temperature of kneading machine as 160 DEG C, be added in kneading machine 175 DEG C and coal tar pitch account for the total ingredients by weight of raw material
22% coal tar pitch carries out wet mixing and kneading is thickener, and the wet mixing time is 40min；
D. after being 120~150 DEG C by the cool material of thickener to temperature, thickener is injected into die for molding silicon covered composite yarn plastic body；
Using roaster carbon material is made at 1050 DEG C in compound plastic body (raw embryo) roasting by step II roasting；
Step III graphitization carries out high-temperature process, charcoal/stone of system to carbon material under the conditions of 2600 DEG C using graphitizing furnace
Ink/silicon clad composite material；
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the spherical shape that partial size is 15um
Or oval charcoal/graphite/silicon coats cathode powder, up to lithium electronics composite negative pole material.
It is not intended to limit the scope of the present invention above, all technical spirits according to the present invention are to above implementation
Any modification, equivalent variations and modification made by example, in the range of still falling within technical solution of the present invention.
Claims (8)
1. a kind of preparation method of lithium electronics composite negative pole material, it is characterised in that, include the following steps:
Step I ingredient, kneading include:
A. by weight percentage by natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination pitch coke and carbon black
It is combined ingredient resulting mixture;
B. the mixture of combined ingredient is dry-mixed uniformly, and coal tar pitch is added and carries out heating kneading, form silicon covered composite yarn plasticity
Body；
Using roaster carbon material is made at 800~1150 DEG C in the roasting of compound plastic body by step II roasting；
Step III graphitization carries out high-temperature process, system to carbon material under the conditions of 2100 DEG C~3100 DEG C using graphitizing furnace
Charcoal/graphite/silicon clad composite material
Step IV smashes, nodularization is by charcoal/graphite/silicon clad composite material crushing and nodularization, obtains the ball that partial size is 5-26um
Shape or oval charcoal/graphite/silicon coat cathode powder, up to lithium electronics composite negative pole material.
2. a kind of preparation method of lithium electronics composite negative pole material according to claim 1, it is characterised in that, in step I
Ingredient and kneading are carried out as following weight percent:
Natural graphite 4~9%；
Nano-silicon 1~5%；
It is calcined petroleum coke powder 25~29%
It is calcined petroleum coke 14~22%；
It is calcined pitch coke 10~16%；
Coal tar pitch 16~22%；
Carbon black 1~5%；
Wherein, the granularity of the natural graphite is 0.9~1mm, and the granularity of the nano-silicon is 40nm~300nm, the calcination
The granularity of petroleum coke powder is 0.06~0.08mm, and the granularity of the calcination petroleum coke is 1~4.5mm, the calcination pitch coke
Granularity is 8~15mm.
3. a kind of preparation method of lithium electronics composite negative pole material according to claim 2, which is characterized in that in step I
The mixture by combined ingredient it is dry-mixed uniformly, and be added coal tar pitch carry out heating kneading include:
Natural graphite, nano-silicon, calcination petroleum coke powder, calcination petroleum coke, calcination pitch coke and carbon black are preset in kneading machine by I
In, preset time is 6~8min;
II sets the temperature of kneading machine as 110~150 DEG C, by preset natural graphite, nano-silicon, calcination petroleum coke powder, calcination
Petroleum coke, calcination pitch coke and the dry-mixed 30~50min of carbon black;
III sets the temperature of kneading machine as 155~165 DEG C, and it is wet that 174 DEG C~185 DEG C of coal tar pitch progress is added in kneading machine
Mixed and kneading is thickener, and the wet mixing time is 40~55min；
After the cool material of thickener to temperature is 120~150 DEG C by IV, thickener is injected into die for molding silicon covered composite yarn plastic body.
4. a kind of preparation method of lithium electronics composite negative pole material according to claim 3, it is characterised in that, it is described natural
Graphite is the amorphous graphite of crystalline flake graphite or low ash.
5. a kind of preparation method of lithium electronics composite negative pole material according to claim 3, it is characterised in that, the carbon black
For conductive black or acetylene carbon black or semi-reinforcing hydrocarbon black.
6. a kind of preparation method of lithium electronics composite negative pole material according to claim 3, it is characterised in that, the coal drip
Blueness is medium temperature coal pitch or modified coal asphalt.
7. a kind of preparation method of lithium electronics composite negative pole material according to claim 3, it is characterised in that, the calcination
Petroleum coke powder and calcination petroleum coke are calcined preparation by petroleum coke under the conditions of 1250 DEG C.
8. a kind of preparation method of lithium electronics composite negative pole material according to claim 3, which is characterized in that the calcination
Pitch coke is calcined preparation by pitch coke under the conditions of 1250 DEG C.
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| CN104882590A (en) * | 2015-06-17 | 2015-09-02 | 田东 | Preparation method of carbon/ graphite/ silicon composited anode material |
| CN104953100A (en) * | 2015-06-17 | 2015-09-30 | 田东 | Preparation method of carbon/graphite/tin composite anode material |
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| CN104882590A (en) * | 2015-06-17 | 2015-09-02 | 田东 | Preparation method of carbon/ graphite/ silicon composited anode material |
| CN104953100A (en) * | 2015-06-17 | 2015-09-30 | 田东 | Preparation method of carbon/graphite/tin composite anode material |
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Application publication date: 20190507 |