CN105977492A - High-capacity high-voltage graphene power battery and a production method thereof - Google Patents
High-capacity high-voltage graphene power battery and a production method thereof Download PDFInfo
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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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- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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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
Abstract
A high-capacity high-voltage graphene power battery comprises a positive aluminum foil collector, a positive graphene coating layer, an organic carbon-cotton (solid state) electrolyte hard carbon-cotton, a negative silicon/wrinkled graphene coating layer and a negative copper foil collector. The battery of the invention is made from graphene and silicon-oxygen/carbon and wrinkled graphene, the cost of the battery is greatly reduced, the battery with the materials is high in charging speed than a traditional lithium cell, and the battery has long cycle life, good safety, zero environmental pollution and long life.
Description
Technical field
The present invention provides a kind of high-tension Graphene of Large Copacity and modified power storage battery thereof.
Background technology
Due to progress and the increase of population of human society, to improving constantly of social material requirements, and cause therewith
The increasing the weight of of environmental pollution, people's urgently expectation to improvement of environment, and vehicle fuel is the key factor polluted, the mankind
Dependence to automobile gets more and more, and Electric power car is the optimum selection of zero-emission, can find the electric power storage of a replacing fuel oil power
Pond is the most important thing, once places high hopes lithium battery, in practice it has proved that lithium battery exists the hidden danger such as easily heating, blast, charging interval
Long, the defects such as course continuation mileage is disconnected, no matter use which brand, it is most important that safety first, next to that the charging interval, the 3rd is continuous
Boat mileage.The every technical measures of the present invention overcome above-mentioned conventional batteries no, reach the expectation of people.
Summary of the invention
Goal of the invention: the present invention provides a kind of high-tension Graphene of Large Copacity and modified power storage battery, its purpose
It is to solve the most existing problem.
Technical scheme:
A kind of Large Copacity high voltage Graphene power accumulator, it is characterised in that: this accumulator includes positive pole aluminium foil collector, just
Pole Graphene coating, organic carbon cotton (solid-state) electrolyte hard carbon cotton, negative pole silicon/fold Graphene coating and negative copper foil afflux
Body, cotton (solid-state) the electrolyte hard carbon of positive pole aluminium foil collector, positive pole Graphene coating, organic carbon is cotton, negative pole silicon/fold Graphene
Coating and negative copper foil collector are arranged in housing；Cotton (solid-state) electrolyte hard carbon cotton of organic carbon is arranged on positive pole aluminium foil afflux
Between body and negative copper foil collector, cotton (solid-state) electrolyte hard carbon cotton of organic carbon is coated with gel (solid-state) electrolyte；Just
It is peripheral that pole Graphene coating is coated on positive pole aluminium foil collector, and negative pole silicon/fold Graphene coating is coated on negative copper foil afflux
Body is peripheral；It is provided with the case lid closing housing in housing upper end, case lid is provided with Positive Poles and negative pole pole, just
Pole pole connects positive pole aluminium foil collector, and negative pole pole connects negative copper foil collector.
Case lid is provided with air outlet valve；Air outlet valve connects the chamber at cotton (solid-state) electrolyte hard carbon cotton place of organic carbon
Body.
Cotton (solid-state) the electrolyte hard carbon of organic carbon is cotton and between positive pole aluminium foil collector and organic carbon cotton (solid-state) electrolysis
It is respectively provided with, between matter hard carbon cotton and negative copper foil collector, the Small Distance becoming bulky capacitor.
Cotton (solid-state) electrolyte hard carbon cotton is made up of, at carbon element organic carbon the carbon element net with insulating polymer microscopic voids
It is provided with the active substance solid electrolyte of hard carbon on the net.
Insulation diaphragm all it is coated with outside positive pole Graphene coating and negative pole silicon/fold Graphene coating.
The preparation method of Large Copacity high voltage Graphene power accumulator described above, it is characterised in that: the step of the method
Rapid as follows:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 50-150g graphene oxide ultrasonic disperse is formed uniform suspension in 400-600ml deionized water；
(2), by silicon dioxide (sio2) 400-600mg ultrasonic disperse that particle diameter is 5-15nm at the deionized water of 50-150ml
In；
(3), by after above two solution mixing ultrasonic disperse 10-40min, freezing in frozen water vessel.
(4), mixed liquor in N2 nitrogen, with 700-1500 DEG C of heat treatment.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon " selects one of following method:
Method 1: the spray drying method as covering with emulsified asphalt and Conventional solid powdered pitch:
With silica flour after water for ball milling, being spray-dried through Emulsified Asphalt Mixture, spraying and inlet temperature are 150-350 DEG C, outlet
Temperature is 90-150 DEG C, obtains when carburizing sintering under inert gas conditions；
Method 2: by carbon monoxide and Delanium by 1-2.5:0.5-1.5(mass ratio) it is contained in ball in the politef of zirconium pearl
After mill 5-15h, revolution is that 350-600 turns/min, under the conditions of room temperature (20-25 DEG C), the mixture in tank is carried out again logical argon
Under the conditions of high-temperature process so that the pressure of the argon in tank is maintained at 0.1MPa, and programming rate is 7-15 DEG C/min, and temperature rise is extremely
150-350 DEG C, then grind to obtain cladding nanometer " silicon ", i.e. sio/c；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 1-with cladding nanometer " silicon " material
25:1(mass ratio) ratio be mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 3-7:70-150 mass mixing stir,
More than 200-350 DEG C carbonization treatment after ultrasonic vibration, grinds and is organic hard carbon, and granularity is 15 20 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
Advantage and effect: patent of the present invention provides a kind of Large Copacity high voltage Graphene power accumulator and preparation side thereof
Method, the present invention uses the most extremely aluminium foil surface coating Graphene, and negative pole is that copper foil surface coats fold Graphene, between both positive and negative polarity
Electrolyte be that solid microporous hard carbon carbon is cotton.
This battery core is a kind of novel battery energy, and it does not contains lithium metal, in charge and discharge process, only graphite ion, silicon,
Carbon ion embed between both positive and negative polarity and deviate from (as it is shown in figure 1) and there is no lithium metal, therefore Graphene ion battery core
Can electric current greatly, high voltage discharge and recharge, more safety and stability, because big 700 times of nano-sized carbon surface area ratio lithium ion material, and graphite
Alkene specific surface area 2600/g, is again the decades of times of nanometer what is said or talked about surface area, considerably increases battery capacity.
As energy storage material, there is not cell reaction, be physical change process in Graphene in charge and discharge process, the present invention
Material therefor is Graphene and silica/carbon and fold Graphene, and it is substantially reduced cost, and uses this material than traditional lithium battery
Charging rate is fast, and it has extended cycle life, security performance is good, non-environmental-pollution, and course continuation mileage is long.
Accompanying drawing illustrates:
Fig. 1 is this monomer battery structure；
Fig. 2 is monomer negative pole or anode structure；
Fig. 3 is equivalent circuit diagram.
1, positive pole aluminium foil collector；
2, positive pole Graphene coating；
3, cotton (solid-state) the electrolyte hard carbon of organic carbon is cotton；
4, negative pole silicon/fold Graphene coating；
5, negative copper foil collector；
6, insulation diaphragm；
7, case lid；
8, Positive Poles；
9, negative pole pole；
10, housing.
Detailed description of the invention: the present invention is described further below in conjunction with the accompanying drawings:
As it is shown in figure 1, the present invention provides a kind of Large Copacity high voltage Graphene power accumulator, a kind of Large Copacity high voltage graphite
Alkene power accumulator, this accumulator includes cotton (solid-state) electrolyte of positive pole aluminium foil collector 1, positive pole Graphene coating 2, organic carbon
Hard carbon cotton 3, negative pole silicon/fold Graphene coating 4 and negative copper foil collector 5, positive pole aluminium foil collector 1, positive pole Graphene are coated with
Cotton (solid-state) electrolyte hard carbon cotton 3 of layer 2, organic carbon, negative pole silicon/fold Graphene coating 4 and negative copper foil collector 5 are arranged on
In housing 10；Cotton (solid-state) electrolyte hard carbon cotton 3 of organic carbon be arranged on positive pole aluminium foil collector 1 and negative copper foil collector 5 it
Between, cotton (solid-state) electrolyte hard carbon cotton 3 of organic carbon is coated with gel (solid-state) electrolyte；；Positive pole Graphene coating 2 is coated on
Positive pole aluminium foil collector 1 is peripheral, and it is peripheral that negative pole silicon/fold Graphene coating 4 is coated on negative copper foil collector 5；At housing 10
Upper end is provided with the case lid 7 closing housing 10, is provided with Positive Poles 8 and negative pole pole 9, Positive Poles 8 in case lid 7
Connecting positive pole aluminium foil collector 1, negative pole pole 9 connects negative copper foil collector 5.
Case lid 7 is provided with air outlet valve 11；Air outlet valve 11 connects cotton 3 places of cotton (solid-state) the electrolyte hard carbon of organic carbon
Cavity, for discharging the excessive gas of generation.
Between cotton (solid-state) electrolyte hard carbon of organic carbon cotton 3 and positive pole aluminium foil collector 1 and organic carbon cotton (solid-state) electricity
Solve and be respectively provided with, between matter hard carbon cotton 3 and negative copper foil collector 5, the Small Distance becoming bulky capacitor.
Cotton (solid-state) electrolyte hard carbon cotton 3 is made up of, at carbon organic carbon the carbon element net with insulating polymer microscopic voids
Element is provided with the active substance solid electrolyte of hard carbon on the net.
Insulation diaphragm 6 all it is coated with outside positive pole Graphene coating 2 and negative pole silicon/fold Graphene coating 4.
Embodiment 1:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 100g graphene oxide ultrasonic disperse is formed uniform suspension in 500ml deionized water；
(2), by silicon dioxide (sio2) 500mg ultrasonic disperse that particle diameter is 10nm in the deionized water of 100ml；
(3), by after above two solution mixing ultrasonic disperse 30min, freezing in frozen water vessel.
(4), mixed liquor is at N2In nitrogen, with 1000 DEG C of heat treatments.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon ":
The spray drying method as covering with emulsified asphalt and Conventional solid powdered pitch:
With silica flour after water for ball milling, being spray-dried through Emulsified Asphalt Mixture, spraying and inlet temperature are 300 DEG C, outlet temperature
It is 110 DEG C, obtains when carburizing sintering under inert gas conditions；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 1:1 with cladding nanometer " silicon " material
The ratio of (mass ratio) is mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 6:100 mass mixing stir, ultrasonic
Shaking rear more than 300 DEG C carbonization treatment, grind and be organic hard carbon, granularity is 15 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
Embodiment 2:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 50g graphene oxide ultrasonic disperse is formed uniform suspension in 400ml deionized water；
(2), by silicon dioxide (sio2) 600mg ultrasonic disperse that particle diameter is 15nm in the deionized water of 150ml；
(3), by after above two solution mixing ultrasonic disperse 10min, freezing in frozen water vessel.
(4), mixed liquor is at N2In nitrogen, with 700 DEG C of heat treatments.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon ":
The spray drying method as covering with emulsified asphalt and Conventional solid powdered pitch:
With silica flour after water for ball milling, being spray-dried through Emulsified Asphalt Mixture, spraying and inlet temperature are 350 DEG C, outlet temperature
It is 150 DEG C, obtains when carburizing sintering under inert gas conditions；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 25:1 with cladding nanometer " silicon " material
The ratio of (mass ratio) is mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 7:150 mass mixing stir, ultrasonic
Shaking rear more than 200 DEG C carbonization treatment, grind and be organic hard carbon, granularity is 20 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
Embodiment 3:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 150g graphene oxide ultrasonic disperse is formed uniform suspension in 600ml deionized water；
(2), by silicon dioxide (sio2) 400mg ultrasonic disperse that particle diameter is 5nm in the deionized water of 50ml；
(3), by after above two solution mixing ultrasonic disperse 10min, freezing in frozen water vessel.
(4), mixed liquor is at N2In nitrogen, with 1500 DEG C of heat treatments.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon ":
The spray drying method as covering with emulsified asphalt and Conventional solid powdered pitch:
With silica flour after water for ball milling, being spray-dried through Emulsified Asphalt Mixture, spraying and inlet temperature are 150 DEG C, outlet temperature
It is 90 DEG C, obtains when carburizing sintering under inert gas conditions；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 15:1 with cladding nanometer " silicon " material
The ratio of (mass ratio) is mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 3:70 mass mixing stir, ultrasonic shake
Swinging rear more than 350 DEG C carbonization treatment, grind and be organic hard carbon, granularity is 18 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
Embodiment 4:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 100g graphene oxide ultrasonic disperse is formed uniform suspension in 500ml deionized water；
(2), by silicon dioxide (sio2) 500mg ultrasonic disperse that particle diameter is 10nm in the deionized water of 100ml；
(3), by after above two solution mixing ultrasonic disperse 30min, freezing in frozen water vessel.
(4), mixed liquor is at N2In nitrogen, with 1000 DEG C of heat treatments.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon ":
By carbon monoxide and Delanium by 2:1(mass ratio) it is contained in the politef of zirconium pearl after ball milling 10h, revolution is
500 turns/min, under the conditions of room temperature (20-25 DEG C), the mixture in tank is carried out high-temperature process under the conditions of logical argon again so that tank
In the pressure of argon be maintained at 0.1MPa, programming rate is 10 DEG C/min, temperature rise to 300 DEG C, then grinds and to obtain cladding nanometer
" silicon ", i.e. sio/c；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 1:1 with cladding nanometer " silicon " material
The ratio of (mass ratio) is mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 6:100 mass mixing stir, ultrasonic
Shaking rear more than 300 DEG C carbonization treatment, grind and be organic hard carbon, granularity is 15 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
Embodiment 5:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 50g graphene oxide ultrasonic disperse is formed uniform suspension in 400ml deionized water；
(2), by silicon dioxide (sio2) 600mg ultrasonic disperse that particle diameter is 15nm in the deionized water of 150ml；
(3), by after above two solution mixing ultrasonic disperse 10min, freezing in frozen water vessel.
(4), mixed liquor is at N2In nitrogen, with 700 DEG C of heat treatments.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon ":
By carbon monoxide and Delanium by 1:1.5(mass ratio) it is contained in the politef of zirconium pearl after ball milling 15h, revolution is
350 turns/min, under the conditions of room temperature (20-25 DEG C), the mixture in tank is carried out high-temperature process under the conditions of logical argon again so that tank
In the pressure of argon be maintained at 0.1MPa, programming rate is 7 DEG C/min, temperature rise to 350 DEG C, then grinds and to obtain cladding nanometer
" silicon ", i.e. sio/c；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 25:1 with cladding nanometer " silicon " material
The ratio of (mass ratio) is mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 7:150 mass mixing stir, ultrasonic
Shaking rear more than 200 DEG C carbonization treatment, grind and be organic hard carbon, granularity is 20 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
Embodiment 6:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material.
The preparation technology of fold Graphene:
(1), 150g graphene oxide ultrasonic disperse is formed uniform suspension in 600ml deionized water；
(2), by silicon dioxide (sio2) 400mg ultrasonic disperse that particle diameter is 5nm in the deionized water of 50ml；
(3), by after above two solution mixing ultrasonic disperse 10min, freezing in frozen water vessel.
(4), mixed liquor is at N2In nitrogen, with 1500 DEG C of heat treatments.
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon ":
By carbon monoxide and Delanium by 2.5:0.5(mass ratio) it is contained in the politef of zirconium pearl after ball milling 5h, revolution
It is 600 turns/min, under the conditions of room temperature (20-25 DEG C), the mixture in tank is carried out high-temperature process under the conditions of logical argon again so that
The pressure of the argon in tank is maintained at 0.1MPa, and programming rate is 15 DEG C/min, temperature rise to 150 DEG C, then grinds to obtain cladding nanometer
" silicon ", i.e. sio/c；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 15:1 with cladding nanometer " silicon " material
The ratio of (mass ratio) is mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 3:70 mass mixing stir, ultrasonic shake
Swinging rear more than 350 DEG C carbonization treatment, grind and be organic hard carbon, granularity is 18 μm.
(2) it is sprayed on after, hard carbon mixes with Signa Gel on high insulation microcosmic porous high temperature resistant carbon cotton and is organic hard carbon
Cotton, organic hard carbon cotton is important element and the carrier of solid electrolyte；As long as hard carbon meets hard with the mixed proportion of Signa Gel
Carbon can be bonded on high insulation microcosmic porous high temperature resistant carbon cotton uniformly.
In above-mentioned " (4) " step, mixed liquor is at N2Nitrogen is carried out, N2The pressure of nitrogen is preferably kept in 0.1MPa.
In the present invention, between positive pole aluminium foil collector and negative copper foil collector 5, space is provided with microscopic voids, organic
Gel (solid-state) electrolyte it is coated with on carbon cotton 3.
The electrolyte being filled in battery container 10 is cured and gel is provided with flowing and overflow condition.Both positive and negative polarity and having
It is respectively provided with, between machine carbon cotton coating, the Small Distance becoming bulky capacitor.Positive pole aluminium foil collector is coated with active material stone
Ink ene coatings 2, it is all under vacuum that negative copper foil collector 5 is provided with activated silica/fold Graphene coating 4. coating
Spray, uniform through roll-in thickness, caking ability is high.
In order to improve the electric conductivity of polarity, add conductive agent and binding agent.As in figure 2 it is shown, support with aluminium foil or aluminium strip
Lead-in wire weld with the Positive Poles in case lid as positive wire.The same positive pole of negative pole processing technology.
There is one layer of carbon cotton between positive pole and negative pole, have the carbon element net of insulating polymer microscopic voids in carbon cotton and have on the net
The active substance solid electrolyte composition of hard carbon, this battery core is a kind of innovative battery power, and it does not contains lithium metal, in discharge and recharge
During only Graphene ion, embed between both positive and negative polarity and deviate from, battery core of shuttling back and forth is internal and does not has lithium metal, institute
With, battery is safer stable.
As in figure 2 it is shown, the equal spray roll-in of positive pole two sides bonds the Graphene active substance on its surface.As it is shown on figure 3, negative pole
Two sides equal spray roll-in bonds fold graphene/nanometer " silicon " active substance on its surface.Positive pole aluminium foil collector 1 top is drawn
Electrode and Positive Poles 8 are welded into one and are monolithically fabricated anode, negative copper foil collector 5 top extraction electrode and negative pole pole
Post 9 is welded into one and is monolithically fabricated battery cathode.Each group of both positive and negative polarity and and hard carbon cotton between have a small-gap suture, small-gap suture
Between formed a farad level bulky capacitor.
As it is shown on figure 3, Large Copacity high voltage Graphene electrokinetic cell is equivalent to a big battery E and an electric capacity C parallel connection,
Its gross energy P=E+W, is the part power sum of two.
The battery of this structure, is shown in mailing carbon cotton between both positive and negative polarity that all possessing Small Distance forms large bulk capacitance, has
Farad level electric capacity and the characteristic of high power battery.
From Fig. 3 analysis, when charging, first electric capacity charge, and is equivalent to external circuit multiple Absorption Capacitances in parallel, can prevent electricity
Flow through big and explode, be particularly suited for big electric current and fill soon.Because charging current is equal to electric capacity and battery charge sum, work as wink
Between electric discharge time because electric capacity has an advance angle characteristic, first electric discharge adapts to the needs of heavy-current discharge, if discharged for a long time,
Battery just adapts to the needs of slow play electricity and long-time slow play is electric, and general load needs work long hours, and are mistakes for slow play electricity
Journey, discharge current is also equal to electric capacity and battery discharge current sum, and this is also the advantage of capacitive cell.
From battery equivalent circuit it can be seen that electric capacity and battery are owing to being parallel operation, voltage is equal, can't produce
Raw streaming current, if the electric current of battery is I, its power is E=IV, if the capacity of electric capacity is C, its power W=1/2CV, gross energy
P=E+W, i.e. two element power sums, so, the cell body gross energy of this process structure has exceeded cell and monomer
Electric capacity.
Owing to gross energy is greatly improved, so producing the battery of identical energy, its volume and weight alleviates the most significantly,
Alleviate the transport burden of vehicle, alleviate the volume of power set, add power.
In sum, Large Copacity high voltage Graphene power accumulator of the present invention belongs to capacitive cell, bulky capacitor capacity
From more than several farads to thousands of farads, power is up to more than during Wan An, and energy capacity density can be more than 300Wh/L.Gravimetric
Density can reach 125Wh/L.
Big 700 times of the surface area ratio conventional lithium ion material that carbon nano-fiber is formed, and the surface area of Activated Graphite alkene, again
Being the decades of times of carbon nano-fiber, therefore, graphene battery Capacity Ratio carbon nano-fiber capacity to be greatly improved, graphene battery
Can charge with the big current high voltage of safety and stability, and the charging interval only needs even several seconds a few minutes to complete, course continuation mileage is significantly
Improve.This battery can be used with electrical domain planted agent at all.
Claims (6)
1. a Large Copacity high voltage Graphene power accumulator, it is characterised in that: this accumulator includes positive pole aluminium foil collector
(1), positive pole Graphene coating (2), cotton (solid-state) the electrolyte hard carbon of organic carbon cotton (3), negative pole silicon/fold Graphene coating (4)
With negative copper foil collector (5), cotton (solid-state) electrolyte of positive pole aluminium foil collector (1), positive pole Graphene coating (2), organic carbon
Hard carbon cotton (3), negative pole silicon/fold Graphene coating (4) and negative copper foil collector (5) are arranged in housing (10)；Organic carbon
Cotton (solid-state) electrolyte hard carbon cotton (3) is arranged between positive pole aluminium foil collector (1) and negative copper foil collector (5), organic carbon
It is coated with gel (solid-state) electrolyte on cotton (solid-state) electrolyte hard carbon cotton (3)；；Positive pole Graphene coating (2) is coated on positive pole
Aluminum foil current collector (1) is peripheral, and it is peripheral that negative pole silicon/fold Graphene coating (4) is coated on negative copper foil collector (5)；At housing
(10) upper end is provided with the case lid (7) closing housing (10), is provided with Positive Poles (8) and negative pole pole in case lid (7)
Post (9), Positive Poles (8) connects positive pole aluminium foil collector (1), and negative pole pole (9) connects negative copper foil collector (5).
Large Copacity high voltage Graphene power accumulator the most according to claim 1, it is characterised in that: in case lid (7)
On be provided with air outlet valve (11)；Air outlet valve (11) connects the cavity at cotton (3) place of cotton (solid-state) the electrolyte hard carbon of organic carbon.
Large Copacity high voltage Graphene power accumulator the most according to claim 1, it is characterised in that: organic carbon cotton (Gu
State) between electrolyte hard carbon cotton (3) and positive pole aluminium foil collector (1) and cotton (solid-state) the electrolyte hard carbon of organic carbon cotton (3) and
Negative copper foil collector is respectively provided with, between (5), the Small Distance becoming bulky capacitor.
Large Copacity high voltage Graphene power accumulator the most according to claim 1, it is characterised in that: organic carbon cotton (Gu
State) electrolyte hard carbon cotton (3) is made up of the carbon element net with insulating polymer microscopic voids, is provided with hard carbon on the net at carbon element
Active substance solid electrolyte.
Large Copacity high voltage Graphene power accumulator the most according to claim 1, it is characterised in that: at positive pole Graphene
Coating (2) and negative pole silicon/fold Graphene coating (4) are the most all coated with insulation diaphragm (6).
6. the preparation method of Large Copacity high voltage Graphene power accumulator as claimed in claim 1, it is characterised in that: the party
The step of method is as follows:
Positive electrode: direct spraying Graphene；
Negative material: fold Graphene and nanometer " silicon " meet material；
The preparation technology of fold Graphene:
(1), 50-150g graphene oxide ultrasonic disperse is formed uniform suspension in 400-600ml deionized water；
(2), by silicon dioxide (sio2) 400-600mg ultrasonic disperse that particle diameter is 5-15nm at the deionized water of 50-150ml
In；
(3), by after above two solution mixing ultrasonic disperse 10-40min, freezing in frozen water vessel；
(4), mixed liquor in N2 nitrogen, with 700-1500 DEG C of heat treatment；
(5), with Fluohydric acid. (FH) solution, etch away silicon dioxide (sio2), drying and fold Graphene；
The preparation technology of cladding nanometer " silicon " selects one of following method:
Method 1: the spray drying method as covering with emulsified asphalt and Conventional solid powdered pitch:
With silica flour after water for ball milling, being spray-dried through Emulsified Asphalt Mixture, spraying and inlet temperature are 150-350 DEG C, outlet
Temperature is 90-150 DEG C, obtains when carburizing sintering under inert gas conditions；
Method 2: by carbon monoxide and Delanium by 1-2.5:0.5-1.5(mass ratio) it is contained in ball in the politef of zirconium pearl
After mill 5-15h, revolution is that 350-600 turns/min, under the conditions of room temperature (20-25 DEG C), the mixture in tank is carried out again logical argon
Under the conditions of high-temperature process so that the pressure of the argon in tank is maintained at 0.1MPa, and programming rate is 7-15 DEG C/min, and temperature rise is extremely
150-350 DEG C, then grind to obtain cladding nanometer " silicon ", i.e. sio/c；
After fold Graphene and cladding nanometer " silicon " complete, fold Graphene is pressed 1-with cladding nanometer " silicon " material
25:1(mass ratio) ratio be mixed into the composite of silicon/fold Graphene as negative pole；
Hard carbon and the preparation technology of hard carbon cotton:
(1), the graphite modified technology of hard carbon, native graphite is crushed, screening with stearic acid press 3-7:70-150 mass mixing stir,
More than 200-350 DEG C carbonization treatment after ultrasonic vibration, grinds and is organic hard carbon, and granularity is 15 20 μm；
(2), hard carbon be sprayed on after mixing with Signa Gel that to be organic hard carbon on high insulation microcosmic porous high temperature resistant carbon cotton cotton, have
Machine hard carbon cotton is important element and the carrier of solid electrolyte；Can be equal as long as hard carbon and the mixed proportion of Signa Gel meet hard carbon
Even is bonded on high insulation microcosmic porous high temperature resistant carbon cotton.
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