CN109534318A - A kind of graphene preparation method in battery - Google Patents

A kind of graphene preparation method in battery Download PDF

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Publication number
CN109534318A
CN109534318A CN201811442139.6A CN201811442139A CN109534318A CN 109534318 A CN109534318 A CN 109534318A CN 201811442139 A CN201811442139 A CN 201811442139A CN 109534318 A CN109534318 A CN 109534318A
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graphene
oxide
preparation
solution
battery
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CN201811442139.6A
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王圣婴
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Beijing Holy Alliance Technology Co Ltd
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Beijing Holy Alliance Technology Co Ltd
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Priority to CN201811442139.6A priority Critical patent/CN109534318A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention proposes a kind of graphene preparation methods in battery, and specific step is as follows, and the preparation of (1) graphene oxide solution: using natural flake graphite for raw material, prepare graphite oxide by modified Hummers method;By the graphite oxide of preparation ultrasonic disperse in water, after centrifugation removes unstripped graphite, graphene oxide solution is prepared;(2) graphene oxide solution cold quenching in liquid nitrogen: by graphene oxide solution and the Fe for being added to surfactant3O4Heating is put into cold quenching in liquid nitrogen after boiling after solution combined ultrasound, until freeze completely, it is dry then to be carried out In-situ condensation, obtains stannic oxide/graphene nano and rolls up;(3) stannic oxide/graphene nano volume reduction: by dry stannic oxide/graphene nano volume heating reduction or electronation, to obtain graphene nano volume composite material.The inventive method is simple and easy to control, and short preparation period is, it can be achieved that prepared by the inexpensive magnanimity of graphene-based composite material.

Description

A kind of graphene preparation method in battery
Technical field
The present invention relates to graphene apparatus fields, particularly relate to a kind of graphene preparation method in battery.
Background technique
Graphene has excellent electricity and mechanical property, it is expected in lithium-ion electric as a kind of Novel Carbon Nanomaterials Obtained in pond using.But graphene can not be used alone due to itself not having apparent voltage platform, and by its with it is traditional Metal oxide negative electrode material is compound, can get the electrode material for having both height ratio capacity and high stability.Currently, graphene and gold Belonging to the compound mode of oxide, there are many kinds, but composite construction is mostly loose, and the mechanism study in relation to its compound interface is even more It is relatively fewer.
Therefore, using the composite material of graphene and ferroso-ferric oxide as research object, with the structure in different composite constructions Building the stabilization chemical interface between graphene and metal oxide is research purpose, improves metal oxidation by surfactant The zeta current potential on object surface, and then change the property of itself and graphene contact interface, it realizes between graphene and metal oxide Stablize constructing for chemical interface, to improve the electric conductivity of electrode material, improves the high rate performance of composite material, obtaining has very The lithium ion battery negative material of good high rate performance and cyclical stability.
Summary of the invention
The present invention proposes a kind of graphene preparation method in battery, and this method is at low cost, process is simple, achievable Large-scale production.
The technical scheme of the present invention is realized as follows:
A kind of graphene preparation method in battery, the specific steps are as follows:
(1) preparation of graphene oxide solution: using natural flake graphite for raw material, passes through modified Hummers method preparation Graphite oxide;By the graphite oxide of preparation, ultrasonic disperse prepares graphene oxide after centrifugation removes unstripped graphite in water Solution;
(2) graphene oxide solution cold quenching in liquid nitrogen: by graphene oxide solution that step (1) obtains and it is added to table The Fe of face activating agent3O4It is heated after solution combined ultrasound, obtains mixed solution;Until above-mentioned mixed solution is put into liquid nitrogen after boiling Then cold quenching is carried out In-situ condensation drying until being drawn off after freezing completely, obtain stannic oxide/graphene nano volume;
(3) dry stannic oxide/graphene nano volume stannic oxide/graphene nano volume reduction: is passed through into heating reduction or chemistry The mode of reduction removes oxygen-containing functional group therein, to obtain graphene nano volume composite material.
Preferably, 100 μm of natural flake graphite graphite size > in the step (1).
Preferably, when modified Hummers method prepares graphite oxide in the step (1), oxidizing temperature is 0~90 DEG C, oxygen The change time is 1~10h.
Preferably, when modified Hummers method prepares graphite oxide in the step (1), oxidizing temperature is 0~35 DEG C, oxygen Changing the time is preferably 2~4h.
Preferably, the time ultrasonic in the step (1) is 20s~1h, and power is 50~600W;The revolving speed of centrifugation is 1000~7000rmp, centrifugation time are 1~30min.
Preferably, the time ultrasonic in the step (1) is preferably 20s~15min, and ultrasonic power is preferably 400 ~600W;The revolving speed of centrifugation is 3000~6000rmp, and centrifugation time is 5~15min.
Preferably, the concentration of graphene oxide solution needed for liquid nitrogen cold quenching is 0.5~8mg/ml in the step (2);Institute Stating surfactant is anionic surfactant, and concentration is 0.05~5mg/ml;Graphene oxide solution and Fe3O4Solution The temperature heated after composite ultraphonic is 0~100 DEG C;The In-situ condensation drying time is 8~40h.
Preferably, the concentration of graphene oxide solution needed for liquid nitrogen cold quenching is 1~3mg/ml in the step (2), described Surfactant is anionic surfactant, and concentration is 0.01~2mg/ml, graphene oxide solution and Fe3O4Solution is multiple Closing the temperature heated after ultrasound is 80~100 DEG C;The In-situ condensation drying time is 10~20h.
Preferably, the heating temperature of heating reduction is 300~900 DEG C in the step (3), and electronation is hydrazine hydrate steaming Vapour reduction, the time of electronation are 8~40h.
Preferably, the time of step (3) electronation is 8~16h.
The present invention provides a kind of method for preparing nanometer roll by graphene under liquid nitrogen environment, this method uses large scale Natural flake graphite is raw material, is aoxidized using modified Hummers method to graphite, it is molten to prepare large-sized graphene oxide Liquid, by graphene oxide solution and the graphene oxide solution Hybrid Heating for being added to anionic surfactant, then in liquid Cold quenching is carried out in nitrogen, prepares the charcoal nanometer roll of oxidation, and charcoal nanometer roll then will be aoxidized by way of heating or electronation It is restored, to prepare graphene nano volume.Graphene nano volume and metal oxide progress is compound, and by containing The surfactant of oxygen functional group modifies oxide, and then is formed in conjunction with the oxygen-containing functional group of surface of graphene oxide Oxygen bridge structure improves the capacity and cyclical stability of its lithium ion battery to construct more stable chemical interface.
The invention has the benefit that
The present invention uses large scale natural flake graphite, prepares graphene oxide solution using modified Hummers method, leads to The mode of graphene oxide solution cold quenching in liquid nitrogen by the graphene oxide of heating and addition anionic surfactant is crossed, Preparation oxidation charcoal nanometer roll, and the charcoal nanometer roll composite material of magnanimity, present invention reaction are obtained using In-situ condensation dry technology Process control, simple process, short preparation period, at low cost and to prepare charcoal nanometer roll quality high, can be expected to realize graphene nano Roll up the magnanimity preparation of composite material.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without creative efforts belongs to the model that the present invention protects It encloses.
Embodiment 1
(1) graphite oxide is prepared using modified Hummers method using 32 mesh natural flake graphites, crystalline flake graphite is 35 DEG C, prepare graphite oxide under conditions of 2h, graphite oxide is dispersed in water, the ultrasonic time is 10min, and ultrasonic power is Then 600W removes visible particles by centrifugal rotational speed 3000rpm, obtains graphene oxide solution;
(2) Fe is prepared using solvent-thermal method3O4: 1.35g FeCl first3·6H2O is dissolved in the ethylene glycol of 25ml, and It is stirred;Then the sodium acetate of 2.7g and the trisodium citrate of 1.0g, stirring are added thereto;Mixed solution is transferred to In the polytetrafluoro reaction kettle of 50ml, 200 DEG C of hydro-thermal, 10h is reacted.After being cooled to room temperature, reaction kettle is opened, sediment is used Ethyl alcohol and distilled water clean for several times repeatedly, then dry in 25 DEG C of vacuum oven, it is dry after both available Fe3O4It receives Rice grain;
The graphene oxide solution and 1mg/ml Fe for being 1mg/ml by concentration3O4After solution ULTRASONIC COMPLEX 30min, it is heated to It is put into cold quenching in liquid nitrogen after in 100 DEG C of merging test tubes, until solution freezes completely, In-situ condensation drying is then carried out, done Stannic oxide/graphene nano volume is obtained after dry;
(3) stannic oxide/graphene nano volume is subjected to 500 DEG C of reduction under Ar gas shielded again, to obtain graphene nano volume Composite material.
Graphene and the iron oxide package of the present embodiment 1 are obvious, but iron oxide Aggregate size distribution is uneven, graphene It is thicker to wrap up lamella.
Embodiment 2
Graphene oxide solution and Fe3O4The preparation method is the same as that of Example 1 for nano particle.
The Fe for being 1mg/ml by concentration3O4Nano particle is surface modified using the citric acid three sodium solution of 0.5mg/ml Afterwards, by the Fe of the graphene oxide solution of 1mg/ml and 1mg/ml3O4After solution ULTRASONIC COMPLEX 30min, it is heated to 100 DEG C of mergings It is put into cold quenching in liquid nitrogen after in test tube, until solution freezes completely, is then carried out In-situ condensation dry heat and set to 100 DEG C It is put into cold quenching in liquid nitrogen after entering in test tube, until solution freezes completely, is then carried out In-situ condensation drying, is obtained after dry Stannic oxide/graphene nano roll of material, then 500 DEG C of reduction under Ar gas shielded by it, so that it is multiple to obtain graphene nano volume iron oxide Condensation material.
Originally be strength 2 graphene roll knee-piece layer it is less, and Fe3O4Aggregation size is distributed within the scope of 80~100nm It is even.
Embodiment 3
Graphene oxide solution and Fe3O4The preparation method is the same as that of Example 1 for nano particle.
The Fe for being 1mg/ml by concentration3O4After nano particle is surface modified using the citric acid three sodium solution of 1mg/ml, By the Fe of the graphene oxide solution of 1mg/ml and 1mg/ml3O4After solution ULTRASONIC COMPLEX 30min, it is heated to 100 DEG C of merging test tubes In after be put into cold quenching in liquid nitrogen, until solution freezes completely, then carried out In-situ condensation dry heat to 100 DEG C of mergings and tried Guan Zhonghou is put into cold quenching in liquid nitrogen, until solution freezes completely, is then carried out In-situ condensation drying, is aoxidized after dry Graphene nano volume, then 500 DEG C of reduction under Ar protection by it, to obtain graphene nano volume ferric oxide composite material.
The graphene roll knee-piece layer of the present embodiment 3 is less, and Fe3O4Aggregation size is distributed within the scope of 80~120nm It is even.
Embodiment 4
Graphene oxide solution and Fe3O4The preparation method is the same as that of Example 1 for nano particle.
The Fe for being 1mg/ml by concentration3O4After nano particle is surface modified using the citric acid three sodium solution of 2mg/ml, By the Fe of the graphene oxide solution of 1mg/ml and 1mg/ml3O4After solution ULTRASONIC COMPLEX 30min, it is heated to 100 DEG C of merging test tubes In after be put into cold quenching in liquid nitrogen, until solution freezes completely, then carried out In-situ condensation dry heat to 100 DEG C of mergings and tried Guan Zhonghou is put into cold quenching in liquid nitrogen, until solution freezes completely, is then carried out In-situ condensation drying, is aoxidized after dry Graphene nano volume, then 500 DEG C of reduction under Ar protection by it, to obtain graphene nano volume ferric oxide composite material.
The graphene roll knee-piece layer of the present embodiment 4 is less, and Fe3O4Aggregation size is distributed within the scope of 100~150nm Uniformly.
Embodiment 5
Graphene oxide solution and Fe3O4The preparation method is the same as that of Example 1 for nano particle.
The Fe for being 1mg/ml by concentration3O4Nano particle carries out table using the neopelex (SDBS) of 1mg/ml After the modification of face, by the Fe of the graphene oxide solution of 1mg/ml and 1mg/ml3O4After solution ULTRASONIC COMPLEX 30min, it is heated to 100 It is put into cold quenching in liquid nitrogen after in DEG C merging test tube, until solution freezes completely, is then carried out In-situ condensation dry heat extremely It is put into cold quenching in liquid nitrogen after in 100 DEG C of merging test tubes, until solution freezes completely, In-situ condensation drying is then carried out, done Stannic oxide/graphene nano volume, then 500 DEG C of reduction under Ar protection by it are obtained after dry, to obtain graphene nano volume iron oxide Composite material.
The graphene nano volume structure dispersion of the present embodiment 5 is more uniform, and Fe3O4Aggregation size is in 80~200nm model It is evenly distributed in enclosing.
Embodiment 6
Graphene oxide solution and Fe3O4The preparation method is the same as that of Example 1 for nano particle.
The Fe for being 1mg/ml by concentration3O4Nano particle using 1mg/ml cetyl trimethylammonium bromide (CTAB) into It goes after surface modification, by the Fe of the graphene oxide solution of 1mg/ml and 1mg/ml3O4After solution ULTRASONIC COMPLEX 30min, it is heated to It is put into cold quenching in liquid nitrogen after in 100 DEG C of merging test tubes, until solution freezes completely, is then carried out In-situ condensation dry heat It is put into cold quenching in liquid nitrogen after into 100 DEG C of merging test tubes, until solution freezes completely, is then carried out In-situ condensation drying, Stannic oxide/graphene nano volume, then 500 DEG C of reduction under Ar protection by it are obtained after drying, to obtain graphene nano volume oxidation Iron composite material.
The graphene sheet layer of the present embodiment 6 stacks obviously, and Fe3O4Aggregation size size has big difference, graphene nano Volume is to Fe3O4Obvious variation wrapped.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of graphene preparation method in battery, which is characterized in that specific step is as follows:
(1) preparation of graphene oxide solution: using natural flake graphite for raw material, passes through modified Hummers method preparation oxidation Graphite;By the graphite oxide of preparation, it is molten to prepare graphene oxide after centrifugation removes unstripped graphite for ultrasonic disperse in water Liquid;
(2) graphene oxide solution cold quenching in liquid nitrogen: the graphene oxide solution that step (1) obtains is lived with surface is added to The Fe of property agent3O4It is heated after solution combined ultrasound, obtains mixed solution;Until above-mentioned mixed solution is put into cold quenching in liquid nitrogen after boiling, Until being drawn off after freezing completely, In-situ condensation drying is then carried out, obtains stannic oxide/graphene nano volume;
(3) dry stannic oxide/graphene nano volume stannic oxide/graphene nano volume reduction: is passed through into heating reduction or electronation Mode oxygen-containing functional group therein is removed, thus obtain graphene nano volume composite material.
2. a kind of graphene preparation method in battery as described in claim 1, which is characterized in that the step (1) Middle 100 μm of natural flake graphite graphite size >.
3. a kind of graphene preparation method in battery as described in claim 1, which is characterized in that the step (1) When middle modified Hummers method prepares graphite oxide, oxidizing temperature is 0~90 DEG C, and oxidization time is 1~10h.
4. a kind of graphene preparation method in battery as claimed in claim 3, which is characterized in that the step (1) When middle modified Hummers method prepares graphite oxide, oxidizing temperature is 0~35 DEG C, and oxidization time is preferably 2~4h.
5. a kind of graphene preparation method in battery as described in claim 1, which is characterized in that the step (1) The time of middle ultrasound is 20s~1h, and power is 50~600W;The revolving speed of centrifugation be 1000~7000rmp, centrifugation time be 1~ 30min。
6. a kind of graphene preparation method in battery as claimed in claim 5, which is characterized in that the step (1) The time of middle ultrasound is preferably 20s~15min, and ultrasonic power is preferably 400~600W;The revolving speed of centrifugation be 3000~ 6000rmp, centrifugation time are 5~15min.
7. a kind of graphene preparation method in battery as described in claim 1, which is characterized in that the step (2) The concentration of graphene oxide solution needed for middle liquid nitrogen cold quenching is 0.5~8mg/ml;The surfactant is living for anionic surface Property agent, concentration be 0.05~5mg/ml;Graphene oxide solution and Fe3O4After solution combined ultrasound the temperature that heats be 0~ 100℃;The In-situ condensation drying time is 8~40h.
8. a kind of graphene preparation method in battery as claimed in claim 7, which is characterized in that the step (2) The concentration of graphene oxide solution needed for middle liquid nitrogen cold quenching is 1~3mg/ml, and the surfactant is anion surface active Agent, concentration are 0.01~2mg/ml, graphene oxide solution and Fe3O4The temperature heated after solution combined ultrasound is 80~100 ℃;The In-situ condensation drying time is 10~20h.
9. a kind of graphene preparation method in battery as described in claim 1, which is characterized in that the step (3) The heating temperature of middle heating reduction is 300~900 DEG C, and electronation is hydrazine hydrate steam reduction, time of electronation is 8~ 40h。
10. a kind of graphene preparation method in battery as claimed in claim 9, which is characterized in that the step (3) The time of electronation is 8~16h.
CN201811442139.6A 2018-11-29 2018-11-29 A kind of graphene preparation method in battery Pending CN109534318A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110323443A (en) * 2019-05-27 2019-10-11 北京理工大学 A kind of spherical N doping redox graphene material and its application
CN110451497A (en) * 2019-08-26 2019-11-15 上海利物盛纳米科技有限公司 A kind of method of quick free from admixture redox graphene
CN111252760A (en) * 2020-01-22 2020-06-09 哈尔滨工业大学 Preparation method of graphene oxide nano roll and composite material thereof
CN112340842A (en) * 2020-10-09 2021-02-09 神美科技有限公司 Preparation method of denitrification solid carbon source
CN112436111A (en) * 2020-10-26 2021-03-02 滨州双峰石墨密封材料有限公司 Preparation method and application of graphene modified nickel oxide nanocomposite
CN114284635A (en) * 2021-12-28 2022-04-05 厦门大学 Diaphragm modification method for lithium metal negative electrode protection

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106531990A (en) * 2016-11-07 2017-03-22 北京圣盟科技有限公司 Preparation method for graphene composite electrode material for lithium ion battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106531990A (en) * 2016-11-07 2017-03-22 北京圣盟科技有限公司 Preparation method for graphene composite electrode material for lithium ion battery

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110323443A (en) * 2019-05-27 2019-10-11 北京理工大学 A kind of spherical N doping redox graphene material and its application
CN110451497A (en) * 2019-08-26 2019-11-15 上海利物盛纳米科技有限公司 A kind of method of quick free from admixture redox graphene
CN111252760A (en) * 2020-01-22 2020-06-09 哈尔滨工业大学 Preparation method of graphene oxide nano roll and composite material thereof
CN111252760B (en) * 2020-01-22 2021-01-05 哈尔滨工业大学 Preparation method of graphene oxide nano roll and composite material thereof
CN112340842A (en) * 2020-10-09 2021-02-09 神美科技有限公司 Preparation method of denitrification solid carbon source
CN112436111A (en) * 2020-10-26 2021-03-02 滨州双峰石墨密封材料有限公司 Preparation method and application of graphene modified nickel oxide nanocomposite
CN114284635A (en) * 2021-12-28 2022-04-05 厦门大学 Diaphragm modification method for lithium metal negative electrode protection

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