CN108232166A - A kind of graphene battery - Google Patents
A kind of graphene battery Download PDFInfo
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- CN108232166A CN108232166A CN201810050246.8A CN201810050246A CN108232166A CN 108232166 A CN108232166 A CN 108232166A CN 201810050246 A CN201810050246 A CN 201810050246A CN 108232166 A CN108232166 A CN 108232166A
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- 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
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- 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
- H01M4/386—Silicon or alloys based on silicon
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- 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
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Abstract
The invention discloses a kind of graphene batteries, it is characterized in that, it is formed after being laminated by anode pole piece, semiconductor and cathode pole piece, the anode pole piece is in strip, and section is elliptic cross-section, the anode pole piece has at least three pieces, and it is set in qually spaced in semiconductor forepart in non-, the cathode pole piece has a piece of, is square, rectangular cross-section is attached to the rear portion of the semiconductor；The anode pole piece includes positive pole aluminium foil collector and is located at the LiFePO4 active material layer of the positive pole aluminium foil collector inner surface；Gel-type electrolyte liquid is brushed on the LiFePO4 active material layer, to form electrolyte layer.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of graphene batteries.
Background technology
With the development of human society, people are increasing to the demand of the energy, the fossils energy such as coal, oil, natural gas
Source is still the main body of current energy supply, but fossil energy is non-renewable energy resources, and the mouth benefit exhaustion of fossil energy is the mankind
A major challenge that social development faces.These fuel are also the main source of environmental pollution simultaneously, are found novel reproducible clear
The clean energy becomes the theme of the world today.Electrochmical power source substitute original fossil energy can effectively alleviate energy problem and
The development of problem of environmental pollution, wherein secondary power supply effectively advances the development of electrochmical power source.It is small-sized with electronic device
Change, the demand to the high-capacity power supply of portable multifunctional gradually increases, clang ion battery since its excellent performance takes off grain husk and
Go out, become the main Types in secondary power supply.
Graphene has excellent electronic conductivity, big specific surface area（2600 m2/g）, good thermal property and machine
Tool property becomes the multi-field research hotspot such as the energy, chemical industry, biology.In storage lithium aspect of performance, the theoretical of graphene holds
Amount reaches 744 mAh/g, better than graphite（Theoretical capacity：372mAh/g）, and graphene can increase the binding site with clang, make
Obtaining graphene becomes one of the selection of substitution graphite as clang ion negative material.But research shows that simple graphene conduct
Clang ion battery cathode material there are it is certain the defects of, such as:Irreversible degree is big in cyclic process for the first time, and capacitance loss is more,
Coulombic efficiency is low etc. in following cycle, so becoming optimization graphene negative material with the compound composite material for preparing of other materials
Prefered method.However in charge and discharge process, the removal lithium embedded of silicon reacts the acute variation along with silicon volume（>300%）, cause
Inside battery high pressure, causes electrode to crush, and active material comes off so that electrode cycle penalty, battery capacity drastically drop
It is low.
Invention content
The purpose of the present invention is to solve shortcoming in the prior art, and a kind of graphene battery proposed.
To achieve these goals, present invention employs following technical solutions：A kind of graphene battery, which is characterized in that
It being formed after being laminated by anode pole piece, semiconductor and cathode pole piece, the anode pole piece is in strip, and section is elliptic cross-section,
The anode pole piece has an at least three pieces, and is set in qually spaced in semiconductor forepart in non-, the cathode pole piece have it is a piece of,
It is square, rectangular cross-section is attached to the rear portion of the semiconductor；The thickness of the anode pole piece, multi-lager semiconductor and cathode pole piece
It is 1 to spend ratio:3:2；The anode pole piece includes positive pole aluminium foil collector and is located at the positive pole aluminium foil collector inner surface
LiFePO4 active material layer；Gel-type electrolyte liquid is brushed on the LiFePO4 active material layer, to form electrolyte layer；
Gel-type electrolyte liquid includes：The safe electrolyte of 28 mass parts, the trifluoromethanesulp-onyl -onyl imide ionic liquid of 37 mass parts, 35 matter
Measure the polyethylene glycol methacrylate polymers of part；The safe electrolyte includes the conventional electrolysis liquid of 87 mass parts, 8
The triphenyl phosphate of mass parts and the fluoromethane of 5 mass parts are for butyl ether；The semiconductor is close to the electrolyte layer；It is described negative
Pole pole piece is composite material, is obtained in graphene surface successively carbon coated and silicon carbide, wherein, graphene, carbon and silicon carbide
Mass ratio be 0.5: 0.03: 0.3；The preparation method of the cathode pole piece composite material is as follows：(1) dispersed graphite alkene：Graphite
Alkene is dispersed under the action of Emulsifier EL-60 in ethylene glycol；(2) carbon coated：By dispersed graphite obtained by step (1)
Alkene is added in organic carbon source aqueous solution, is stirred 5 hours, then after 156 DEG C are continued stirring evaporation solvent, in 780 DEG C of high temperature pyrolysis
10 hours to get carbon-coated graphene；(3) silicon carbide is coated：By graphene one carbon-coated obtained by silicon carbide and step (1)
Be placed in grinding in ball mill, by gained powder be placed in tube furnace heat roast, then with stove be down to room temperature to get.
Preferably, the silicon carbide in step (3) is prepared by the following method to obtain：(31) silicon carbide precursor is prepared
Body；(32) silicon carbide precursor is warming up to 1500~1550 under helium atmosphere protection with the heating rate of 18~20 DEG C/min
DEG C, 10~12 hours are kept the temperature, cooled to room temperature obtains blackish green initial stage silicon carbide；It (33) will be first obtained by step (32)
Phase silicon carbide is added in the hydrofluoric acid solution of mass concentration 35%, removes unreacted silica, is washed, and is filtered, drying, i.e.,
.
Preferably, the cathode pole piece can also be negative electrode active material, the anode active material layer (142) it is main
Ingredient is silicon/charcoal-graphene composite material；Silicon/charcoal-the graphene composite material is prepared as steps described below：By silicon
Powder is placed in ultra-fine ball mill, and using water as medium, ball material mass ratio is 4:1, ball milling 10h obtain silicon slurry；By the silicon slurry
With Delanium, conductive black, emulsified asphalt according to 65:20:5:10 mass ratio is uniformly mixed, and obtains mixture；To described
Mixture carries out spray drying treatment, obtains spherical particle；
By the spherical particle and graphene oxide according to 2:1 mass ratio mixes, and under the rotating speed of 1000r/min, stirring 2-3 is small
When；The spherical particle after stirring and the mixture of graphene oxide are placed in the nitrogen environment that temperature is 900 DEG C and are sintered 2
Hour, obtain silicon/charcoal-graphene composite material.
A kind of graphene battery provided by the invention, compared with prior art, the present invention is using with using safety
Gel-type electrolyte liquid, mobility is suitable, is easy to be brushed on anode pole piece, is in close contact with LiFePO4 active material layer；
As negative electrode active material, silicon/charcoal-graphene composite material has huge specific surface area and capacity, and high conductivity is being answered
During for graphene lithium ion battery so that battery has the advantages such as high conductivity, high power capacity, superior performance.The stone of the present invention
Black alkene battery cathode composite material has higher coulombic efficiency for the first time, reduces positive electrode dosage, thereby reduces entire
The cost of battery.The present invention is in graphene surface successively carbon coated and silicon carbide, gained graphene battery anode material
There is high power capacity and high circulation stability.The graphene dispersion that preparation method of the present invention is related to, using polyoxyethylene castor
Sesame oil passes through and the dosage of dispersant is controlled to realize the homodisperse of graphene as dispersant, improves electric property.
Using the graphene battery, super-pressure is can be resistant to, improves its scope of application and application space.
Description of the drawings
Fig. 1 is the structural diagram of the present invention；
Fig. 2 is the schematic cross-section of this present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
The present invention provides a kind of graphene batteries as shown in Figs. 1-2, which is characterized in that by anode pole piece 1, semiconductor
2 and cathode pole piece 3 be laminated after form, the anode pole piece 1 be in strip, section is elliptic cross-section, and the anode pole piece 1 has
There are an at least three pieces, and semiconductor forepart is set in qually spaced in non-, the cathode pole piece 3 has a piece of, is square, section is
Rectangle is attached to the rear portion of the semiconductor 2；The thickness ratio of the anode pole piece, multi-lager semiconductor and cathode pole piece is 1:3:
2；The anode pole piece 1 includes positive pole aluminium foil collector and is located at the LiFePO4 work of the positive pole aluminium foil collector inner surface
Property material layer；Gel-type electrolyte liquid is brushed on the LiFePO4 active material layer, to form electrolyte layer；Gel-type electrolyte liquid
Including：The safe electrolyte of 28 mass parts, the trifluoromethanesulp-onyl -onyl imide ionic liquid of 37 mass parts, 35 mass parts polyethylene
Glycolmethacrylate polymer；The phosphoric acid of conventional electrolysis liquid of the safe electrolyte including 87 mass parts, 8 mass parts
Triphenylmethyl methacrylate and the fluoromethane of 5 mass parts are for butyl ether；The semiconductor is close to the electrolyte layer；The cathode pole piece is compound
Material is obtained in graphene surface successively carbon coated and silicon carbide, wherein, the mass ratio of graphene, carbon and silicon carbide is 0.5
∶0.03∶0.3；The preparation method of the cathode pole piece composite material is as follows：(1) dispersed graphite alkene：Graphene is in polyoxyethylene castor
It is dispersed in ethylene glycol under the action of sesame oil；(2) carbon coated：Dispersed graphite alkene obtained by step (1) is added in into organic carbon source
It in aqueous solution, stirs 5 hours, then after 156 DEG C are continued stirring evaporation solvent, in 780 DEG C of high temperature pyrolysis 10 hours to get carbon packet
The graphene covered；(3) silicon carbide is coated：Graphene one carbon-coated obtained by silicon carbide and step (1) is placed in ball mill
Grinding, by gained powder be placed in tube furnace heat roast, then with stove be down to room temperature to get.
Preferably, the silicon carbide in step (3) is prepared by the following method to obtain：(31) silicon carbide precursor is prepared
Body；(32) silicon carbide precursor is warming up to 1500~1550 under helium atmosphere protection with the heating rate of 18~20 DEG C/min
DEG C, 10~12 hours are kept the temperature, cooled to room temperature obtains blackish green initial stage silicon carbide；It (33) will be first obtained by step (32)
Phase silicon carbide is added in the hydrofluoric acid solution of mass concentration 35%, removes unreacted silica, is washed, and is filtered, drying, i.e.,
.
Preferably, the cathode pole piece 3 can also be negative electrode active material, the master of the anode active material layer (142)
It is silicon/charcoal-graphene composite material to want ingredient；Silicon/charcoal-the graphene composite material is prepared as steps described below：It will
Silica flour is placed in ultra-fine ball mill, and using water as medium, ball material mass ratio is 4:1, ball milling 10h obtain silicon slurry；The silicon is starched
Material is with Delanium, conductive black, emulsified asphalt according to 65:20:5:10 mass ratio is uniformly mixed, and obtains mixture；To institute
It states mixture and carries out spray drying treatment, obtain spherical particle；
By the spherical particle and graphene oxide according to 2:1 mass ratio mixes, and under the rotating speed of 1000r/min, stirring 2-3 is small
When；The spherical particle after stirring and the mixture of graphene oxide are placed in the nitrogen environment that temperature is 900 DEG C and are sintered 2
Hour, obtain silicon/charcoal-graphene composite material.
In summary：Compared with prior art, the present invention is using with using safe gel-type electrolyte liquid, mobility
It is suitable, it is easy to be brushed on anode pole piece, is in close contact with LiFePO4 active material layer；As negative electrode active material, silicon/
Charcoal-graphene composite material has huge specific surface area and capacity, high conductivity, applied to graphene lithium ion battery
When so that battery has the advantages such as high conductivity, high power capacity, superior performance.The graphene battery anode material of the present invention
With higher coulombic efficiency for the first time, positive electrode dosage is reduced, thereby reduces the cost of entire battery.The present invention exists
There is graphene surface high power capacity and high circulation to stablize for carbon coated and silicon carbide, gained graphene battery anode material successively
The features such as property.The graphene dispersion that preparation method of the present invention is related to using Emulsifier EL-60 as dispersant, and passes through
The dosage of control dispersant realizes the homodisperse of graphene, improves electric property.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (3)
1. a kind of graphene battery, which is characterized in that by anode pole piece, semiconductor and cathode pole piece be laminated after form, it is described just
Pole pole piece is in strip, and section is elliptic cross-section, and the anode pole piece has at least three pieces, and is set in qually spaced in half in non-
Conductor forepart, the cathode pole piece have a piece of, are square, rectangular cross-section is attached to the rear portion of the semiconductor；It is described just
The thickness ratio of pole pole piece, multi-lager semiconductor and cathode pole piece is 1:3:2；The anode pole piece include positive pole aluminium foil collector and
It is located at the LiFePO4 active material layer of the positive pole aluminium foil collector inner surface；It is brushed on the LiFePO4 active material layer
Gel-type electrolyte liquid is applied, to form electrolyte layer；Gel-type electrolyte liquid includes：The safe electrolyte of 28 mass parts, 37 mass parts
Trifluoromethanesulp-onyl -onyl imide ionic liquid, 35 mass parts polyethylene glycol methacrylate polymers；The safety
Electrolyte includes the fluoromethane of the conventional electrolysis liquid of 87 mass parts, the triphenyl phosphate of 8 mass parts and 5 mass parts for butyl ether；
The semiconductor is close to the electrolyte layer；The cathode pole piece is composite material, be in graphene surface successively carbon coated and
Silicon carbide and obtain, wherein, the mass ratio of graphene, carbon and silicon carbide is 0.5: 0.03: 0.3；The cathode pole piece composite material
Preparation method it is as follows：(1) dispersed graphite alkene：Graphene is dispersed in ethylene glycol under the action of Emulsifier EL-60
In；(2) carbon coated：Dispersed graphite alkene obtained by step (1) is added in organic carbon source aqueous solution, is stirred 5 hours, then at 156 DEG C
After continuing stirring evaporation solvent, in 780 DEG C of high temperature pyrolysis 10 hours to get carbon-coated graphene；(3) silicon carbide is coated：It will
Silicon carbide is placed in grinding in ball mill with carbon-coated graphene one obtained by step (1), and gained powder is placed in tube furnace
Heating roasting, then with stove be down to room temperature to get.
2. novel graphite alkene battery according to claim 1, the silicon carbide in step (3) is to be prepared by the following method
It arrives：(31) silicon carbide precursor is prepared；(32) silicon carbide precursor is under helium atmosphere protection, with the liter of 18~20 DEG C/min
Warm rate is warming up to 1500~1550 DEG C, keeps the temperature 10~12 hours, cooled to room temperature, obtains blackish green initial stage carbonization
Silicon；(33) initial stage silicon carbide obtained by step (32) is added in the hydrofluoric acid solution of mass concentration 35%, removes unreacted two
Silica, wash, filtering, dry to get.
3. graphene battery according to claim 1, the cathode pole piece can also be negative electrode active material, the cathode
The main component of active material layer (142) is silicon/charcoal-graphene composite material；Silicon/charcoal-the graphene composite material according to
Following step is prepared：Silica flour is placed in ultra-fine ball mill, using water as medium, ball material mass ratio is 4:1, ball milling 10h,
Obtain silicon slurry；By the silicon slurry and Delanium, conductive black, emulsified asphalt according to 65:20:5:10 mass ratio mixing
Uniformly, mixture is obtained；Spray drying treatment is carried out to the mixture, obtains spherical particle；By the spherical particle and oxygen
Graphite alkene is according to 2:1 mass ratio mixes, and under the rotating speed of 1000r/min, stirs 2-3 hours；It will be described spherical after stirring
The mixture of particle and graphene oxide is placed in the nitrogen environment that temperature is 900 DEG C and is sintered 2 hours, obtains silicon/charcoal-graphene
Composite material.
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| CN201810050246.8A CN108232166A (en) | 2018-01-18 | 2018-01-18 | A kind of graphene battery |
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| CN201810050246.8A CN108232166A (en) | 2018-01-18 | 2018-01-18 | A kind of graphene battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421037A (en) * | 2020-11-04 | 2021-02-26 | 成都新柯力化工科技有限公司 | Hydrophobic NCA positive electrode material of lithium battery and preparation method |
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| CN105576242A (en) * | 2016-03-08 | 2016-05-11 | 黑龙江聚拢华玺智能科技有限公司 | Graphene battery |
| CN206250304U (en) * | 2016-07-26 | 2017-06-13 | 上海航天工业（集团）有限公司 | Ternary high-energy-density electrokinetic cell and power battery module |
| CN107180954A (en) * | 2017-05-24 | 2017-09-19 | 张廷祥 | A kind of ultra-thin graphite alkene lithium ion single battery and graphene lithium ion battery group |
| CN107507967A (en) * | 2017-07-13 | 2017-12-22 | 贵州鼎玺烯材高科技有限公司 | A kind of graphene battery anode material |
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2018
- 2018-01-18 CN CN201810050246.8A patent/CN108232166A/en not_active Withdrawn
Patent Citations (4)
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|---|---|---|---|---|
| CN105576242A (en) * | 2016-03-08 | 2016-05-11 | 黑龙江聚拢华玺智能科技有限公司 | Graphene battery |
| CN206250304U (en) * | 2016-07-26 | 2017-06-13 | 上海航天工业（集团）有限公司 | Ternary high-energy-density electrokinetic cell and power battery module |
| CN107180954A (en) * | 2017-05-24 | 2017-09-19 | 张廷祥 | A kind of ultra-thin graphite alkene lithium ion single battery and graphene lithium ion battery group |
| CN107507967A (en) * | 2017-07-13 | 2017-12-22 | 贵州鼎玺烯材高科技有限公司 | A kind of graphene battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112421037A (en) * | 2020-11-04 | 2021-02-26 | 成都新柯力化工科技有限公司 | Hydrophobic NCA positive electrode material of lithium battery and preparation method |
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Application publication date: 20180629 |