CN103579626A - Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery - Google Patents

Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery Download PDF

Info

Publication number
CN103579626A
CN103579626A CN201210259414.7A CN201210259414A CN103579626A CN 103579626 A CN103579626 A CN 103579626A CN 201210259414 A CN201210259414 A CN 201210259414A CN 103579626 A CN103579626 A CN 103579626A
Authority
CN
China
Prior art keywords
graphene
composite material
tin
preparation
tin composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201210259414.7A
Other languages
Chinese (zh)
Inventor
周明杰
钟辉
王要兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201210259414.7A priority Critical patent/CN103579626A/en
Publication of CN103579626A publication Critical patent/CN103579626A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a graphene/tin composite material and its preparation method and use. The preparation method of the graphene/tin composite material utilizes a high-temperature 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

Graphene/tin composite material and preparation method thereof, lithium ion battery and preparation method thereof
Technical field
The present invention relates to lithium ion battery field, relate in particular to a kind of Graphene/tin composite material and preparation method thereof, 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.
A preparation method for Graphene/tin composite material, comprises the steps:
Graphite oxide is dispersed in deionized water, and the ratio that is 1 ~ 5:1 according to graphite oxide and tin ash mass ratio adds tin ash in described solvent, and ultrasonic dispersion, obtains mixed solution;
Filter described mixed solution, obtain the compound of graphene oxide and tin ash; And
Described compound is placed under reproducibility atmosphere, with the heating rates of 15 ℃/min ~ 30 ℃/min, is warming up to 700 ~ 1000 ℃, react after 1 ~ 2 hour and obtain 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 mixed solution is 0.5 ~ 1mg/mL therein.
Therein in an embodiment, the mist atmosphere that described reproducibility atmosphere is protective gas and reducibility gas, wherein, the flow of described protective gas is 300 ~ 400mL/ minute, the flow-rate ratio of described protective gas and described reducibility gas is 8 ~ 20:1.
/ tin composite material, it is to prepare according to the preparation method of above-mentioned Graphene/tin composite material.
The compound of graphene oxide and tin ash in addition, is also necessary to provide a kind of lithium ion battery that uses above-mentioned Graphene/tin composite material and preparation method thereof.
, comprising positive pole, described positive pole comprises collector and is coated in the positive electrode on described collector, described positive electrode comprises conductive agent, binding agent and positive electrode active materials; Wherein, described 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 high-temp in-situ reduction compound, the size of tin particles is less, therefore not only can make tin and Graphene mix, and can increase substantially the conductivity of Graphene/tin, 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 solvent, and the ratio that is 1 ~ 5:1 according to graphite oxide and tin ash mass ratio adds tin ash in solvent, 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 is stirred to and forms uniform mixture under the environment of bathing in frozen water mixing; 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 preferred purity of graphite is not less than 99.5% natural flake graphite.The volume of the volume of the volume of the quality of graphite raw material, 98% concentrated sulfuric acid, 65% concentrated sulfuric acid, the quality of potassium permanganate and hydrogen peroxide preferably adds according to following ratio 1g:85 ~ 95mL:24 ~ 25mL:4 ~ 6g:6 ~ 10mL.
Graphite oxide can form graphene oxide after ultrasonic dispersion.In the mixed solution obtaining, the concentration of graphene oxide is 0.5 ~ 1mg/mL, and the concentration of tin ash is 0.2 ~ 0.5mg/mL.
Step S120, walks the mixed solution obtaining in filtration, obtain the compound of graphene oxide and tin ash.
Step S130, is placed in compound under reproducibility atmosphere, with the heating rates of 15 ℃/min ~ 30 ℃/min, is warming up to 700 ~ 1000 ℃, reacts after 1 ~ 2 hour and obtains Graphene/tin composite material; Wherein, slash "/" represents the compound of Graphene and tin.
In the present embodiment, reproducibility atmosphere adopts the mist atmosphere of reducing gas and protective gas, and wherein, the flow that passes into of protective gas is 300 ~ 400mL/ minute, and the flow-rate ratio of protective gas and reducibility gas is 8 ~ 20:1.Protective gas can be nitrogen or inert gas etc.In other embodiments, reproducibility atmosphere can also be the pure gas atmosphere of reducibility gas.
Adopt slow intensification can guarantee that in Graphene/tin composite material, oxygen content is lower.
In Graphene/tin composite material that present embodiment obtains, 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 is as the positive electrode active materials of lithium ion battery, 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, improve the cycle performance of tin, thus stability in use and the life-span of improving whole battery.
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, general-Graphene/tin composite material, binding agent and conductive agent mix, and obtain positive electrode.
Wherein, binding agent can be Kynoar.
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.
Utilize high-temp in-situ reduction compound, not only can make tin and Graphene mix, and the size of tin particles is less, and can increase substantially the conductivity of Graphene/tin, 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 tin ash, and the technological process of preparing Graphene/tin composite material finally by pyrolysis and reduction is as follows:
Compound → Graphene/the tin composite material of graphite raw material → graphite oxide → graphene oxide and tin ash
Graphite raw material: 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 raw material 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.
The compound of graphene oxide and tin ash: the graphite oxide that upper step is obtained is dispersed in deionized water, the concentration of graphite oxide is 1mg/mL, add afterwards tin ash, the concentration of tin ash is 0.5mg/mL, the ultrasonic machine that is 1000W with power carries out ultrasonic to mixed solution, continue, after 2 hours, to filter, the vacuum drying oven that solid product is placed in to 60 ° of C is dried 12 hours, obtains the compound of graphene oxide and tin ash.
Graphene/tin composite material: the compound obtaining is placed under the mist atmosphere that flow velocity is the hydrogen of 50mL/ minute and the flow velocity argon gas that is 400mL/ minute, with 20 ° of C/ minute heating rates, compound temperature is around risen to 900 ° of C, and keep 1 hour, the last argon gas atmosphere that is 400mL/ minute at flow velocity drops to room temperature, obtains Graphene/tin composite material.
Embodiment 2
The graphite oxide of the present embodiment is through peeling off and mixing with tin ash, and the technological process of preparing Graphene/tin composite material finally by pyrolysis and reduction is as follows:
Compound → Graphene/the tin composite material of graphite raw material → graphite oxide → graphene oxide and tin ash
Graphite raw material: 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 raw material 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 92mL 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 10 hours in 60 ° of C vacuum drying ovens.
The compound of graphene oxide and tin ash: the graphite oxide that upper step is obtained is dispersed in deionized water, the concentration of graphite oxide is 0.5mg/mL, add afterwards tin ash, the concentration of tin ash is 0.5mg/mL, the ultrasonic machine that is 500W with power carries out ultrasonic to mixed solution, continue, after 2 hours, to filter, the vacuum drying oven that solid product is placed in to 60 ° of C is dried 12 hours, obtains the compound of graphene oxide and tin ash.
Graphene/tin composite material: the compound of the graphene oxide obtaining and tin ash is placed under the mist atmosphere that flow velocity is the hydrogen of 30mL/ minute and the flow velocity argon gas that is 300mL/ minute, with 30 ° of C/ minute heating rates, compound temperature is around risen to 800 ° of C, and keep 1 hour, the last argon gas atmosphere that is 300mL/ minute at flow velocity drops to room temperature, obtains Graphene/tin composite material.
Embodiment 3
The graphite oxide of the present embodiment is through peeling off and mixing with tin ash, and the technological process of preparing Graphene/tin composite material finally by pyrolysis and reduction is as follows:
Compound → Graphene/the tin composite material of graphite raw material → graphite oxide → graphene oxide and tin ash
Graphite raw material: 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 raw material concentrated sulfuric acid that to be added to by 425mL 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 250mL 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 400mL watery hydrochloric acid and 600mL 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.
The compound of graphene oxide and tin ash: the graphite oxide that upper step is obtained is dispersed in deionized water, the concentration of graphite oxide is 1mg/mL, add afterwards tin ash, the concentration of tin ash is 0.2mg/mL, the ultrasonic machine that is 800W with power carries out ultrasonic to mixed solution, continue, after 3 hours, to filter, the vacuum drying oven that solid product is placed in to 60 ° of C is dried 12 hours, obtains the compound of graphene oxide and tin ash.
Graphene/tin composite material: the graphene oxide tin ash compound obtaining is placed under the mist atmosphere that flow velocity is the hydrogen of 20mL/ minute and the flow velocity argon gas that is 300mL/ minute, with 15 ° of C/ minute heating rates, compound temperature is around risen to 700 ° of C, and keep 2 hours, the last argon gas atmosphere that is 400mL/ minute at flow velocity drops to room temperature, obtains Graphene/tin composite material.
Embodiment 4
The graphite oxide of the present embodiment is through peeling off and mixing with tin ash, and the technological process of preparing Graphene/tin composite material finally by pyrolysis and reduction is as follows:
Compound → Graphene/the tin composite material of graphite raw material → graphite oxide → graphene oxide and tin ash
Graphite raw material: 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 raw material 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 92mL 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.
The compound of graphene oxide and tin ash: the graphite oxide that upper step is obtained is dispersed in deionized water, the concentration of graphite oxide is 0.5mg/mL, add afterwards tin ash, the concentration of tin ash is 0.4mg/mL, the ultrasonic machine that is 500W with power carries out ultrasonic to mixed solution, continue, after 3 hours, to filter, the vacuum drying oven that solid product is placed in to 60 ° of C is dried 12 hours, obtains the compound of graphene oxide and tin ash.
Graphene/tin composite material: the graphene oxide tin ash compound obtaining is placed under the mist atmosphere that flow velocity is the hydrogen of 20mL/ minute and the flow velocity argon gas that is 400mL/ minute, with 20 ° of C/ minute heating rates, compound temperature is around risen to 1000 ° of C, and keep 1 hour, the last argon gas atmosphere that is 400mL/ minute at flow velocity drops to room temperature, obtains Graphene/tin composite material.
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 1g, 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 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 0.5g, 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, 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 80:10:10, take respectively Graphene/tin composite material of preparing in the embodiment 1 of 8.0g, the Kynoar of 1g and the acetylene black of 1g, 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 83:9:8, take respectively Graphene/tin composite material of preparing in the embodiment 1 of 8.5g, the Kynoar of 0.9g and the acetylene black of 0.8g, 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
Figure BDA00001932540400101
Figure BDA00001932540400111
By upper table 1, can be found out, adopt Graphene/tin composite material prepared by this method to enclose rear capability retention all more than 68% in circulation 300, be up to more than 83%, cyclical stability is better, and higher than traditional tin-based negative electrode materials for lithium-ion battery than electric capacity conservation rate.
Table 2 carries out the stored energy capacitance of charge-discharge test for embodiment 5 ~ 8 under 0.1C and 2C electric current.
Table 2
While adopting Graphene/tin composite material prepared by this method to rise to 2C from 0.1C, capability retention, all more than 65%, is up to 82%, 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 1 ~ 5:1 according to graphite oxide and tin ash mass ratio adds tin ash in described solvent, and ultrasonic dispersion, obtains mixed solution;
Filter described mixed solution, obtain the compound of graphene oxide and tin ash; And
Described compound is placed under reproducibility atmosphere, with the heating rates of 15 ℃/min ~ 30 ℃/min, is warming up to 700 ~ 1000 ℃, react after 1 ~ 2 hour and obtain 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 mixed solution is 0.5 ~ 1mg/mL.
5. the preparation method of Graphene/tin composite material as claimed in claim 1; it is characterized in that; the mist atmosphere that described reproducibility atmosphere is protective gas and reducibility gas; wherein; the flow of described protective gas is 300 ~ 400mL/ minute, and the flow-rate ratio of described protective gas and described reducibility gas is 8 ~ 20:1.
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 1-5.
7. a lithium ion battery, comprises positive pole, and described positive pole comprises collector and be 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, described positive electrode active materials is Graphene/tin composite material claimed in claim 6.
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.
CN201210259414.7A 2012-07-25 2012-07-25 Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery Pending CN103579626A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210259414.7A CN103579626A (en) 2012-07-25 2012-07-25 Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210259414.7A CN103579626A (en) 2012-07-25 2012-07-25 Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery

Publications (1)

Publication Number Publication Date
CN103579626A true CN103579626A (en) 2014-02-12

Family

ID=50050937

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210259414.7A Pending CN103579626A (en) 2012-07-25 2012-07-25 Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery

Country Status (1)

Country Link
CN (1) CN103579626A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104198553A (en) * 2014-09-25 2014-12-10 普旭力 Biosensor sensitive film as well as preparation method and application thereof
CN105552347A (en) * 2016-03-08 2016-05-04 上海中聚佳华电池科技有限公司 Negative material for sodium-ion battery and preparation method for negative material and sodium-ion battery
CN106450231A (en) * 2016-11-29 2017-02-22 中南大学 Preparation method of stannic oxide particle/graphene nano-composite negative electrode material
CN108565410A (en) * 2018-02-09 2018-09-21 中南大学 Lithium ion battery stannic oxide/graphene composite negative pole and preparation method thereof
CN108707998A (en) * 2018-04-11 2018-10-26 杭州牛墨科技有限公司 Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof
CN109904433A (en) * 2019-03-18 2019-06-18 山东星火科学技术研究院 Large capacity fast charging and discharging graphene lithium ion battery and its synthesis technology

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHUZHAO LIANG等: "Superior cycle performance of Sn@C/graphene nanocomposite as an anode material for lithium-ion batteries", 《JOURNAL OF SOLID STATE CHEMISTRY》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104198553A (en) * 2014-09-25 2014-12-10 普旭力 Biosensor sensitive film as well as preparation method and application thereof
CN105552347A (en) * 2016-03-08 2016-05-04 上海中聚佳华电池科技有限公司 Negative material for sodium-ion battery and preparation method for negative material and sodium-ion battery
CN106450231A (en) * 2016-11-29 2017-02-22 中南大学 Preparation method of stannic oxide particle/graphene nano-composite negative electrode material
CN108565410A (en) * 2018-02-09 2018-09-21 中南大学 Lithium ion battery stannic oxide/graphene composite negative pole and preparation method thereof
CN108565410B (en) * 2018-02-09 2020-09-15 中南大学 Tin dioxide/graphene composite negative electrode material of lithium ion battery and preparation method thereof
CN108707998A (en) * 2018-04-11 2018-10-26 杭州牛墨科技有限公司 Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof
CN109904433A (en) * 2019-03-18 2019-06-18 山东星火科学技术研究院 Large capacity fast charging and discharging graphene lithium ion battery and its synthesis technology

Similar Documents

Publication Publication Date Title
US20200373566A1 (en) Composite Negative Electrode Material and Method for Preparing Composite Negative Electrode Material, Negative Electrode Plate of Lithium Ion Secondary Battery, and Lithium Ion Secondary Battery
CN103035890B (en) Silicon and graphene composite electrode material and preparation method thereof
CN102208608B (en) Preparation method of carbon-sulfur composite material for lithium ion battery carbon cathode material
CN103490044B (en) Preparation method of cobalt oxide (II,III)-graphene composite material
CN103078092B (en) A kind of method preparing silicon-carbon composite cathode material of lithium ion battery
CN105762360A (en) Graphene-silicon-coated composite negative electrode material and preparing method and application thereof
CN106450265B (en) A kind of situ Nitrogen Doping carbon coating lithium titanate combination electrode material and preparation method thereof
CN103236530B (en) Si-C composite material and preparation method thereof, lithium ion battery containing this material
CN104064735A (en) Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof
CN108172775A (en) Phosphorus-doped silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN102306757A (en) Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material
CN103515609B (en) THAQ/ graphene composite material, its preparation method, anode and lithium ion battery
CN103579627A (en) Graphene-tin composite material, preparation method of graphene-tin composite material, lithium ion battery and preparation method of lithium ion battery
CN111785949B (en) Modified conductive polymer coated silicon-based negative electrode material, and preparation method and application thereof
CN104269555A (en) Soft carbon anode material for lithium-ion power and energy storage battery as well as preparation method and application of soft carbon anode material
CN103579626A (en) Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery
CN106960954A (en) A kind of preparation method and application of Prussian blue/graphene/sulphur composite
CN110148730A (en) High-first-efficiency long-life silicon-based negative electrode material and preparation method and application thereof
CN103490040A (en) Preparation method of lithium titanate-graphene composite material
CN104282894B (en) A kind of preparation method of porous Si/C complex microsphere
CN105161690B (en) The method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide
CN104064755B (en) Cobaltosic oxide-graphene-carbon nano tube composite material and its preparation method and application
CN103456937A (en) Preparation methods of lithium titanate-graphene composite material and lithium ion battery
CN103515604A (en) Silicon nanowire-graphene composite and preparation method thereof, and lithium ion battery
CN103050692A (en) Preparation method of grapheme-lithium manganese silicate anode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140212

WD01 Invention patent application deemed withdrawn after publication