CN106410155A - Preparing method of graphene silica carbon negative material - Google Patents
Preparing method of graphene silica carbon negative material Download PDFInfo
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Abstract
The invention discloses a preparing method of a graphene silica carbon negative material. The method adopts expanded graphite and biomass containing silicon as raw materials and phosphoric acid as a catalyst, and comprises the steps of dispersing the silicon dioxide into a glucose solution through a grinding miller at room temperature, then conducting carbonization and excitation at high temperature to form an uniform Si/C nano-compound, wherein the use of amorphous porous carbon with ductility can suppress and ease effectively volume expansion of silicon in charging and discharging processes, and establishing a three-dimensional conductive network based on alkene silicon carbon compound, wherein, the three-dimensional conductive network makes the conductivity of the graphene silica carbon negative material improve by 20-100 times faster than that of the porous activated carbon, improves sharply the conductivities of the amorphous porous carbon and the silicon in the charging and discharging processes, and shortens sharply charging time of the battery; in addition, obtaining of carbon covering graphene Si/C compound is achieved, and cycle performance is improved greatly so that the negative material has a good cycle performance. According to the preparing method of the graphene silica carbon negative material, advantages such as high conductivity of the graphene, high specific capacitance of the silicide and porosity of the activated carbon are given full play to; in addition, lithium ion battery negative material has high specific capacitance.
Description
Technical field
The present invention relates to new forms of energy energy storage field, more particularly, to a kind of preparation method of Graphene silica carbon negative pole material.
Background technology
Lithium ion battery is due to having the advantages that specific energy is big, running voltage is high, safe, environmental pollution is little, each
The fields such as portable electric appts, electric automobile and new forms of energy storage of planting 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 discharge and recharge is very urgent, but is limited by negative
The relatively low 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 that can form alloy with lithium, such as silicon, stannum etc..Silicon
There is the specific capacity of maximum in theory（4200mAhg-1）, and wide material sources, it is preferable height ratio capacity negative material.But
Be, different from carbons material, silicon materials during the embedded of lithium ion and abjection, along with serious change in volume, can be high
Reach 300%, so that active substance in charge and discharge process is come off, efflorescence etc. and affect its cycle life.
At present, scientific research personnel has invested silicon-carbon complex, the material such as oxide of silicon sight.SiO2Be wherein it
One, work as SiO2Granule very little or during for unformed form, have higher capacity, cycle performance is also more preferable, but nanometer
Granular size or the SiO of unformed form2The preparation technology of granule is typically more complicated, such as utilizes teos hydrolysis system
Standby, wherein need the parameter controlling more；Meanwhile, the electric conductivity of this material is poor, and its carbon shell structure fine and close although portion
Point alleviating silicon change in volume in charge and discharge process brings stress problem, however be also be difficult in electrolyte completely, quick
React 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.Logical
Often the materials such as carbon can be added during preparing to be coated, improve its performance, so technique is more complicated, cost is difficult to control
System.
Furthermore, although above-mentioned preparation method improves specific capacity first to a certain extent, improve cyclical stability,
It is because mostly said method is directly to adopt active nano silica flour to be raw material, prepare silicon composite cathode material, nano silica fume cost
Too high；Simultaneously after multiple charge and discharge cycles, specific discharge capacity starts to decay rapidly again.Therefore, develop a kind of process is simple,
Low cost, the preparation method of silicon bulk effect of effectively suppressing, are the keys preparing height ratio capacity silicon composite cathode material.
Graphene is the peace moral strong K sea nurse of Univ Manchester UK（Andre K.Geim）Prepare Deng in 2004
Go 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 high connductivity property, the knot of the nanoscale of big specific surface property and its monolayer two dimension
Structure property, can be used as electrode material in ultracapacitor and lithium ion battery.Up to the present, known prepare graphite
The method of alkene has multiple, such as：（1）Micromechanics stripping method, this method can only produce quantity and be extremely limited graphene film, can conduct
Basic research；（2）Ultrahigh vacuum Graphene epitaxial growth method, the high cost of this method and the structure of sequin limit it
Application；（3）Chemical vapour deposition technique（CVD）, the method can meet the requirement of prepare with scale high-quality graphene, but cost
Higher, complex process；（4）Solvent stripping method, the method shortcoming is that yield is very low, limits its business application.
In a word, also there is technical sophistication, high cost in the preparation field of ion cathode material lithium at this stage, product resistance is high,
The problems such as specific capacitance is low, charge and discharge cycles stability is poor.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, provide a kind of preparation of Graphene silica carbon negative pole material
Method, using natural or reproducible raw material（Graphite, rice husk）For the presoma of negative material, by simple mechanochemistry
Force method, manufactures high capacitance, high stability, low resistance and cheap lithium battery.
The technical solution used in the present invention is：
A kind of preparation method of Graphene silica carbon negative pole material, with expanded graphite and silicon containing biomass as raw material, phosphoric acid is to urge
Agent, motorized educational level method makes negative material, and described mechanochemistry force method comprises the following steps：
（1）Expanded graphite is carried out the silicon containing biomass after expanded rear and cleaning-drying according to mass ratio 1-5:5-20 adds at a high speed
10-50 minute pulverized by pulverizer, and makes the material particles after pulverizing be not more than 325 mesh sieves；
（2）Material particles after pulverizing and the phosphoric acid as catalyst are according to mass ratio 1:1-5 is sufficiently stirred for being filtrated to get pulpous state
Thing；Slurry is put into grinder grinding 24-48 hour sticky carbohydrate admixture is obtained；In process of lapping, graphite is peeled off shape
Become finely dispersed few layer graphene oxide, simultaneously by silicon oxide nanorize and dispersed, the grain of wherein Graphene and silica
Degree is between 20-50nm；
（3）After sticky carbohydrate admixture is agglomerating, section obtains tablet, ripening in drying baker, curing temperature by tablet
For 120 DEG C, the curing time is 24-48 hour；
（4）By the tablet carbonization 2-3 hour after ripening, graphene oxide is reduced into Graphene, and by saccharide carbonization, obtains
Carbonized material, carbonization temperature is 450 DEG C -500 DEG C；
（5）Carbonized material is washed to be reclaimed after phosphoric acid, using 5% HCl solution steaming and decocting；Again by the solution after steaming and decocting with 5% NaOH
Solution is neutralized to neutrality, the solution exclusion filtrate after neutralization is obtained wet carbon, and wet carbon is added water boils dechlorination；
（6）Wet carbon after dechlorination is dried, and completely cuts off air and described stone is obtained in 1300-1800 DEG C of temperature lower calcination 2-3 hour
Black alkene silica carbon negative pole material；
Described step（1）Described in expanded graphite expansion rate be not less than 250, expanded graphite is in the puffing furnace being preheated to 900 DEG C
In expanded.
Described step（1）Middle silicon containing biomass is rice husk, and described rice husk is the garbage after paddy processing.
Described step（1）Described in high speed disintegrator rotating speed be more than 3500r/min.
Described step（1）The more high Graphene silica Carbon anode material being finally obtained of the mass content of the expanded graphite of middle addition
Material conductivity is higher.
Described step（2）The middle phosphoric acid concentration as catalyst is 85%.
Described 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.
Described step（2）The more long Graphene silica carbon negative pole material being finally obtained of the milling time of middle grinder is first
Reversible capacitance is bigger.
Described step（5）In wet carbon add water and boil the concrete grammar of dechlorination and be：Wet 2.5 times of quality of 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.
Described step（6）In wet carbon calcining heat more high finally be obtained Graphene silica carbon negative pole material through continuously filling
Electricity conservation rate after electric discharge measures is higher.
The present invention adopts above technical scheme, is raw material using rice husk, with phosphoric acid as catalyst, passes through at room temperature to grind
Silicon dioxide is dispersed in dextran solution machine, then carries out carbonization-activation at high temperature, forms uniform Si/C nano combined
Thing, can effectively be suppressed using the unformed porous carbon of ductility and alleviate volumetric expansion in charge and discharge process for the silicon, and be based on
Alkene silicon-carbon complex 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；Additionally, realize the Graphene Si/C complex of carbon coating by mechanochemical reaction,
Cycle performance obtains larger improvement, good cycle（Through 30 discharge and recharges, electricity conservation rate is not less than 82%）.
The present invention has given full play to the high specific capacitance of the high conductivity of Graphene, silicide, the spy such as porous of activated carbon
Levy.The lithium ion battery negative material of the present invention has high-specific capacitance super.
Brief description
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details；
Fig. 1 is a kind of schematic flow sheet of the preparation method of present invention Graphene silica carbon negative pole material.
Specific embodiment
In order to realize high-capacitance, high connductivity, 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 nanorize of silica and prevent silica
The reuniting again of microgranule；Third, dispersed in porous activated carbon of nano-graphene and nanometer silica microgranule 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 with contain
Silicon biomass are raw material, and phosphoric acid is catalyst, and motorized educational level method makes negative material, described mechanochemistry force method include with
Lower step：
（1）Expanded graphite is carried out the silicon containing biomass after expanded rear and cleaning-drying according to mass ratio 1-5:5-20 adds at a high speed
10-50 minute pulverized by pulverizer, and makes the material particles after pulverizing be not more than 325 mesh sieves；Its mean diameter is at 1 μm -50 μm
Between；Material particles nor too small, particularly Graphene require the ratio having larger aspect width and thickness, are conducive to setting up three
Dimension conductive network, reduces percolation threshold.When that is too pulverizing, the ratio of aspect width and thickness reduces, and identical to be reached is led
Electrically need to add more Graphenes.
（2）Material particles after pulverizing and the phosphoric acid as catalyst are according to mass ratio 1:1-5 is sufficiently stirred for being filtrated to get
Slurry；Slurry is put into grinder grinding 24-48 hour sticky carbohydrate admixture is obtained；In process of lapping, graphite is shelled
From the finely dispersed few layer graphene oxide of formation, simultaneously by silicon oxide nanorize and dispersed, wherein Graphene and silica
Granularity between 20-50nm；
There are sufficiently complex physical and chemical changes in process of lapping：Such as, the lignin in rice husk, cellulose are urged in phosphoric acid
Agent position hydrolyzes, and produces the glucosan of molecular weight, disaccharide, polysaccharide, glucose residue, silica residue, water,
CO2 etc., these small molecules are mutually condensed again or polymerization becomes other larger molecules；For example, expanded graphite particles are in hydrolysis
In glucosan viscous solution in addition the shearing force of three-roll grinder, in the presence of drag force, graphite oxide just starts stripping and forms list
Layer or few layer graphene oxide, just the surface of graphene oxide peeled off or edge contain functional group（As carboxyl, hydroxyl）With Fructus Vitis viniferae
Hydroxyl in sugar or aldehyde radical reaction form amide glycolylate, effectively stop the reunion of graphene oxide；Silica chemical combination in rice husk
With the carrying out of saccharifying, silica gradually forms nano level Particle distribution in syrup to thing；In order to improve mechanical dispersion effect,
The roller of three-roll grinder should have different rotating speeds, step of the present invention（2）Described in three-roll grinder slow rollers rotating speed
For 31r/min, the rotating speed of central roll is 83 r/min, and the rotating speed of fast roller is 220r/min.
（3）After sticky carbohydrate admixture is agglomerating, section obtains tablet, ripening in drying baker, ripening by tablet
Temperature is 120 DEG C, and the curing time is 24-48 hour；In maturing process, various small molecules are relied on and itself are had with adjacent molecule
Functional group is had to be bound to each other to form netted firm solid chemical compound, its hardness（Ball-milling method）More than 95%.
（4）By the tablet carbonization 2-3 hour after ripening, graphene oxide is reduced into Graphene, and by saccharide carbonization,
Obtain carbonized material, carbonization temperature is 450 DEG C -500 DEG C；During this just there is following chemical reaction in saccharide：
CXHYOZ→aC+bCO2+cH2O （1）
Glucide is pyrolyzed under isolation air and just forms unformed charcoal（Activated carbon）, carbon dioxide and water.Unformed charcoal is one
Plant the solid with porous, the macropore that charcoal is stayed due to the effusion of carbon dioxide and water when activating, can be used as lithium during discharge and recharge
Ion and the passage of electrolyte ion.
（5）Carbonized material is washed to be reclaimed after phosphoric acid, using 5% HCl solution steaming and decocting；Again by the solution after steaming and decocting with 5%
NaOH solution is neutralized to neutrality, the solution exclusion filtrate after neutralization is obtained wet carbon, and wet carbon is added water boils dechlorination；
There is phosphoric acid or pyrophosphoric acid molecule between not scrubbed carbonized material charcoal and charcoal, after washing, leave mesopore or middle aperture,
Some middle apertures allow lithium ions by and do not allow electrolyte ion pass through, the active carbon layer with this middle aperture can substitute
The SEI film being formed during lithium cell charging, it is to avoid lithium electrode and electrolyte react the loss of caused reversible charge volume.
（6）Wet carbon after dechlorination is dried, and completely cuts off air and institute is obtained in 1300-1800 DEG C of temperature lower calcination 2-3 hour
State Graphene silica carbon negative pole material；The pore size of activated carbon both can be controlled by by adjusting the concentration of phosphoric acid, dense phosphorus
Acid forms macropore, and aperture can use phosphoric acid,diluted instead it is also possible to enter to activated carbon under isolation or inert gas shielding by activated carbon
Row high-temperature process is realizing.
Described 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 expanded in stove.
Described step（1）Middle silicon containing biomass is rice husk, and described rice husk is the garbage after paddy processing.
Described step（1）Described in high speed disintegrator rotating speed be more than 3500r/min.
Described step（1）The more high Graphene silica Carbon anode material being finally obtained of the mass content of the expanded graphite of middle addition
Material conductivity is higher.
Described step（2）The middle phosphoric acid concentration as catalyst is 85%.
Described step（2）The more long Graphene silica carbon negative pole material being finally obtained of the milling time of middle grinder is first
Reversible capacitance is bigger.
Described step（5）In wet carbon add water and boil the concrete grammar of dechlorination and be：Wet 2.5 times of quality of 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.
Described step（6）In wet carbon calcining heat more high finally be obtained Graphene silica carbon negative pole material through continuously filling
Electricity conservation rate after electric discharge measures is higher.
Concrete principle with regard to 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 this reference embodiment, comprise the steps：
The first step, weighs 300 grams of expanded graphites, plus rice husk 50 adds high-speed grinder, pulverizes 10-50min, until material particles
Till can be all by 325 mesh sieves.
Second step, adds phosphoric acid in the mixture of expanded graphite and rice husk（85%）450ml, filters after stirring；Pulpous state
Thing is put in three-roll grinder and is ground, and is initially formed sticky glucide, and cooperation is ground and expanded graphite is peeled off, and is formed and divides
Dissipate few layer of good graphene oxide, be silicon oxide nanorize simultaneously in saccharifying, and dispersed；Milling time is about
48 hours, control Graphene silica carbon granule degree so that the granularity of Graphene silica carbon is between 20-50nm.
3rd step, section after material to be ground is agglomerating obtains tablet, and the thickness of tablet is 2-3mm, and tablet is put into
120 DEG C of drying baker ripening 24-48 hour.
4th step, by the tablet carbonization 2-3 hour after ripening, carbonization temperature is 450 DEG C -500 DEG C；At this moment graphite oxide
Alkene is reduced into Graphene, and, by nanorize, saccharide is by carbonization, then is activated for silicon oxide.
5th step, activated material takes out after washing recovery phosphoric acid with water, first uses 5%HCl steaming and decocting, then with 5%NaOH neutralization, washs
Exclusion filtrate, wet carbon adds 2.5 times of decocting in water boiling 20min, repeatedly repeatedly, till no Cl ion（Use AgNO3Test）；
6th step, is dried wet carbon and completely cuts off air and process at 1300-1800 DEG C, stops 2-3 hour, removes oxygen-containing sense
Group, and make product densification.Product cools down under vacuum or inert gas conditions, pulverize, sieve obtain Graphene silica carbon bear
Pole material.The assay method of the Graphene silica carbon compound cathode materials of sample 1 is entered by GB GB/T 24533-2009 annex G
OK.
Comparative example's group 1, comparative example organizes material prescription and its operation and the reference embodiment of 1 each embodiment
Difference is：In second step, compound is different in the milling time of three-roll grinder.The operating time of comparative example's group 1 divides
It is not：Tetra- kinds of 24h, 48h, 72h, 96h, the sample of each embodiment of comparative example's group 1 is designated as GSC respectively24、GSC48、
GSC72, and GSC96.Through mensure its first reversible capacitance be respectively 480mAhg-1,560mAhg-1,580mAhg-1,600mAhg-
1.As can be seen here, the more long prepared Graphene silica carbon negative pole material capacitance of milling time is higher.
Comparative example's group 2, comparative example organizes material prescription and its operation and the reference embodiment of 2 each embodiment
Difference is：The difference of high-temperature process temperature during the isolation air of the 6th step；The high-temperature process of each embodiment of embodiment group 2
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's group 2 is remembered respectively
For GSC800、GSC900、GSC1100, and GSC1300.Through 30 continuous charge and discharge electrometric determinations, each embodiment of comparative example's group 2
Sample electricity conservation rate is respectively 75%, 80%, 81.5%, 82%.As can be seen here, the more high Graphene silicon being finally obtained for the treatment of temperature
The sample electricity conservation rate of oxygen carbon negative pole material is longer.
Comparative example's group 3, comparative example organizes material prescription and its operation and the reference embodiment of 3 each embodiment
Difference is：In the first step, the addition of expanded graphite is different；Comparative example organizes the quality of the Graphene of 3 each embodiment
Content is respectively 1%, 5%, 10%, 20%, and the sample that comparative example organizes 3 each embodiment is designated as GSC respectively0.01、GSC0.05、
GSC0.1, and GSC0.2.Measure comparative example group 2 the sample of each embodiment conductivity be respectively 0.1s/cm, 1s/cm,
2s/cm and 5s/cm.As can be seen here, the more many Graphene silica carbon negative pole materials being finally obtained of the mass content of Graphene are through even
Conductivity after continuous charge and discharge electrometric determination is higher.
The present invention adopts above technical scheme, is raw material using rice husk, with phosphoric acid as catalyst, passes through at room temperature to grind
Silicon dioxide is dispersed in dextran solution machine, then carries out carbonization-activation at high temperature, forms uniform i/C nano combined
Thing, can effectively be suppressed using the unformed porous carbon of ductility and alleviate volumetric expansion in charge and discharge process for the silicon, and be based on
Alkene silicon-carbon complex builds up three-dimensional conductive network so that bright negative material conductivity（5s-10s/cm）More conductive than porous activated carbon
Rate（0.01s-0.1s/cm）Improve 20-100 times, greatly improve the conduction in charge and discharge process of amorphous porous carbon and silicon
Property, greatly shorten battery charge time, realize the Graphene Si/C complex of carbon coating in addition by mechanochemical reaction, cyclicity
Larger improvement, good cycle can be obtained（Through 30 discharge and recharges, electricity conservation rate is not less than 82%）.
The present invention has given full play to the high specific capacitance of the high conductivity of Graphene, silicide, the spy such as porous of activated carbon
Levy.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：With expanded graphite and silicon containing biomass it is
Raw material, phosphoric acid is catalyst, and motorized educational level method makes negative material, and described mechanochemistry force method comprises the following steps：
（1）Expanded graphite is carried out the silicon containing biomass after expanded rear and cleaning-drying according to mass ratio 1-5:5-20 adds at a high speed
10-50 minute pulverized by pulverizer, and makes the material particles after pulverizing be not more than 325 mesh sieves；
（2）Material particles after pulverizing and the phosphoric acid as catalyst are according to mass ratio 1:1-5 is sufficiently stirred for being filtrated to get pulpous state
Thing；Slurry is put into grinder grinding 24-48 hour sticky carbohydrate admixture is obtained；In process of lapping, graphite is peeled off shape
Become finely dispersed few layer graphene oxide, simultaneously by silicon oxide nanorize and dispersed, the grain of wherein Graphene and silica
Degree is between 20-50nm；
（3）After sticky carbohydrate admixture is agglomerating, section obtains tablet, ripening in drying baker, curing temperature by tablet
For 120 DEG C, the curing time is 24-48 hour；
（4）By the tablet carbonization 2-3 hour after ripening, graphene oxide is reduced into Graphene, and by saccharide carbonization, obtains
Carbonized material, carbonization temperature is 450 DEG C -500 DEG C；
（5）Carbonized material is washed to be reclaimed after phosphoric acid, using 5% HCl solution steaming and decocting；Again by the solution after steaming and decocting with 5% NaOH
Solution is neutralized to neutrality, the solution exclusion filtrate after neutralization is obtained wet carbon, and wet carbon is added water boils dechlorination；
（6）Wet carbon after dechlorination is dried, and completely cuts off air and described stone is obtained in 1300-1800 DEG C of temperature lower calcination 2-3 hour
Black alkene silica carbon negative pole material.
2. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（1）Described in expanded graphite expansion rate be not less than 250, expanded graphite is expanded in being preheated to 900 DEG C of puffing furnace.
3. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（1）Middle silicon containing biomass is rice husk, and described rice husk is the garbage after paddy processing.
4. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（1）Described in high speed disintegrator rotating speed be more than 3500r/min.
5. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（1）The more high Graphene silica carbon negative pole material conductivity being finally obtained of the mass content of the expanded graphite of middle addition is higher.
6. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（2）The middle phosphoric acid concentration as catalyst is 85%.
7. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
Suddenly（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/
Min, the rotating speed of fast roller is 220r/min.
8. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（2）The reversible capacitance first of the more long Graphene silica carbon negative pole material being finally obtained of the milling time of middle grinder is bigger.
9. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
（5）In wet carbon add water and boil the concrete grammar of dechlorination and be：The water adding wet 2.5 times of quality of carbon in wet carbon carries out boiling and boils, repeatedly
Repeatedly to through AgNO3Not chloride ion-containing in wet carbon after test.
10. according to claim 1 a kind of preparation method of Graphene silica carbon negative pole material it is characterised in that：Described step
Suddenly（6）In wet carbon the more high electricity after continuous charge and discharge electrometric determination for the Graphene silica carbon negative pole material being finally obtained of calcining heat
Amount conservation rate is higher.
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