CN109273675A - A kind of graphene composite material and preparation method thereof and negative electrode of lithium ion battery - Google Patents
A kind of graphene composite material and preparation method thereof and negative electrode of lithium ion battery Download PDFInfo
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- 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
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Abstract
The invention discloses a kind of graphene composite material and preparation method thereof and its in negative electrode of lithium ion battery, including the use of improved Hummers method redox graphite powder, yellow starch gum is added simultaneously as stabilizer, and alanine makees the graphene that amino functional is prepared with hydrazine hydrate collective effect graphene oxide.Further pass through high-energy ball milling and SnO2The mixing of/SiO powder, then graphene/SnO is prepared through high-temperature calcination2/ SiO composite material.The composite material that the present invention is prepared be effectively reduced graphene reunion degree and large specific surface area, electric conductivity it is high.Furthermore also disclose it is a kind of a kind of negative electrode of lithium ion battery is prepared using this composite material, the cycle performance of lithium ion battery can be greatly improved.
Description
Technical field
The present invention relates to a kind of technical field of graphene preparation, and in particular to a kind of graphene composite material and its preparation side
Method and its application in negative electrode of lithium ion battery technology.
Background technique
Graphene is a kind of new material for possessing unique texture and excellent properties, it is monoatomic layer bi-dimensional cellular shape knot
Structure, it is considered to be the basic structural unit of fullerene, carbon nanotube and graphite.Zero dimension fullerene is to bend to football by graphene
What shape obtained, one-dimensional carbon nanotube is crimped by graphene, and the graphite of three-dimensional structure is then considered as graphene sheet layer
Close stack.It has become about the theoretical research of graphene, experiment preparation and application etc. and studies both at home and abroad in recent years
Hot spot.Since graphene has many good characteristics such as high conductivity, high-termal conductivity, high-specific surface area, high intensity and rigidity,
The numerous areas such as energy storage, photoelectric device, chemical catalysis have been widely used, wherein especially prominent in field of lithium ion battery
It cries.Lithium ion battery is the highest secondary cell of specific energy so far, has best comprehensive performance, it has also become portable electric
The first choice of sub- equipment and electrical source of power, especially the latter propose energy density, the power density of lithium ion battery higher
It is required that.Current commercialized lithium ion battery mostly uses greatly graphite as cathode, but the poor high rate performance of graphite and lower
Theoretical capacity (372mAh/g) is one of the main bottleneck for restricting lithium ion battery as the following extensive energy storage device.Therefore,
It is extremely urgent to develop novel high-energy negative electrode material.
The appearance of graphene is that the high performance breakthrough of lithium ion battery brings possibility, to be high capacity, high magnification, length
The research of the lithium ion battery material in service life starts the research boom of a new round.
Prior art CN106960959A discloses a kind of negative electrode of lithium ion battery and lithium ion battery, it by collector and
It is constituted coated in the negative electrode material on the collector, the negative electrode material is by graphite-like active material, conductive agent, binder and adds
Agent is added to form；The lithium ion of its additive initial charge receives the 0.2wt%-4wt% that ability is the graphite-like active material.
This negative electrode of lithium ion battery, directly active material of the selection graphite as negative electrode material, due to the theoretical capacity of graphite, electric conductivity
Can be relatively low, the capacity of cathode therefrom will also be limited.
Prior art CN107359308A discloses the Preparation equipment and method of a kind of graphene silicon lithium cell cathode material,
Preparation method mainly using Hummers method prepares graphene oxide, then by it with nano-silicon, business carbon nanotube certain
Under the conditions of compound obtain graphene/carbon nano-tube/silicium cathode material.In this invention, the negative electrode material obtained its dispersibility not
Height, and be easy to happen and assemble again, to influence the cycle performance of lithium ion battery.
Summary of the invention
In view of this, technical problem to be solved by the invention is to provide a kind of preparation method of graphene composite material,
The reunion degree and large specific surface area, electric conductivity of graphene can be effectively reduced with the graphene composite material that the method obtains
It is high.
At the same time, another technical problems to be solved of the invention are to provide a kind of negative electrode of lithium ion battery, this cathode
The formation that SEI film can effectively be inhibited, substantially increases the cycle performance of lithium ion battery.
In order to solve the above technical problems, the present invention provides a kind of preparation method of graphene composite material, including following step
It is rapid:
A, oxidation-reduction method prepares graphene
(1) by H3PO4、H2SO4Mixed solution is stirred with graphite powder, mixing speed 400-600r/min, when stirring
Between 0.5-1.5h, be added potassium permanganate in batches, keep temperature to be lower than 30 DEG C in reaction；
(2) it is warming up to 30-40 DEG C, deionized water is added, is continuously heating to 50-60 DEG C, reacts 0.5-1h；
(3) it is cooled to 35-45 DEG C, hydrogen peroxide is added dropwise and obtains mixed liquor, the hydrogen peroxide mass fraction is 20-
40%；
(4) gained mixed liquor is centrifugated, removes upper liquid, obtained solid uses hydrochloric acid, distillation water washing respectively；
(5) repeat above-mentioned centrifugation, wash twice, obtain lower layer's solid distilled water is added, yellow starch gum ultrasonic mixing must be stable
Graphene oxide water solution；
(6) above-mentioned graphene oxide water solution pH to 10-11 is adjusted, alanine, hydrazine hydrate is added at 30-35 DEG C in temperature control,
3-6h is reacted, centrifuge separation takes lower layer's solid, uses methanol, water washing, filtering, dry graphene respectively；
B, SnO is prepared2/ SiO mixed powder
SnCl is added in ethyl alcohol2.2H2In O aqueous solution, ultrasonic 1-2h is added ammonium hydroxide to precipitating completely, precipitating is obtained by filtration
Object uses ethyl alcohol, water washing respectively, is ground into SnO after vacuum drying2Gained powder is mixed to get by powder in proportion with SiO
SnO2/ SiO mixed powder；
C, graphene/SnO is prepared2/ SiO composite material
(1) by the SnO of the graphene of step A and step B2/ SiO mixed powder is placed in ball grinder, in inert gas ring
Ball milling is carried out under border；
(2) mixture after ball milling is placed in the tube furnace full of inert gas and calcines 4-6h, calcination temperature 500-
900℃。
The preparation method of graphene has mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, liquid phase stripping method, changes
Learn synthetic method, chemical stripping method etc..Wherein chemical stripping method is an extremely simple generating process, it is considered to be most industrial
Change one of the method for productive value.So far, Brodie method, Standenmaier method, Hummers method are commonly used for producing stone
Black alkene, the present invention utilize improved Hummers method, H in preparation process3PO4、H2SO4Mixed acid system can be substantially reduced routine
The pyroreaction of Hummers method is also prepared without the generation of toxic gas in reaction process to reduce production energy consumption
Graphene oxide compound with regular structure.
Preferred H3PO4With H2SO4Molar ratio is 1:7-9.
Furthermore distilled water and yellow starch gum is added simultaneously in step A (5), the effect of yellow starch gum main stabilization agent herein,
Its addition considerably increases the stability of graphene oxide in aqueous solution, obtained graphene oxide good dispersion, thus
Also improve the reunion degree of graphene composite material.The addition that alanine is added in step A (6) simultaneously can simultaneously obtain part
Amino acid functionalised graphene, so that the conductivity of graphene obtains certain raising.
In numerous investigation of materials systems, Sn and Si can release 994mAhg respectively-1And 4200mAhg-1
High theoretical capacity, however Sn and Si sill be used for negative electrode of lithium ion battery when there are biggish bulk effect, Jin Eryin
Play the rapid decay of capacity.In order to improve this performance, the present invention selects SnO2It is compound with graphene with SiO, it not only improves
The bulk effect of Sn and Si sill, while also substantially increasing the conductivity of composite material.
As a preference, it is control feed time in 20-30min that potassium permanganate is added in step A (1) in batches, divide
Batch, which is slowly added to potassium permanganate, can allow graphite powder oxidation complete.
As a preference, the mass ratio of distilled water described in step A (5), yellow starch gum is 30-60:1, the ultrasound is mixed
It is 200-400W, ultrasonic time 2-5h that conjunction technique, which is power,.
Further, the revolving speed of the centrifuging process being related in step, centrifugation is 5000-8000r/min, when centrifugation
Between be 20-30min.
As a preference, the mass ratio of alanine described in step A (6) and hydrazine hydrate is 1-2:5-10.
As a preference, ratio described in step B is SnO2With SiO mass ratio 1-2:7-10.Select proper ratio
SiO and SnO2, the electric conductivity and cyclical stability of composite material can be improved.
As a preference, ball milling described in step C specifically: abrading-ball is Ceramic Balls, rotational speed of ball-mill 300-500r/
Min, mixed material and mill ball quality ratio are 1:10-20, Ball-milling Time 6-9h.Make graphene, SnO by ball milling2With SiO
It is sufficiently mixed, the graphene/SnO being evenly distributed2/ SiO mixed powder.
The second object of the present invention is to provide a kind of graphene composite material, and the composite material is answered by above-mentioned graphene
Obtained by the preparation method of condensation material.
The third object of the present invention is to provide a kind of negative electrode of lithium ion battery, including negative current collector and is coated in afflux
Negative electrode material on body, negative electrode material graphene composite material, conductive agent, binder and the dispersion provided by the present invention
Agent is mixed to prepare.
As a preference, the graphene composite material accounts for 93-95%, described on the basis of negative electrode material total weight
Conductive agent accounts for 2-4%, and the binder accounts for 1.5-3.5%, and the dispersing agent accounts for 0.2-1%.
Further, the conductive agent is acetylene black；The binder is butadiene-styrene rubber, polyacrylate, polyimides
Any one of；The dispersing agent is sodium carboxymethylcellulose.
The beneficial effects of the present invention are:
1) the present invention provides a kind of graphene composite material, the graphene being prepared using improved Hummers method
With SnO2Compound with SiO, the reunion degree and large specific surface area, electric conductivity of graphene can be effectively reduced in obtained material
It is high.
2) the present invention also provides a kind of negative electrode of lithium ion battery, this cathode can effectively inhibit the formation of SEI film, significantly
Improve the cycle performance of lithium ion battery.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
The preparation of 1 graphene composite material of embodiment
A, graphene is prepared
The H for being 1:8 by 500ml molar ratio3PO4/H2SO4It is added in 5g graphite powder, magnetic agitation 1.5h, mixing speed is
400r/min, control temperature are lower than 30 DEG C, 20g potassium permanganate are added in reaction system in batches, control adding for potassium permanganate
The material time is 30min.40 DEG C are warming up to, deionized water 100ml is added, is continuously heating to 60 DEG C, reacts 0.5h.Adjusting temperature is
45 DEG C, the hydrogen peroxide 5ml that mass fraction is 40% is added dropwise and obtains mixed liquor, by the centrifugation of gained mixed liquor, washing 3 times, washing
Shi Yici hydrochloric acid, distillation water washing.It takes lower layer's solid that distilled water 300ml, yellow starch gum 10g is added, surpasses under the power of 200W
Sonication 5h, then the pH value of adjusting solution to 11,35 DEG C of temperature, is added alanine 0.5g, hydrazine hydrate 5g, is stirred to react 3h,
After centrifugation, use methanol respectively, water washing, after filtration drying graphene.Above-mentioned centrifugal rotational speed selects 5000r/min, centrifugation
Time is 30min.
B, SnO is prepared2/ SiO mixed powder
The ethyl alcohol of 20ml is taken to be slowly added to the SnCl of 50ml2··2H2It is ultrasonically treated 1h in O aqueous solution, ammonium hydroxide is added to heavy
It forms sediment completely, sediment is obtained by filtration, use ethyl alcohol, water washing respectively, be dried in vacuo 45min, be ground into SnO2Powder, by SnO2Powder
Last and SiO is mixed to get SnO in the ratio of 1:72/ SiO mixed powder.
C, graphene/SnO is prepared2/ SiO composite material
By the graphene and SnO of step A2/ SiO mixed powder mixes to obtain mixed material, and mixed material and Ceramic Balls press 1:
10 ratio is placed in the ball grinder full of Ar gas, rotational speed of ball-mill 300r/min, is carried out ball milling 9h and is obtained graphene/SnO2/SiO
Mixed powder, then by graphene/SnO2/ SiO mixed powder, which is placed in the tube furnace full of Ar gas, calcines 4h, and calcination temperature is
900 DEG C to get graphene/SnO2/ SiO composite material.
Obtained graphene composite material is subjected to electrical detection, conductivity 6700S/m.
The preparation of 2 graphene composite material of embodiment
A, graphene is prepared
The H for being 1:7 by 500ml molar ratio3PO4/H2SO4It is added in 5g graphite powder, mechanical stirring 0.5h, mixing speed is
600r/min, control temperature are lower than 30 DEG C, 20g potassium permanganate are added in reaction system in batches, control adding for potassium permanganate
The material time is 20min.30 DEG C are warming up to, deionized water 100ml is added, is continuously heating to 50 DEG C, reacts 1h.Adjusting temperature is 35
DEG C, the hydrogen peroxide 5ml that mass fraction is 20% is added dropwise and obtains mixed liquor, by the centrifugation of gained mixed liquor, washing 3 times, when washing
Successively with hydrochloric acid, distillation water washing.Take lower layer's solid that distilled water 600ml, yellow starch gum 10g is added, it is ultrasonic under the power of 400W
2h is handled, the pH value of solution is then adjusted to 10,30 DEG C of temperature, alanine 1g, hydrazine hydrate 5g is added, is stirred to react 6h, is centrifuged
Afterwards, use methanol respectively, water washing, after filtration drying graphene.Above-mentioned centrifugal rotational speed selects 7000r/min, centrifugation time
For 25min.
B, SnO is prepared2/ SiO mixed powder
The ethyl alcohol of 20ml is taken to be slowly added to the SnCl of 50ml2··2H2It is ultrasonically treated 2h in O aqueous solution, ammonium hydroxide is added to heavy
It forms sediment completely, sediment is obtained by filtration, use ethyl alcohol, water washing respectively, be dried in vacuo 1h, be ground into SnO2Powder, by SnO2Powder with
SiO is mixed to get SnO in the ratio of 1:102/ SiO mixed powder.
C, graphene/SnO is prepared2/ SiO composite material
By the graphene and SnO of step A2/ SiO mixed powder mixes to obtain mixed material, and mixed material and Ceramic Balls press 1:
20 ratio is placed in the ball grinder full of helium, rotational speed of ball-mill 500r/min, is carried out ball milling 6h and is obtained graphene/SnO2/
SiO mixed powder, then by graphene/SnO2/ SiO mixed powder, which is placed in the tube furnace full of helium, calcines 5h, calcination temperature
For 700 DEG C to get graphene/SnO2/ SiO composite material.
Obtained graphene composite material is subjected to electrical detection, conductivity 7100S/m.
The preparation of 3 graphene composite material of embodiment
A, graphene is prepared
The H for being 1:9 by 800ml molar ratio3PO4/H2SO4It is added in 10g graphite powder, magnetic agitation 1h, mixing speed is
600r/min, control temperature are lower than 30 DEG C, 30g potassium permanganate are added in reaction system in batches, control adding for potassium permanganate
The material time is 28min.35 DEG C are warming up to, deionized water 200ml is added, is continuously heating to 55 DEG C, reacts 1h.Adjusting temperature is 40
DEG C, the hydrogen peroxide 10ml that mass fraction is 30% is added dropwise and obtains mixed liquor, by the centrifugation of gained mixed liquor, washing 3 times, when washing
Successively with hydrochloric acid, distillation water washing.Take lower layer's solid that distilled water 600ml, yellow starch gum 15g is added, it is ultrasonic under the power of 300W
4h is handled, the pH value of solution is then adjusted to 10,33 DEG C of temperature, alanine 1g, hydrazine hydrate 9g is added, is stirred to react 5h, is centrifuged
Afterwards, use methanol respectively, water washing, after filtration drying graphene.Above-mentioned centrifugal rotational speed selects 8000r/min, centrifugation time
For 20min.
B, SnO is prepared2/ SiO mixed powder
The ethyl alcohol of 30ml is taken to be slowly added to the SnCl of 80ml2··2H2It is ultrasonically treated 2h in O aqueous solution, ammonium hydroxide is added to heavy
It forms sediment completely, sediment is obtained by filtration, use ethyl alcohol, water washing respectively, be dried in vacuo 1h, be ground into SnO2Powder, by SnO2Powder with
SiO is mixed to get SnO in the ratio of 2:72/ SiO mixed powder.
C, graphene/SnO is prepared2/ SiO composite material
By the graphene and SnO of step A2/ SiO mixed powder mixes to obtain mixed material, and mixed material and Ceramic Balls press 1:
15 ratio is placed in the ball grinder full of nitrogen, rotational speed of ball-mill 500r/min, carry out ball milling 8h i.e. obtain graphene/
SnO2/ SiO mixed powder, then by graphene/SnO2/ SiO mixed powder, which is placed in the tube furnace full of nitrogen, calcines 6h, calcining
Temperature is 500 DEG C to get graphene/SnO2/ SiO composite material.
Obtained graphene composite material is subjected to electrical detection, conductivity 6500S/m.
4 comparative example of embodiment (yellow starch gum and alanine is not added)
A, graphene is prepared
The H for being 1:9 by 800ml molar ratio3PO4/H2SO4It is added in 10g graphite powder, mechanical stirring 1h, mixing speed is
500r/min, control temperature are lower than 30 DEG C, 30g potassium permanganate are added in reaction system in batches, control adding for potassium permanganate
The material time is 25min.40 DEG C are warming up to, deionized water 200ml is added, is continuously heating to 60 DEG C, reacts 1h.Adjusting temperature is 45
DEG C, the hydrogen peroxide 10ml that mass fraction is 30% is added dropwise and obtains mixed liquor, by the centrifugation of gained mixed liquor, washing 3 times, when washing
Successively with hydrochloric acid, distillation water washing.It takes lower layer's solid that distilled water 500ml is only added, 3h is ultrasonically treated under the power of 400W, so
The pH value of solution is adjusted afterwards to 10,35 DEG C of temperature, and hydrazine hydrate 5g is added, is stirred to react 4h, after centrifugation, uses methanol, washing respectively
It washs, graphene is obtained after filtration drying.Above-mentioned centrifugal rotational speed selects 8000r/min, centrifugation time 25min.
B, SnO is prepared2/ SiO mixed powder
The 0.4mol/L ethyl alcohol of 40ml is taken to be slowly added to the SnCl of 80ml2··2H2It is ultrasonically treated 1.5h in O aqueous solution, is added
Enter ammonium hydroxide to precipitating completely, sediment is obtained by filtration, uses ethyl alcohol, water washing respectively, is dried in vacuo 1h, is ground into SnO2Powder,
By SnO2Powder and SiO are mixed to get SnO in the ratio of 1:82/ SiO mixed powder.
C, graphene/SnO is prepared2/ SiO composite material
By the graphene and SnO of step A2/ SiO mixed powder mixes to obtain mixed material, and mixed material and Ceramic Balls press 1:
10 ratio is placed in the ball grinder full of nitrogen, rotational speed of ball-mill 450r/min, carry out ball milling 7h i.e. obtain graphene/
SnO2/ SiO mixed powder, then by graphene/SnO2/ SiO mixed powder, which is placed in the tube furnace full of nitrogen, calcines 6h, calcining
Temperature is 800 DEG C to get graphene/SnO2/ SiO composite material.
Obtained graphene composite material is subjected to electrical detection, conductivity 5800S/m.
5 negative electrode of lithium ion battery of embodiment
On the basis of negative electrode material total weight, form according to following components: embodiment 1 prepares resulting graphene composite wood
Material 93%, acetylene black 4%, butadiene-styrene rubber 2.8%, sodium carboxymethylcellulose pyce 0.2% are mixed to prepare negative electrode material, resulting materials are applied
It overlays on copper foil of affluxion body, negative electrode of lithium ion battery obtained by drying.
6 negative electrode of lithium ion battery of embodiment
On the basis of negative electrode material total weight, form according to following components: embodiment 2 prepares resulting graphene composite wood
Material 94%, acetylene black 3%, polyacrylate 2.5%, sodium carboxymethylcellulose pyce 0.5% is mixed to prepare negative electrode material, by resulting materials
Coated on copper foil of affluxion body, negative electrode of lithium ion battery obtained by drying.
7 negative electrode of lithium ion battery of embodiment
On the basis of negative electrode material total weight, form according to following components: embodiment 3 prepares resulting graphene composite wood
Material 94%, acetylene black 2%, polyimides 3.5%, sodium carboxymethylcellulose pyce 0.5% are mixed to prepare negative electrode material, resulting materials are applied
It overlays on copper foil of affluxion body, negative electrode of lithium ion battery obtained by drying.
8 negative electrode of lithium ion battery of embodiment
On the basis of negative electrode material total weight, form according to following components: embodiment 4 prepares resulting graphene composite wood
Material 95%, acetylene black 2.5%, butadiene-styrene rubber 1.5%, sodium carboxymethylcellulose pyce 1% are mixed to prepare negative electrode material, resulting materials are applied
It overlays on copper foil of affluxion body, negative electrode of lithium ion battery obtained by drying.
The performance test of 9 negative electrode of lithium ion battery of embodiment
At room temperature, 100mA/g 3.5V charges, 100mA/g 2.7V electric discharge, with identical anode, electrolyte point
Battery A, B, C, D are not assembled into the resulting negative electrode of lithium ion battery of above-described embodiment 5-8 and carries out cycle performance test.As a result such as
Under:
| Battery | Cycle efficieny for the first time | 50 weeks specific capacities of circulation are kept | 100 weeks specific capacities of circulation are kept |
| A | 95% | 632.9mA/g | 613.5mA/g |
| B | 96.2% | 647.3mA/g | 621.4mA/g |
| C | 94.3% | 628.8mA/g | 610.7mA/g |
| D | 89% | 607.1mA/g | 526.8mA/g |
As can be seen from the above table, the resulting graphene composite material of comparative example 4 is used as negative electrode of lithium ion battery material
Expect resulting battery D, compared to battery A, B and C, cycle efficieny is low for the first time, and cycle performance is also poor.It can be seen that by this hair
The cycle performance for the negative electrode of lithium ion battery that graphene composite material provided by bright is prepared greatly improves, specific capacity
It improves.
In the description of this specification, reference term " embodiment ", " another embodiment ", " other embodiments " or "
The description of one embodiment~X embodiment " etc. mean specific features described in conjunction with this embodiment or example, structure, material or
Person's feature is included at least one embodiment or example of the invention.In the present specification, to the schematic table of above-mentioned term
Stating may not refer to the same embodiment or example.Moreover, specific features, structure, material, method and step or the spy of description
Point can be combined in any suitable manner in any one or more of the embodiments or examples.
It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that the process, method, article or the device that include a series of elements not only include those elements, and
And further include other elements that are not explicitly listed, or further include for this process, method, article or device institute it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including being somebody's turn to do
There is also other identical elements in the process, method of element, article or device.
The serial number of the above embodiments of the invention is only for description, does not represent the advantages or disadvantages of the embodiments.
The above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferred embodiment to this hair
It is bright to be described in detail, those skilled in the art should understand that, it can modify to technical solution of the present invention
Or equivalent replacement should all cover without departing from the objective and range of technical solution of the present invention in claim of the invention
In range.
Claims (10)
1. a kind of preparation method of graphene composite material, which comprises the following steps:
A, oxidation-reduction method prepares graphene
(1) by H3PO4、H2SO4Mixed solution is stirred with graphite powder, mixing speed 400-600r/min, mixing time
Potassium permanganate is added in batches, keeps temperature to be lower than 30 DEG C in reaction by 0.5-1.5h；
(2) it is warming up to 30-40 DEG C, deionized water is added, is continuously heating to 50-60 DEG C, reacts 0.5-1h；
(3) it is cooled to 35-45 DEG C, hydrogen peroxide is added dropwise and obtains mixed liquor, the hydrogen peroxide mass fraction is 20-40%；
(4) gained mixed liquor is centrifugated, removes upper liquid, obtained solid uses hydrochloric acid, distillation water washing respectively；
(5) it repeats above-mentioned centrifugation, wash twice, obtain the oxygen that distilled water is added in lower layer's solid, yellow starch gum ultrasonic mixing must be stable
Graphite aqueous solution；
(6) above-mentioned graphene oxide water solution pH to 10-11 is adjusted, alanine, hydrazine hydrate, reaction is added at 30-35 DEG C in temperature control
3-6h, centrifuge separation take lower layer's solid, use methanol, water washing, filtering, dry graphene respectively；
B, SnO is prepared2/ SiO mixed powder
SnCl is added in ethyl alcohol2.2H2In O aqueous solution, ultrasonic 1-2h is added ammonium hydroxide to precipitating completely, sediment is obtained by filtration, point
Not Yong ethyl alcohol, water washing, be ground into SnO after vacuum drying2Gained powder and SiO are mixed to get SnO by powder in proportion2/SiO
Mixed powder；
C, graphene/SnO is prepared2/ SiO composite material
(1) by the SnO of the graphene of step A and step B2/ SiO mixed powder is placed in ball grinder, under inert gas environment into
Row ball milling；
(2) mixture after ball milling is placed in the tube furnace full of inert gas and calcines 4-6h, calcination temperature 500-900
℃。
2. a kind of preparation method of graphene composite material according to claim 1, which is characterized in that described to add in batches
Entering potassium permanganate is control feed time in 20-30min.
3. a kind of preparation method of graphene composite material according to claim 1, which is characterized in that institute in step A (5)
State distilled water, yellow starch gum mass ratio be 30-60:1, the ultrasonic mixing technique is that power is 200-400W, ultrasonic time 2-
5h。
4. a kind of preparation method of graphene composite material according to claim 1, which is characterized in that institute in step A (6)
The mass ratio for stating alanine and hydrazine hydrate is 1-2:5-10.
5. a kind of preparation method of graphene composite material according to claim 1, which is characterized in that described in step B
Ratio is SnO2With SiO mass ratio 1-2:7-10.
6. a kind of preparation method of graphene composite material according to claim 1, which is characterized in that described in step C
Ball milling specifically: abrading-ball is Ceramic Balls, and rotational speed of ball-mill 300-500r/min, mixed material and mill ball quality ratio are 1:10-20,
Ball-milling Time is 6-9h.
7. a kind of graphene composite material, which is characterized in that the composite material is by side of any of claims 1-6
Method preparation gained.
8. a kind of negative electrode of lithium ion battery, the negative electrode material including negative current collector and coating on a current collector, which is characterized in that
The negative electrode material is made by graphene composite material as claimed in claim 7, conductive agent, binder and dispersant.
9. negative electrode of lithium ion battery according to claim 8, which is characterized in that on the basis of negative electrode material total weight, institute
It states graphene composite material and accounts for 93-95%, the conductive agent accounts for 2-4%, and the binder accounts for 1.5-3.5%, the dispersing agent
Account for 0.2-0.8%.
10. according to any negative electrode of lithium ion battery of claim 8-9, which is characterized in that the conductive agent is acetylene black；
The binder is any one of butadiene-styrene rubber, polyacrylate, polyimides；The dispersing agent is carboxymethyl cellulose
Sodium.
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