CN103579627A - Graphene-tin composite material, preparation method of graphene-tin composite material, lithium ion battery and preparation method of lithium ion battery - Google Patents
Graphene-tin composite material, preparation method of graphene-tin composite material, lithium ion battery and preparation method of lithium ion battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/387—Tin or alloys based on tin
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The invention relates to a preparation method and a use of a graphene-tin composite material. The preparation method of the graphene-tin composite material utilizes a hydro-thermal in-situ reduction compounding technology. Tin particle sizes are small so that tin and graphene can be mixed uniformly and graphene-tin conductivity is greatly improved and thus a cycle life and multiplying power of the graphene-tin composite material as a lithium ion battery cathode material are improved. The preparation method of the graphene-tin composite material has low equipment and process requirements, can be operated easily, adopts low-cost raw materials and easily realizes large-scale industrial production.
Description
Technical field
The present invention relates to lithium ion battery field, relate in particular to a kind of Graphene-tin composite material, its preparation method, lithium ion battery and preparation method thereof.
Background technology
Constantly perfect along with the development of various electronic products and function, the performance of traditional lithium ion battery more and more can not meet the demand of various consumer products.Negative material has important function for the raising of performance of lithium ion battery.The negative material of tradition lithium ion battery is mainly used graphite, and the theoretical capacity of graphite is only up to 372mAh/g, has greatly limited the performance of lithium ion battery, cannot meet the demand of people to high-capacity battery.Kamash alloy material, with features such as high-energy-density (994mAh/g), high magnification, high securities, has caused people's extensive concern.Although tin has the advantage of high power capacity as negative material, its change in volume in the process of embedding lithium and de-lithium is larger, causes electrode material powdered, and inner forfeiture of active material electrically contacts, and electrode capacity is decayed rapidly, thereby shortens the life-span of lithium ion battery.In order to improve the cyclical stability of tin material, main method is: (1) Nanoalloy, and utilize the superplasticity of nano material to discharge the stress that lithiumation process produces, thereby reduce efflorescence, improve the invertibity of lithiation; (2) intermetallic compound, comprises that active metal and activity or inactive metal are compound, utilize the different and matrix each other of lithiumation current potential between different activities metal, or inactive metal comes buffer volumes to expand as matrix; (3) alloy-carbon composite, the volumetric expansion while utilizing the high resiliency buffering alloy lithiumation of material with carbon element, improves electrically contacting of alloying pellet, for lithium ion and electronics provide diffusion admittance.
Graphene is a kind of two-dimentional monolayer material, has excellent flexibility, tin material and Graphene carry out compound can effectively reduce tin material expand and contraction process in destruction to electrode material, thereby the cycle performance of raising device.Graphene-the tin composite material of tradition report directly carries out high energy with Graphene by tin particles often to be mixed, and tin particles particle diameter is larger, and is difficult to mix, and causes Graphene can not give full play to its effect.
Summary of the invention
Based on this, be necessary to provide a kind of and can make Graphene and the mixed uniformly Graphene-tin composite material of tin and preparation method thereof.
A preparation method for Graphene-tin composite material, comprises the steps:
Graphite oxide is dispersed in deionized water, and the ratio that is 10:2 ~ 4 according to graphite oxide and butter of tin mass ratio adds butter of tin in described deionized water, and ultrasonic dispersion, obtains mixed solution;
In described mixed solution, add reducing agent, at 80 ~ 100 ℃, carry out reduction reaction, obtain Graphene-Xi suspension; And
Filter described Graphene-Xi suspension, after filter residue is washed, is dried, obtain described Graphene-tin composite material.
In an embodiment, described graphite oxide is prepared according to following step therein:
Graphite is added in the mixed solution of 98% concentrated sulfuric acid and 65% red fuming nitric acid (RFNA) composition, and is stirred to and forms uniform mixture under the environment of bathing in frozen water mixing; And
In described mixture, add potassium permanganate, after stirring and be warming up to 85 ℃, keep temperature 30 minutes, keep temperature to add after deionized water standing 30 minutes, adding volumetric concentration is 30% hydrogenperoxide steam generator again, stir after 10 minutes, reaction system is carried out to suction filtration processing, and the filter residue obtaining is used watery hydrochloric acid and deionized water washing repeatedly successively, obtains graphite oxide after oven dry.
In an embodiment, the volume of the quality of described graphite raw material, described 98% concentrated sulfuric acid, the volume of described 65% concentrated sulfuric acid, the volume ratio of the quality of described potassium permanganate and described hydrogen peroxide are 1g:85 ~ 95mL:24 ~ 25mL:4 ~ 6g:6 ~ 10mL therein.
In an embodiment, the concentration of described graphite oxide in described graphite oxide butter of tin mixed solution is 0.5 ~ 1mg/mL therein.
In an embodiment, described reducing agent is sodium borohydride or hydrazine hydrate therein.
-tin composite material, it is to prepare according to the preparation method of above-mentioned Graphene-tin composite material.
In addition, be also necessary to provide lithium ion battery using above-mentioned Graphene-tin composite material and preparation method thereof.
A kind of lithium ion battery, comprise positive pole, described positive pole comprises collector and is coated in the positive electrode on described collector, and described positive electrode comprises conductive agent, binding agent and positive electrode active materials, wherein, positive electrode active materials is above-mentioned Graphene-tin composite material.
A preparation method for lithium ion battery, comprises the steps:
The ratio that is 80 ~ 85:5 ~ 10:5 ~ 10 according to mass ratio, mixes above-mentioned Graphene-tin composite material with binding agent and conductive agent, obtain positive electrode;
Described positive electrode is coated on Copper Foil, after drying, slicing treatment, obtains positive plate;
Using lithium sheet as negative plate, described lithium sheet, barrier film, described positive plate are assembled into battery core;
Described battery core is encapsulated in battery container, and injects electrolyte in described battery container, after sealing, obtain lithium ion battery.
In an embodiment, described binding agent is Kynoar therein; Described conductive agent is acetylene black.
In an embodiment, the electrolyte in described electrolyte is LiPF therein
6, LiBF
4, LiN (SO
2cF
3)
2or LiN (SO
2f)
2, the solvent in described electrolyte is dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate or acetonitrile, the concentration of described electrolyte in described electrolyte is 1mol/L.
Said method utilizes hydro-thermal in-situ reducing compound, the size of tin particles is lower, therefore not only can make tin and Graphene mix, and can increase substantially the conductivity of Graphene-Xi, thereby improve cycle life and multiplying power property that Graphene-tin composite material is applied to lithium ion battery negative material.The preparation process of above-mentioned Graphene-tin composite material is low to equipment, technological requirement, and easy to operate, and the cheap cost of raw material is low, easily realizes large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the Graphene-tin composite material of an execution mode;
Fig. 2 is the preparation flow figure of the lithium ion battery of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments Graphene-tin composite material and its preparation method and application is described in further detail below.
As shown in Figure 1, the preparation method of the Graphene-tin composite material of present embodiment, comprises the steps:
Step S110, is dispersed in graphite oxide in deionized water, and the ratio that is 10:2 ~ 4 according to graphite oxide and butter of tin mass ratio adds butter of tin in described deionized water, and ultrasonic dispersion, obtains mixed solution.
Wherein, graphite oxide can be adopted preparation with the following method:
Graphite is added in the mixed solution of 98% concentrated sulfuric acid and 65% red fuming nitric acid (RFNA) composition, and mixes under the environment of bathing and be stirred to and form uniform mixture at frozen water, wherein, the preferred purity of graphite is not less than 99.5% natural flake graphite; In mixture, add potassium permanganate, after stirring and be warming up to 85 ℃, keep temperature 30 minutes, keep temperature to add after deionized water standing 30 minutes, adding volumetric concentration is 30% hydrogenperoxide steam generator again, stir after 10 minutes, reaction system is carried out to suction filtration processing, and the filter residue obtaining is used watery hydrochloric acid and deionized water washing repeatedly successively, obtains graphite oxide after oven dry.
In the present embodiment, the volume of the quality of graphite raw material, 98% concentrated sulfuric acid, the volume of 65% concentrated sulfuric acid, the volume of the quality of potassium permanganate and hydrogen peroxide preferably add according to following ratio 1g:85 ~ 95mL:24 ~ 25mL:4 ~ 6g:6 ~ 10mL.
The concentration of graphite oxide in mixed solution is 0.5 ~ 1mg/mL.The concentration of butter of tin in mixed solution is 0.1 ~ 0.3mg/mL.
Ultrasonic power can be 500 ~ 800W, and ultrasonic time is 2 ~ 3 hours.After the ultrasonic dispersion treatment of mixed solution, graphite oxide is stripped from into graphene oxide, and ultrasonic dispersion can make graphite oxide mix with butter of tin.
Step S120 adds reducing agent in mixed solution, carries out reduction reaction at 80 ~ 100 ℃, obtains Graphene-Xi suspension.
Reducing agent can be hydrazine hydrate or sodium borohydride.
Step S130, filtering graphite alkene-Xi suspension, obtains Graphene-tin composite material after filter residue is washed, is dried, and wherein, middle horizontal line "-" represents the compound of Graphene and tin.
In Graphene-tin composite material that present embodiment makes, tin metal particle embeds in graphene sheet layer structure or is distributed between the lamella of Graphene, thereby, graphene film interts between tin metal particle, suppress on the one hand volumetric expansion, prevent the secondary agglomeration after metal differentiation, increase on the other hand contacting of active material and electrolyte, improve conductivity, even repeatedly discharge and recharge use after, still keep good contacting between active material and collector, in addition, be different from traditional method of modifying to tin negative pole, graphene film can provide extra capacity, while having reduced use inert material to the modification of tin negative pole, cause capacitance loss, give full play of the cooperative effect of bi-material.
In addition, present embodiment also provides a kind of lithium ion battery and preparation method thereof.The positive pole of this lithium ion battery comprises collector and is coated in the positive electrode on collector, and wherein, positive electrode comprises conductive agent, binding agent and above-mentioned Graphene-tin composite material.Graphene-tin composite material, as the positive electrode active materials of lithium ion battery, can effectively suppress the change in volume of tin particles in charge and discharge process, and the stability of whole lithium ion battery strengthens, and increase useful life.
As shown in Figure 2, the preparation method of this lithium ion battery comprises the steps:
Step S210, prepares Graphene-tin composite material according to the preparation method of above-mentioned Graphene-tin composite material.
Step S220, the ratio that is 80 ~ 85:5 ~ 10:5 ~ 10 according to mass ratio, mixes Graphene 3 SiC 2/graphite alkene composite material, binding agent and conductive agent, obtains positive electrode.
Wherein, binding agent can be Kynoar.Conductive agent can be acetylene black or carbon nano-tube etc.
Step S230, is coated in positive electrode on Copper Foil, after drying, slicing treatment, obtains positive plate.
Step S240, usings lithium sheet as negative plate, and lithium sheet, barrier film, positive plate are assembled into battery core.
Step S250, is encapsulated in battery core in battery container, and injects electrolyte in battery container, obtains lithium ion battery after sealing.
Electrolyte in electrolyte can be LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2) or LiFSI (LiN (SO
2f)
2) etc.; Solvent in electrolyte is dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate or acetonitrile etc.The concentration of electrolyte in electrolyte is 1mol/L.
Said method utilizes hydro-thermal in-situ reducing compound, the size of tin particles is lower, therefore not only can make tin and Graphene mix, and can increase substantially the conductivity of Graphene-Xi, thereby improve cycle life and multiplying power property that Graphene-tin composite material is applied to lithium ion battery negative material.The preparation process of above-mentioned Graphene-tin composite material is low to equipment, technological requirement, and easy to operate, and the cheap cost of raw material is low, easily realizes large-scale industrial production.
Be below specific embodiment part:
Embodiment 1
The graphite oxide of the present embodiment is through peeling off and mixing with butter of tin, then it is as follows through reduction, to prepare the technological process of Graphene-tin composite material:
Graphite → graphite oxide → Graphene-tin composite material
Graphite: the natural flake graphite of purity 99.5%.
Graphite oxide: take in the mixed solution that red fuming nitric acid (RFNA) that the 1g graphite concentrated sulfuric acid that to be added to by 90mL mass fraction be 98% and 25mL mass fraction are 65% forms, obtain mixture, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 6g potassium permanganate lentamente again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add 92mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 10mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes, mixture is carried out to suction filtration, use successively 100mL watery hydrochloric acid and 150mL deionized water to wash solid matter, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
Graphene-tin composite material: get the above-mentioned graphite oxide preparing and be dispersed in deionized water, the concentration of graphite oxide is 0.5mg/mL, and adds butter of tin, and the concentration of butter of tin is 0.1mg/mL, obtain mixed solution, with 500W power to mixed solution ultrasonic 2 hours; In mixed solution, add sodium borohydride again, sodium borohydride concentration is 0.2mg/mL, stirs and be warming up to 80 ° of C, react 24 hours, filter, extremely neutral with deionized water cyclic washing, solid product is placed in to 60 ° of C baking ovens dry 12 hours, obtains Graphene-tin composite.
Embodiment 2
The graphite oxide of the present embodiment is through peeling off and mixing with butter of tin, then it is as follows through reduction, to prepare the technological process of Graphene-tin composite material:
Graphite → graphite oxide → Graphene-tin composite material
Graphite: the natural flake graphite of purity 99.5%.
Graphite oxide: take in the mixed solution that red fuming nitric acid (RFNA) that the 2g graphite concentrated sulfuric acid that to be added to by 190mL mass fraction be 98% and 48mL mass fraction are 65% forms, obtain mixture, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 8g potassium permanganate lentamente again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add 180mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 12mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes, mixture is carried out to suction filtration, use successively 200mL watery hydrochloric acid and 300mL deionized water to wash solid matter, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
Graphene-tin composite material: get the above-mentioned graphite oxide preparing and be dispersed in deionized water, the concentration of graphite oxide is 0.8mg/mL, and adds butter of tin, and the concentration of butter of tin is 0.2mg/mL, obtain mixed solution, with 800W power to mixed solution ultrasonic 2 hours; In mixed solution, add sodium borohydride again, sodium borohydride concentration is 0.4mg/mL, stirs and be warming up to 90 ° of C, react 36 hours, filter, extremely neutral with deionized water cyclic washing, solid product is placed in to 60 ° of C baking ovens dry 12 hours, obtains Graphene-tin composite.
Embodiment 3
The graphite oxide of the present embodiment is through peeling off and mixing with butter of tin, then it is as follows through reduction, to prepare the technological process of Graphene-tin composite material:
Graphite → graphite oxide → Graphene-tin composite material
Graphite: the natural flake graphite of purity 99.5%.
Graphite oxide: take in the mixed solution that red fuming nitric acid (RFNA) that the 5g graphite concentrated sulfuric acid that to be added to by 420mL mass fraction be 98% and 120mL mass fraction are 65% forms, obtain mixture, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 20g potassium permanganate lentamente again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add 460mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 40mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes, mixture is carried out to suction filtration, use successively 300mL watery hydrochloric acid and 500mL deionized water to wash solid matter, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
Graphene-tin composite material: get the above-mentioned graphite oxide preparing and be dispersed in deionized water, the concentration of graphite oxide is 0.5mg/mL, and adds butter of tin, and the concentration of butter of tin is 0.2mg/mL, obtain mixed solution, with 500W power to mixed solution ultrasonic 3 hours; In mixed solution, add sodium borohydride again, sodium borohydride concentration is 0.5mg/mL, stirs and be warming up to 100 ° of C, react 24 hours, filter, extremely neutral with deionized water cyclic washing, solid product is placed in to 60 ° of C baking ovens dry 12 hours, obtains Graphene-tin composite.
Embodiment 4
The graphite oxide of the present embodiment is through peeling off and mixing with butter of tin, then it is as follows through reduction, to prepare the technological process of Graphene-tin composite material:
Graphite → graphite oxide → Graphene-tin composite material
Graphite: the natural flake graphite of purity 99.5%.
Graphite oxide: take in the mixed solution that red fuming nitric acid (RFNA) that the 1g graphite concentrated sulfuric acid that to be added to by 90mL mass fraction be 98% and 25mL mass fraction are 65% forms, obtain mixture, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 4g potassium permanganate lentamente again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add 95mL deionized water to continue to keep 30 minutes under 85 ° of C, finally adding 9mL mass fraction is 30% hydrogenperoxide steam generator, stir 10 minutes, mixture is carried out to suction filtration, use successively 100mL watery hydrochloric acid and 150mL deionized water to wash solid matter, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
Graphene-tin composite material: get the above-mentioned graphite oxide preparing and be dispersed in deionized water, the concentration of graphite oxide is 1mg/mL, and adds butter of tin, and the concentration of butter of tin is 0.2mg/mL, obtain mixed solution, with 500W power to mixed solution ultrasonic 2 hours; In mixed solution, add sodium borohydride again, sodium borohydride concentration is 0.5mg/mL, stirs and be warming up to 100 ° of C, react 24 hours, filter, extremely neutral with deionized water cyclic washing, solid product is placed in to 60 ° of C baking ovens dry 12 hours, obtains Graphene-tin composite.
Embodiment 5
1. according to the mass ratio of 85:5:10, take respectively Graphene-tin composite material of preparing in the embodiment 1 of 8.5g, the Kynoar of 0.5g and the acetylene black of 1.0g, obtain positive electrode after mixing;
2. positive electrode is coated on Copper Foil, drying, slicing treatment, obtain positive plate.
3. using lithium sheet as negative plate, by the positive plate making in lithium sheet, barrier film and upper step in order stack of laminations dress up battery core.
4. the battery core making is encapsulated in battery container, then in battery container, injects the LiPF that electrolyte concentration is 1mol/L by the liquid injection port on battery container
6/ dimethyl carbonate electrolyte (represents that electrolyte is LiPF
6, solvent is the electrolyte of dimethyl carbonate), sealing liquid injection port, obtains lithium ion battery.
Embodiment 6
1. according to the mass ratio of 80:10:10, take respectively Graphene-tin composite material of preparing in the embodiment 1 of 8.0g, the Kynoar of 1.0g and the acetylene black of 1.0g, obtain positive electrode after mixing;
2. positive electrode is coated on Copper Foil, drying, slicing treatment, obtain positive plate.
3. using lithium sheet as negative plate, by the positive plate making in lithium sheet, barrier film and upper step in order stack of laminations dress up battery core.
4. the battery core making is encapsulated in battery container, then in battery container, injects the LiBF that electrolyte concentration is 1mol/L by the liquid injection port on battery container
4/ diethyl carbonate electrolyte (represents that electrolyte is LiBF
4, solvent is the electrolyte of diethyl carbonate), sealing liquid injection port, obtains lithium ion battery.
Embodiment 7
1. according to the mass ratio of 85:10:5, take respectively Graphene-tin composite material of preparing in the embodiment 1 of 8.5g, the Kynoar of 1g and the acetylene black of 5g, obtain positive electrode after mixing;
2. positive electrode is coated on Copper Foil, drying, slicing treatment, obtain positive plate.
3. using lithium sheet as negative plate, by the positive plate making in lithium sheet, barrier film and upper step in order stack of laminations dress up battery core.
4. the battery core making is encapsulated in battery container, by the liquid injection port on battery container, in battery container, inject the LiTFSI/ propene carbonate electrolyte that electrolyte concentration is 1mol/L (representing that electrolyte is that LiTFSI, solvent are the electrolyte of propene carbonate) again, sealing liquid injection port, obtains lithium ion battery.
Embodiment 8
1. according to the mass ratio of 83:8:9, take respectively Graphene-tin composite material of preparing in the embodiment 1 of 8.3g, the Kynoar of 0.8g and the acetylene black of 0.9g, obtain positive electrode after mixing;
2. positive electrode is coated on Copper Foil, drying, slicing treatment, obtain positive plate.
3. using lithium sheet as negative plate, by the positive plate making in lithium sheet, barrier film and upper step in order stack of laminations dress up battery core.
4. the battery core making is encapsulated in battery container, by the liquid injection port on battery container, in battery container, inject LiFSI/ ethylene carbonate/acetonitrile electrolyte that electrolyte concentration is 1mol/L (representing that electrolyte is that LiFSI, solvent are the electrolyte of the mixed solvent formation of ethylene carbonate and acetonitrile) again, sealing liquid injection port, obtains lithium ion battery.
Table 1 encloses for embodiment 5 ~ 8 carries out charge-discharge test the 2nd circle and the 301st under 0.1C electric current the stored energy capacitance obtaining.
Table 1
By upper table 1, can be found out, the specific capacity that the Graphene-tin composite material that adopts said method to prepare obtains is higher, all more than 600mAh/g, particularly circulate specific capacity conservation rate after 300 circles all more than 70%, be up to 83%, be significantly higher than traditional tin-based negative electrode materials for lithium-ion battery than electric capacity conservation rate.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for Graphene-tin composite material, is characterized in that, comprises the steps:
Graphite oxide is dispersed in deionized water, and the ratio that is 10:2 ~ 4 according to graphite oxide and butter of tin mass ratio adds butter of tin in described deionized water, and ultrasonic dispersion, obtains mixed solution;
In described mixed solution, add reducing agent, at 80 ~ 100 ℃, carry out reduction reaction, obtain Graphene-Xi suspension; And
Filter described Graphene-Xi suspension, after filter residue is washed, is dried, obtain described Graphene-tin composite material.
2. the preparation method of Graphene-tin composite material as claimed in claim 1, is characterized in that, described graphite oxide is prepared according to following step:
Graphite is added in the mixed solution of 98% concentrated sulfuric acid and 65% red fuming nitric acid (RFNA) composition, and is stirred to and forms uniform mixture under the environment of bathing in frozen water mixing; And
In described mixture, add potassium permanganate, after stirring and be warming up to 85 ℃, keep temperature 30 minutes, keep temperature to add after deionized water standing 30 minutes, adding volumetric concentration is 30% hydrogenperoxide steam generator again, stir after 10 minutes, reaction system is carried out to suction filtration processing, and the filter residue obtaining is used watery hydrochloric acid and deionized water washing repeatedly successively, obtains graphite oxide after oven dry.
3. the preparation method of Graphene-tin composite material as claimed in claim 2, it is characterized in that, the volume of the quality of described graphite raw material, described 98% concentrated sulfuric acid, the volume of described 65% concentrated sulfuric acid, the volume ratio of the quality of described potassium permanganate and described hydrogen peroxide are 1g:85 ~ 95mL:24 ~ 25mL:4 ~ 6g:6 ~ 10mL.
4. the preparation method of Graphene-tin composite material as claimed in claim 1, is characterized in that, the concentration of described graphite oxide in described graphite oxide butter of tin mixed solution is 0.5 ~ 1mg/mL.
5. the preparation method of Graphene-tin composite material as claimed in claim 1, is characterized in that, described reducing agent is sodium borohydride or hydrazine hydrate.
6. Graphene-tin composite material, is characterized in that, described composite material is to prepare according to the preparation method of the Graphene-tin composite material as described in any one in claim 1-6.
7. a lithium ion battery, comprise positive pole, described positive pole comprises collector and is coated in the positive electrode on described collector, and described positive electrode comprises conductive agent, binding agent and positive electrode active materials, it is characterized in that, positive electrode active materials is Graphene-tin composite material claimed in claim 7.
8. a preparation method for lithium ion battery, is characterized in that, comprises the steps:
The ratio that is 80 ~ 85:5 ~ 10:5 ~ 10 according to mass ratio, Graphene-tin composite material mixes with binding agent and conductive agent as described in claim 7, obtains positive electrode;
Described positive electrode is coated on Copper Foil, after drying, slicing treatment, obtains positive plate;
Using lithium sheet as negative plate, described lithium sheet, barrier film, described positive plate are assembled into battery core;
Described battery core is encapsulated in battery container, and injects electrolyte in described battery container, after sealing, obtain lithium ion battery.
9. the preparation method of lithium ion battery as claimed in claim 8, is characterized in that, described binding agent is Kynoar; Described conductive agent is acetylene black.
10. the preparation method of lithium ion battery as claimed in claim 8, is characterized in that, the electrolyte in described electrolyte is LiPF
6, LiBF
4, LiN (SO
2cF
3)
2or LiN (SO
2f)
2, the solvent in described electrolyte is dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate or acetonitrile, the concentration of described electrolyte in described electrolyte is 1mol/L.
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| CN105161697A (en) * | 2015-07-18 | 2015-12-16 | 东北师范大学 | Micro-nano structure compound with stable chemical bond and preparation method of micro-nano structure compound |
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| CN107863522B (en) * | 2017-11-20 | 2020-10-30 | 安徽师范大学 | Preparation method of tin/reduced graphene oxide nanocomposite, lithium ion battery cathode and lithium ion battery |
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| CN110212185A (en) * | 2019-06-04 | 2019-09-06 | 中国地质大学（北京） | A kind of Sn-P-CNT composite material and its purposes for preparing lithium ion battery negative material |
| CN110212185B (en) * | 2019-06-04 | 2021-01-05 | 中国地质大学（北京） | Sn-P-CNT composite material and application thereof in preparation of lithium ion battery negative electrode material |
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