CN106410155B - A kind of preparation method of graphene silica carbon negative pole material - Google Patents
A kind of preparation method of graphene silica carbon negative pole material Download PDFInfo
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- H01M4/00—Electrodes
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- H01M10/00—Secondary cells; Manufacture thereof
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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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
The present invention discloses a kind of preparation method of graphene silica carbon negative pole material, using expanded graphite and silicon containing biomass as raw material, phosphoric acid is catalyst, silica is dispersed in dextran solution by grinder at room temperature, carry out carbonization-activation at high temperature again, form uniform Si/C nano-complexes, it effectively can inhibit and alleviate volume expansion of the silicon in charge and discharge process using the unformed porous carbon of ductility, and three-dimensional conductive network is built up based on alkene silicon-carbon compound, so that negative material conductivity of the present invention improves 20-100 times than porous activated carbon conductivity, greatly improve the electric conductivity in charge and discharge process of amorphous porous carbon and silicon, greatly shorten battery charge time, in addition carbon-coated graphene Si/C compounds are realized, cycle performance obtains larger improvement, good cycle.The present invention given full play to the high conductivity of graphene, silicide high specific capacitance, the features such as porosity of activated carbon.The lithium ion battery negative material of the present invention has high-specific capacitance super.
Description
Technical field
The present invention relates to new energy energy storage field more particularly to a kind of preparation methods of graphene silica carbon negative pole material.
Background technology
Lithium ion battery is due to having many advantages, such as that bigger than energy, operating voltage is high, safe, environmental pollution is small, each
The fields such as kind portable electronic device, electric vehicle and new energy storage have a wide range of applications.However, with to high energy
The growth of power supply requirement, to high-energy-density, quickly the lithium ion battery demand of high-power charge and discharge is very urgent, but is limited by negative
The lower specific capacity of pole material and high rate performance, lithium ion battery can't fully meet high-energy density, powerful requirement.
The negative material that large-scale commercial uses at present is graphite, but its theoretical specific capacity is only 372mAhg-1, phase
To relatively low.In order to improve battery capacity, people begin to focus on some elements, such as silicon, tin etc. that alloy can be formed with lithium.Silicon
There is maximum specific capacity in theory（4200mAhg-1）, and derive from a wealth of sources, it is ideal height ratio capacity negative material.But
It is to be different from Carbon materials, silicon materials, can be high along with serious volume change during the insertion of lithium ion and abjection
Up to 300%, so that active material is fallen off, dusting etc. and influence its cycle life.
Currently, sight has been invested silicon-carbon compound, the materials such as oxide of silicon by scientific research personnel.SiO2Be wherein it
One, work as SiO2Particle it is very small or for unformed form when, have higher capacity, cycle performance is also more preferable, but nanometer
The SiO of granular size or unformed form2The preparation process of particle is generally more complex, for example utilizes teos hydrolysis system
It is standby, wherein needing the parameter controlled more；Meanwhile the electric conductivity of this material is poor, and its carbon shell structure is fine and close, although portion
It point alleviates the silicon volume change in charge and discharge process and brings stress problem, however be also in electrolyte be difficult completely, quickly
Reacted with silicon active material, therefore tend not to give full play to the maximum capacity of silicon materials, and be difficult to fast charging and discharging.It is logical
Often the materials such as carbon can be added during preparation to be coated, improve its performance, so technique is more complex, cost is difficult to control
System.
Furthermore although above-mentioned preparation method improves specific capacity for the first time to a certain extent, cyclical stability is improved,
It is to prepare silicon composite cathode material, nano silica fume cost since the above method is mostly directly to use active nano silica flour for raw material
It is too high；Simultaneously after multiple charge and discharge cycles, specific discharge capacity starts to decay rapidly again.Therefore, exploitation it is a kind of it is simple for process,
Preparation method that is at low cost, can effectively inhibiting silicon bulk effect, is the key that prepare height ratio capacity silicon composite cathode material.
Graphene is the strong seas the K nurse of peace moral of Univ Manchester UK（Andre K.Geim）It is prepared Deng in 2004
Going out a kind of new material, single-layer graphene has high intensity, Young mole,（1,100GPa）, fracture strength：（125GPa）；
High heat conductance（5,000W/mK）；High conductivity, carrier transport rate（200,000㎝2/V*s）；High-specific surface area（Theoretical calculation
Value：2,630m2/g）.Especially its highly conductive property, the knot of big specific surface property and the two-dimensional nanoscale of its monolayer
Structure property can be used as electrode material in ultracapacitor and lithium ion battery.Up to the present, known to prepare graphite
There are many ways to alkene, such as：（1）Micromechanics stripping method, this method can only generate quantity and be extremely limited graphene film, can be used as
Basic research；（2）Ultrahigh vacuum graphene epitaxial growth method, the high cost of this method and the structure of sequin limit it
Using；（3）Chemical vapour deposition technique（CVD）, the method can meet the requirement of prepare with scale high-quality graphene, but cost
It is higher, complex process；（4）Solvent stripping method, the method limit its business application the disadvantage is that yield is very low.
In short, at this stage the preparation field of ion cathode material lithium there is also technical sophistication, of high cost, product resistance is high,
The problems such as specific capacitance is low, charge and discharge cycles stability is poor.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparations of graphene silica carbon negative pole material
Method, using natural or reproducible raw material（Graphite, rice husk）For the presoma of negative material, pass through simple mechanochemistry
Force method, manufacture high capacitance, high stability, low resistance and cheap lithium battery.
The technical solution adopted by the present invention is：
A kind of preparation method of graphene silica carbon negative pole material, using expanded graphite and silicon containing biomass as raw material, phosphoric acid
For catalyst, negative material is made in motorized educational level method, and the mechanochemistry force method includes the following steps：
（1）Expanded graphite is subjected to the puffing rear silicon containing biomass with after cleaning-drying according to mass ratio 1-5:5-20 is added
High speed disintegrator crushes 10-50 minutes, and the material particles after crushing are sieved no more than 325 mesh；
（2）Material particles after crushing are with the phosphoric acid as catalyst according to mass ratio 1:1-5, which is sufficiently stirred, to be obtained by filtration
Slurry；Slurry input grinder is ground into the 24-48 hours carbohydrate admixtures for being made sticky；Graphite is shelled in process of lapping
From forming finely dispersed few layer graphene oxide, while by silica nanosizing and evenly dispersed, wherein graphene and silica
Granularity between 20-50nm；
（3）Slice obtains tablet after sticky carbohydrate admixture is agglomerating, and tablet is cured in drying box, cures
Temperature is 120 DEG C, and the curing time is 24-48 hours；
（4）Tablet after curing is carbonized 2-3 hours, graphene oxide is reduced into graphene, and carbohydrate is carbonized,
Carbonized material is obtained, carbonization temperature is 450 DEG C -500 DEG C；
（5）After carbonized material is washed recycling phosphoric acid, 5% HCl solution boiling is used；Again by the solution after boiling with 5%
NaOH solution is neutralized to neutrality, and the solution after neutralization, which is excluded filtrate, obtains wet carbon, and wet carbon is added boiling boiling dechlorination；
（6）By the wet carbon drying after dechlorination, and completely cuts off air and institute is made within 2-3 hours in 1300-1800 DEG C of temperature lower calcination
State graphene silica carbon negative pole material；
The step（1）Described in the expansion rate of expanded graphite be not less than 250, expanded graphite is being preheated to 900 DEG C swollen
Change puffing in stove.
The step（1）Middle silicon containing biomass is rice husk, and the rice husk is the waste after paddy processing.
The step（1）Described in high speed disintegrator rotating speed be more than 3500r/min.
The step（1）The higher last graphene silica Carbon anode material obtained of mass content of the expanded graphite of middle addition
Expect that conductivity is higher.
The step（2）The middle phosphoric acid concentration as catalyst is 85%.
The step（2）Described in grinder be three-roll grinder, the slow rollers rotating speed of three-roll grinder is 31r/min, in
The rotating speed of roller is 83 r/min, and the rotating speed of fast roller is 220r/min.
The step（2）The longer last graphene silica carbon negative pole material obtained of milling time of middle grinder is for the first time
Reversible capacitance is bigger.
The step（5）In wet carbon add boiling boiling dechlorination specific method be：2.5 times of quality of wet carbon are added in wet carbon
Water carries out boiling and boils, repeated multiple times to through AgNO3Not chloride ion-containing in wet carbon after test.
The step（6）In wet carbon the higher last obtained graphene silica carbon negative pole material of calcination temperature through continuously filling
Electricity conservation rate after electric discharge measures is higher.
The present invention uses above technical scheme, uses rice husk for raw material, using phosphoric acid as catalyst, passes through grinding at room temperature
Silica is dispersed in dextran solution by machine, then carries out carbonization-activation at high temperature, and it is nano combined to form uniform Si/C
Object effectively can inhibit and alleviate volume expansion of the silicon in charge and discharge process using the unformed porous carbon of ductility, and be based on
Alkene silicon-carbon compound builds up three-dimensional conductive network so that negative material conductivity of the present invention（5s-10s/cm）Compare porous activated carbon
Conductivity（0.01s-0.1s/cm）Improve 20-100 times, greatly improve amorphous porous carbon and silicon in charge and discharge process
Electric conductivity greatly shortens battery charge time；In addition, carbon-coated graphene Si/C compounds are realized by mechanochemical reaction,
Cycle performance obtains larger improvement, good cycle（By 30 charge and discharge, electricity conservation rate is not less than 82%）.
The present invention given full play to the high conductivity of graphene, silicide high specific capacitance, the spies such as porosity of activated carbon
Sign.The lithium ion battery negative material of the present invention has high-specific capacitance super.
Description of the drawings
The present invention is described in further details below in conjunction with the drawings and specific embodiments；
Fig. 1 is a kind of flow diagram of the preparation method of graphene silica carbon negative pole material of the present invention.
Specific implementation mode
In order to realize high-capacitance, highly conductive, high stability and low cost electrode material hope, it is necessary to solve three
Problem：First, the efficient stripping of graphene is to prevent the reunion again of graphene；Secondly, the nanosizing of silica and silica is prevented
Particle is reunited again；Third, evenly dispersed in porous activated carbon of nano-graphene and nanometer silica particle and combining closely.
As shown in Figure 1, the present invention discloses a kind of preparation method of graphene silica carbon negative pole material, with expanded graphite and contain
Silicon biomass is raw material, and phosphoric acid is catalyst, and motorized educational level method is made negative material, the mechanochemistry force method include with
Lower step：
（1）Expanded graphite is subjected to the puffing rear silicon containing biomass with after cleaning-drying according to mass ratio 1-5:5-20 is added
High speed disintegrator crushes 10-50 minutes, and the material particles after crushing are sieved no more than 325 mesh；Its average grain diameter 1 μm-
Between 50 μm；Material particles can not be too small, and especially graphene requires have larger level wide and the ratio of thickness, is conducive to build
Vertical three-dimensional conductive network, reduces percolation threshold.The wide ratio diminution with thickness of level, will reach identical when that is excessively crushing
Electric conductivity need to add more graphenes.
（2）Material particles after crushing are with the phosphoric acid as catalyst according to mass ratio 1:1-5, which is sufficiently stirred, to be obtained by filtration
Slurry；Slurry input grinder is ground into the 24-48 hours carbohydrate admixtures for being made sticky；Graphite is shelled in process of lapping
From forming finely dispersed few layer graphene oxide, while by silica nanosizing and evenly dispersed, wherein graphene and silica
Granularity between 20-50nm；
Sufficiently complex physical and chemical changes occur in process of lapping：For example, the lignin, cellulose in rice husk are in phosphorus
Acid catalyst position hydrolyzes, the smaller glucan of generation molecular weight, disaccharides, polysaccharide, glucose residue, silica residue,
Water, CO2 etc., mutually condensation or polymerization become other larger molecules to these small molecules again；For example, expanded graphite particles are in water
Under the action of solving the shearing force for being subject to three-roll grinder in glucan viscous fluid, drag force, graphite oxide just starts to remove
Single layer or few layer graphene oxide, the surface of graphene oxide or edge just removed contain functional group（Such as carboxyl, hydroxyl）With Portugal
Hydroxyl or aldehyde radical in grape sugar react to form amide glycolylate, effectively prevent the reunion of graphene oxide；Silicon oxidation in rice husk
Progress of the object with saccharification is closed, silica gradually forms nano level Particle distribution in syrup；In order to improve mechanical dispersion effect
The roller of fruit, three-roll grinder should have different rotating speeds, step of the present invention（2）Described in three-roll grinder slow rollers turn
Speed is 31r/min, and the rotating speed of central roll is 83 r/min, and the rotating speed of fast roller is 220r/min.
（3）Slice obtains tablet after sticky carbohydrate admixture is agglomerating, and tablet is cured in drying box, cures
Temperature is 120 DEG C, and the curing time is 24-48 hours；Various small molecules are had by itself with adjacent molecule in maturing process
There is functional group to be bound to each other to form netted firm solid chemical compound, hardness（Ball-milling method）95% or more.
（4）Tablet after curing is carbonized 2-3 hours, graphene oxide is reduced into graphene, and carbohydrate is carbonized,
Carbonized material is obtained, carbonization temperature is 450 DEG C -500 DEG C；Carbohydrate just occurs to chemically react as follows during this：
CXHYOZ→aC+bCO2+cH2O （1）
Glucide is pyrolyzed in the case where completely cutting off air and just forms unformed charcoal（Activated carbon）, carbon dioxide and water.Unformed charcoal
Being one kind, there is porous solid can be used as charge and discharge due to the macropore that the effusion of carbon dioxide and water leaves when charcoal activates
When lithium ion and electrolyte ion channel.
（5）After carbonized material is washed recycling phosphoric acid, 5% HCl solution boiling is used；Again by the solution after boiling with 5%
NaOH solution is neutralized to neutrality, and the solution after neutralization, which is excluded filtrate, obtains wet carbon, and wet carbon is added boiling boiling dechlorination；
There are phosphoric acid or pyrophosphoric acid molecule between not washed carbonized material charcoal and charcoal, mesoporous or medium and small is left after washing
Hole, certain middle apertures allow lithium ions by without allowing electrolyte ion to pass through, and the active carbon layer with this middle aperture can be with
SEI films are formed by when substituting lithium battery charging, the loss of the reversible charge volume caused by avoiding lithium electrode from being reacted with electrolyte.
（6）By the wet carbon drying after dechlorination, and completely cuts off air and institute is made within 2-3 hours in 1300-1800 DEG C of temperature lower calcination
State graphene silica carbon negative pole material；The pore size of activated carbon can be both controlled by adjusting the concentration of phosphoric acid, dense phosphorus
Acid forms macropore, and aperture can use phosphoric acid,diluted instead, can also by activated carbon under isolation or inert gas shielding to activated carbon into
Row high-temperature process is realized.
The step（1）Described in the expansion rate of expanded graphite be not less than 250, expanded graphite is being preheated to 900 DEG C swollen
Change puffing in stove.
The step（1）Middle silicon containing biomass is rice husk, and the rice husk is the waste after paddy processing.
The step（1）Described in high speed disintegrator rotating speed be more than 3500r/min.
The step（1）The higher last graphene silica Carbon anode material obtained of mass content of the expanded graphite of middle addition
Expect that conductivity is higher.
The step（2）The middle phosphoric acid concentration as catalyst is 85%.
The step（2）The longer last graphene silica carbon negative pole material obtained of milling time of middle grinder is for the first time
Reversible capacitance is bigger.
The step（5）In wet carbon add boiling boiling dechlorination specific method be：2.5 times of quality of wet carbon are added in wet carbon
Water carries out boiling and boils, repeated multiple times to through AgNO3Not chloride ion-containing in wet carbon after test.
The step（6）In wet carbon the higher last obtained graphene silica carbon negative pole material of calcination temperature through continuously filling
Electricity conservation rate after electric discharge measures is higher.
Just the concrete principle of the preparation method of the present invention illustrates below：
With reference to embodiment, the preparation method of the graphene silica carbon negative pole material of the reference embodiment includes the following steps：
The first step weighs 300 grams of expanded graphites, adds rice husk 50 that high-speed grinder is added, and crushes 10-50min, until material
Until particle can be sieved all by 325 mesh.
Phosphoric acid is added in the mixture of expanded graphite and rice husk in second step（85%）450ml is filtered after stirring；Pulpous state
Object is put into three-roll grinder and grinds, and is initially formed sticky glucide, and cooperation grinding removes expanded graphite, formed and divided
Good few layer graphene oxide is dissipated, while being silica nanosizing in saccharifying, and is evenly dispersed；Milling time is about
48 hours, control graphene silica carbon particle degree so that the granularity of graphene silica carbon is between 20-50nm.
Third walks, and slice obtains tablet after material to be ground is agglomerating, and the thickness of tablet is 2-3mm, and tablet is put into
120 DEG C of drying box cures 24-48 hours.
4th step carbonizes tablet after curing 2-3 hours, and carbonization temperature is 450 DEG C -500 DEG C；At this moment graphite oxide
Alkene is reduced into graphene, and by nanosizing, carbohydrate is carbonized silica, then is activated.
5th step first uses 5%HCl boilings, then neutralized with 5%NaOH after recycling phosphoric acid is washed with water in activated material taking-up, washs
Filtrate is excluded, wet carbon adds 2.5 times of boiling boiling 20min, repeatedly repeatedly, until no Cl ions（Use AgNO3Test）；
6th step, wet carbon is dry and completely cut off air at 1300-1800 DEG C and handle, it stops 2-3 hours, removes oxygen-containing official
It can roll into a ball, and make product densification.Product is cooling under vacuum or inert gas conditions, crushes, sieving obtains graphene silica carbon
Negative material.The assay method of the graphene silica carbon compound cathode materials of sample 1 presses national standard GB/T 24533-2009 annex G
It carries out.
Comparative example group 1, the material prescription of 1 each embodiment of comparative example group and its operation with reference to embodiment
Difference is：Mixture is different in the milling time of three-roll grinder in second step.The operating time of comparative example group 1 point
It is not：For 24 hours, the sample of tetra- kinds of 48h, 72h, 96h, each embodiment of comparative example group 1 is denoted as GSC respectively24、GSC48、
GSC72And GSC96.By measuring it, reversible capacitance is respectively 480mAhg for the first time-1,560mAhg-1,580mAhg-1,600mAhg-
1.It can be seen that the longer graphene silica carbon negative pole material capacitance obtained of milling time is higher.
Comparative example group 2, the material prescription of 2 each embodiment of comparative example group and its operation with reference to embodiment
Difference is：The difference of high-temperature process temperature when the isolation air of the 6th step；The high-temperature process of 2 each embodiment of embodiment group
Temperature is respectively 800 DEG C, 900 DEG C, 1100 DEG C, 1300 DEG C four kinds, and the sample of each embodiment of comparative example group 2 is remembered respectively
For GSC800、GSC900、GSC1100And GSC1300.Through 30 continuous charge and discharge electrometric determinations, each embodiment of comparative example group 2
Sample electricity conservation rate is respectively 75%, 80%, 81.5%, 82%.It can be seen that the higher last graphene silicon obtained for the treatment of temperature
The sample electricity conservation rate of oxygen carbon negative pole material is longer.
Comparative example group 3, the material prescription of 3 each embodiment of comparative example group and its operation with reference to embodiment
Difference is：The additive amount of expanded graphite is different in the first step；The quality of the graphene of 3 each embodiment of comparative example group
Content is respectively 1%, 5%, 10%, 20%, and the sample of 3 each embodiment of comparative example group is denoted as GSC respectively0.01、GSC0.05、
GSC0.1And GSC0.2.The conductivity for measuring the sample of each embodiment of comparative example group 2 be respectively 0.1s/cm, 1s/cm,
2s/cm and 5s/cm.It can be seen that the more last graphene silica carbon negative pole materials obtained of the mass content of graphene are through even
Conductivity after continuous charge and discharge electrometric determination is higher.
The present invention uses above technical scheme, uses rice husk for raw material, using phosphoric acid as catalyst, passes through grinding at room temperature
Silica is dispersed in dextran solution by machine, then carries out carbonization-activation at high temperature, and it is nano combined to form uniform i/C
Object effectively can inhibit and alleviate volume expansion of the silicon in charge and discharge process using the unformed porous carbon of ductility, and be based on
Alkene silicon-carbon compound builds up three-dimensional conductive network so that bright negative material conductivity（5s-10s/cm）Than porous activated carbon conduction
Rate（0.01s-0.1s/cm）20-100 times is improved, the conduction in charge and discharge process of amorphous porous carbon and silicon is greatly improved
Property, battery charge time is greatly shortened, carbon-coated graphene Si/C compounds are realized by mechanochemical reaction in addition, cyclicity
It can obtain larger improvement, good cycle（By 30 charge and discharge, electricity conservation rate is not less than 82%）.
The present invention given full play to the high conductivity of graphene, silicide high specific capacitance, the spies such as porosity of activated carbon
Sign.The lithium ion battery negative material of the present invention has high-specific capacitance super.
Claims (10)
1. a kind of preparation method of graphene silica carbon negative pole material, it is characterised in that：It is with expanded graphite and silicon containing biomass
Raw material, phosphoric acid are catalyst, and negative material is made in motorized educational level method, and the mechanochemistry force method includes the following steps：
（1）Expanded graphite is subjected to the puffing rear silicon containing biomass with after cleaning-drying according to mass ratio 1-5:High speed is added in 5-20
Pulverizer crushes 10-50 minutes, and the material particles after crushing are sieved no more than 325 mesh；
（2）Material particles after crushing are with the phosphoric acid as catalyst according to mass ratio 1:1-5, which is sufficiently stirred, is obtained by filtration pulpous state
Object；Slurry input grinder is ground into the 24-48 hours carbohydrate admixtures for being made sticky；Graphite is removed into shape in process of lapping
At finely dispersed few layer graphene oxide, while by silica nanosizing and evenly dispersed, the wherein grain of graphene and silica
Degree is between 20-50nm；
（3）Slice obtains tablet after sticky carbohydrate admixture is agglomerating, tablet is cured in drying box, curing temperature
It it is 120 DEG C, the curing time is 24-48 hours；
（4）Tablet after curing is carbonized 2-3 hours, graphene oxide graphene is reduced into, and carbohydrate is carbonized, obtained
Carbonized material, carbonization temperature are 450 DEG C -500 DEG C；
（5）After carbonized material is washed recycling phosphoric acid, 5% HCl solution boiling is used；Again by the solution after boiling with 5% NaOH
Solution is neutralized to neutrality, and the solution after neutralization, which is excluded filtrate, obtains wet carbon, and wet carbon is added boiling boiling dechlorination；
（6）By the wet carbon drying after dechlorination, and completely cuts off air and the stone is made within 2-3 hours in 1300-1800 DEG C of temperature lower calcination
Black alkene silica carbon negative pole material.
2. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（1）Described in expanded graphite expansion rate be not less than 250, expanded graphite is puffing in the puffing furnace for being preheated to 900 DEG C.
3. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（1）Middle silicon containing biomass is rice husk, and the rice husk is the waste after paddy processing.
4. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（1）Described in high speed disintegrator rotating speed be more than 3500r/min.
5. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（1）The higher last graphene silica carbon negative pole material conductivity obtained of mass content of the expanded graphite of middle addition is higher.
6. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（2）The middle phosphoric acid concentration as catalyst is 85%.
7. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（2）Described in grinder be three-roll grinder, the slow rollers rotating speed of three-roll grinder is 31r/min, and the rotating speed of central roll is 83 r/
The rotating speed of min, fast roller are 220r/min.
8. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（2）The reversible capacitance for the first time of the longer last graphene silica carbon negative pole material obtained of milling time of middle grinder is bigger.
9. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
（5）In wet carbon add boiling boiling dechlorination specific method be：Be added in wet carbon 2.5 times of quality of wet carbon water carry out boiling boil, repeatedly
Repeatedly to through AgNO3Not chloride ion-containing in wet carbon after test.
10. a kind of preparation method of graphene silica carbon negative pole material according to claim 1, it is characterised in that：The step
Suddenly（6）In wet carbon higher last obtained electricity of the graphene silica carbon negative pole material after continuous charge and discharge electrometric determination of calcination temperature
It is higher to measure conservation rate.
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| CN106784741B (en) * | 2017-02-17 | 2021-01-08 | 贝特瑞新材料集团股份有限公司 | Carbon-silicon composite material, preparation method thereof and lithium ion battery containing composite material |
| CN107069046A (en) * | 2017-04-27 | 2017-08-18 | 中国科学院宁波材料技术与工程研究所 | A kind of metal air battery cathodes and preparation method thereof, metal-air battery |
| CN109810323B (en) * | 2017-11-20 | 2020-05-19 | 北京化工大学 | Preparation method of white carbon black/graphene oxide nano hybrid filler, nano hybrid filler and application of nano hybrid filler |
| CN109768249B (en) * | 2019-01-04 | 2021-05-25 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery, preparation method of negative electrode material and lithium ion battery |
| CN110498685B (en) * | 2019-08-02 | 2021-12-03 | 中国航发北京航空材料研究院 | Preparation method of carbon fiber reinforced ceramic matrix composite |
| JP7436969B2 (en) | 2019-10-23 | 2024-02-22 | 時空化学株式会社 | Hard carbon derived from biological materials, anode materials, anodes, and alkaline ion batteries |
| CN110867562B (en) * | 2019-11-19 | 2020-12-22 | 成都新柯力化工科技有限公司 | Preparation method of lithium battery silicon-carbon composite film cathode |
| CN111243870B (en) * | 2020-01-14 | 2021-10-26 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Flexible self-supporting hollow activated carbon micro-tube-based composite film electrode, preparation method and application |
| CN111755683A (en) * | 2020-07-06 | 2020-10-09 | 马鞍山科达普锐能源科技有限公司 | Silicon-containing negative electrode material for lithium ion battery and preparation method thereof |
| CN112054188B (en) * | 2020-09-15 | 2023-03-24 | 湖南大昊科技有限公司 | Negative electrode material of ion battery and preparation method and application thereof |
| CN113184858A (en) * | 2021-04-27 | 2021-07-30 | 郑州市博卓科技有限公司 | Silicon-oxygen negative electrode material composition and preparation method thereof |
| CN115924911A (en) * | 2022-12-12 | 2023-04-07 | 林立 | Preparation method of porous carbon material |
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