CN109004232A - A kind of chemical preparation method of novel utter misery aluminium foil and its application - Google Patents
A kind of chemical preparation method of novel utter misery aluminium foil and its application Download PDFInfo
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- CN109004232A CN109004232A CN201810523367.XA CN201810523367A CN109004232A CN 109004232 A CN109004232 A CN 109004232A CN 201810523367 A CN201810523367 A CN 201810523367A CN 109004232 A CN109004232 A CN 109004232A
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- aluminium foil
- utter misery
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- copper
- graphite alkene
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
-
- 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
-
- 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
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
Abstract
Present invention relates particularly to the preparation methods and application that there are the novel utter misery aluminium foil of graphite acetylenic protective layer on a kind of surface, belong to technical field of energy storage.Utter misery aluminium foil includes the ultra-thin charcoal protective layer composition on aluminium foil and surface, mainly includes the following steps: that graphite alkene material is in the deposition of aluminium foil surface in the preparation and solution of the graphite alkene monomer as charcoal protective layer.The utter misery aluminium foil of the method for the invention preparation has preparation process simply controllable, and the feature of material structure stabilization etc., the utter misery aluminium foil of preparation can reduce the corrosion of aluminium foil surface in electrochemical reaction process, promote the capacity and cycle performance of energy storage device.
Description
Technical field
The invention belongs to technical field of energy storage, and in particular to there is the novel utter misery aluminium foil of graphite acetylenic protective layer on a kind of surface
Liquid deposition the preparation method and its application in energy storage device.
Background technique
Metal ion battery (such as lithium ion battery) conduct of abjection mechanism is embedded in carbon material based on metal ion
Large-scale application has been obtained in high commercial secondary energy sources system.As the important component in lithium ion battery,
Aluminium collector plays the role of adhering to positive active material in lithium battery and transmits electronics.Of lithium battery positive pole active substance
Grain partial size is larger, so that the contact between particle and collector is contact of the point with face, reduces the pathway of electronics, thus
Increase resistance.The current solution generallyd use is uniformly to apply scattered conductive nano graphite and carbon black granules
Cloth is on the surface of aluminium foil, so as to which the contact resistance between positive electrode and collector is greatly reduced, to improve battery
Comprehensive performance.(a method of affluxion body in lithium ion batteries utter misery aluminium foil is prepared by raw material of metallurgical coke, Chinese patent:
106505206A) currently most used method is by the method for physical contact by conductions such as deployed graphite or graphene
Slurry is coated on aluminium foil to prepare utter misery aluminium foil, but electrocondution slurry dosage is larger, by adhesive-coated in aluminium foil surface
Carbon-coating be also easy to happen removing, the performance of carbon-coated aluminum foils is not so good, and then influences the performance of prepared battery.Novel two
Dimension carbon nano-graphite alkynes material has both bigger serface, stable structure, ion and advantages (G. Li, the Y. Li, H. such as quickly spreads
Liu, Y. Guo, Y. Li, D. Zhu, Chem. Commun. 2010, 46, 3256；A kind of graphite alkyne film of preparing
Method, Chinese patent: 201010102048.5), the presence of acetylene bond and the structure in multilayer duct assign the unique property of graphite alkene
Matter has tentatively shown excellent performance, such as solar battery, lithium ion secondary battery and capacitor field in multiple fields
(C. Huang.; S. Zhang.;H. Liu.;Y. Li.;G. Cui.; Y. Li. Nano Energy 2015, 11,
481；Application of the graphite alkene in metal ion battery and capacitor, Chinese patent: 201410119705.5).With graphene etc.
Other are compared by carbon material prepared by Polymer-pyrolysis or vapour deposition process, and graphite alkene is reacted by chemical coupling in solution
Middle preparation can both deposit one layer uniformly by the method for primary reconstruction on target substrate (such as aluminium foil, lithium foil, copper foil etc.)
Graphite alkene thin polymer film, various functional groups of introducing that can also be quantitative on monomer using synthetic strategy from bottom to top,
And necessary regulation is carried out to the chemical structure for preparing graphite alkene and molecule aperture by the optimization of reaction condition, in preparation and
There is bigger performance space and regulation possibility in terms of structure control, be expected to improvement while optimizing lithium ion transport performance
Uniform deposition of the lithium ion on graphite alkene surface.Therefore, by graphite alkene and its derivative with excellent mechanical and filming performance
Film is uniformly modified using primary reconstruction polymerization (can react item by control in a metal aluminum foil surface formation protective layer
Part controls film thickness and surface topography), and metal aluminum foil realizes that closer combination can be metal aluminum foil cathode in electricity
Corrosion and deformation in chemical process provide necessary protection.Meanwhile there is the new of graphite acetylenic charcoal protective layer on the surface of preparation
Type utter misery aluminium foil can also be used as the metallic aluminium negative electrode material of Dual-ion cell, effectively slow down aluminium while providing higher capacity
The growth of lithium alloy improves the cycle performance of battery.The experimental results showed that novel utter misery aluminium foil compared with conventional aluminium foil, is applied
Energy density in energy storage device, which is compared with cycle performance compared with normal aluminium foil, to be greatly improved, and is expected in accumulator
It is widely used in part (referring to application examples 1 and 2).
Summary of the invention
The purpose of the present invention is prepare a kind of preparation of the novel utter misery aluminium foil protected by graphite alkene and its derivative and its
Application in lithium ion battery and Dual-ion cell.
To achieve the above object, the present invention uses preparation method are as follows:
The preparation method of the novel utter misery aluminium foil, which comprises the following steps: by the graphite alkene list containing acetylene bond
Body or derivative dissolution in organic solvent, aluminium foil are placed in reaction solution as substrate with copper foil and reacts certain time,
The uniform deposition under copper catalysis of the monomer containing acetylene bond is set then to obtain utter misery aluminium foil by cleaning drying in aluminium foil surface.
The preparation method of the novel utter misery aluminium foil, it is characterised in that: above-mentioned reaction uses the graphite alkene containing acetylene bond
Monomer or derivative include other miscellaneous elements such as hydrogen, halogen, nitrogen, sulphur, phosphorus, boron replace graphite alkenes one or more of；
The preparation method of the novel utter misery aluminium foil, it is characterised in that: it is characterized by: with pyridine, triethylamine, acetone, second
One or more of organic solvents such as alcohol, tetrahydrofuran, methylene chloride, chloroform, petroleum ether, n-hexane are molten as mixing
Agent has specific nanotopography in aluminium surface by the coupling reaction preparation of graphite alkene monomer in a solvent on reactive matrix surface
Graphite alkene protective layer；
The preparation method of the novel utter misery aluminium foil, it is characterised in that: matrix used in above-mentioned reaction include copper sheet, copper foil,
Copper wire, copper mesh, copper powder, copper nano particles etc. contain Copper substrate, and with the aforementioned aluminium flake being used in conjunction with containing Copper substrate, aluminium foil, aluminium
Line, aluminium net etc. contain aluminum substrate；
The preparation method of the novel utter misery aluminium foil, it is characterised in that: above-mentioned reaction temperature be 10~120 DEG C, preferably 50
℃；Reaction time is 1~72h, preferably 12h；Above-mentioned reaction is in nitrogen, argon gas, helium, xenon, under the inert gases such as Krypton
It carries out, preferably argon gas；
The preparation method of the novel utter misery aluminium foil, it is characterised in that: the utter misery aluminium foil of above-mentioned reaction preparation, surface applies layer of charcoal
Thickness is between 10nm-1 μm；
The application of the novel utter misery aluminium foil, it is characterised in that: the energy storage device is metal ion battery or super capacitor
Device or Dual-ion cell, wherein material can be used as collector or electrode material uses；Material can directly make in energy storage device
With, crushed or other forms use.
The application of the novel utter misery aluminium foil, it is characterised in that: the metal be selected from lithium, sodium, potassium, aluminium, magnesium, calcium,
One of zinc, cadmium, nickel, cobalt.
Beneficial effects of the present invention:
The present invention by the solution by with excellent mechanical and filming performance graphite alkene and its derivative film using in situ
Self assembly polymerization uniformly modifies and forms one layer of protection carbon-coating on metal aluminum foil surface, the preparation method phase with existing utter misery aluminium foil
Than can and metal aluminum foil realize closer combination.It can be prepared by the control to reaction condition with ultra-thin stratiform knot
The corrosion and deformation that the graphite alkene Nano carbon protective layer of structure is metal aluminum foil cathode in electrochemical process provide necessary guarantor
Shield.Meanwhile the metal that the surface of preparation has the novel utter misery aluminium foil of graphite acetylenic charcoal protective layer to can also be used as Dual-ion cell
Aluminum honeycomb material, the growth for effectively slowing down aluminium lithium alloy while providing higher capacity improve the cycle performance of battery.This hair
The utter misery aluminium foil of bright the method preparation has preparation process simply controllable, the feature of material structure stabilization etc..Experimental result table
Bright, novel utter misery aluminium foil can reduce the corrosion of aluminium foil surface in electrochemical reaction process compared with conventional aluminium foil and reduce battery
Internal resistance improves the capacity and cycle performance of energy storage device.Applied in energy storage device energy density and cycle performance it is more general
Logical aluminium foil is expected to be widely used in energy storage device compared to being greatly improved
Detailed description of the invention
Fig. 1 is novel utter misery aluminium foil material object photo prepared by the embodiment of the present invention 1.
Fig. 2 is the cross-sectional scans electron microscopic picture of novel utter misery aluminium foil prepared by the embodiment of the present invention 1.
Fig. 3 is that novel utter misery aluminium foil prepared by the embodiment of the present invention 1 and normal aluminium foil are applied to lithium ion battery
Charging and discharging curve comparison diagram of the manganate cathode material for lithium collector under 1 A/g electric current.
Fig. 4 is that novel utter misery aluminium foil prepared by the embodiment of the present invention 1 and normal aluminium foil are applied to lithium ion battery
Manganate cathode material for lithium collector self discharge contrast test result under 1 A/g electric current.
Fig. 5 is that novel utter misery aluminium foil prepared by the embodiment of the present invention 1 and normal aluminium foil are applied to Dual-ion cell
The multiplying power figure comparison diagram of negative electrode material.
Fig. 6 is that novel utter misery aluminium foil prepared by the embodiment of the present invention 1 and normal aluminium foil are applied to Dual-ion cell
The circulation comparison diagram of negative electrode material.
Specific embodiment
The present invention enumerates that embodiment is as follows, and invention is further described in detail, but embodiments of the present invention are unlimited
In this.For researcher in this field, the invention may be variously modified and varied, all in spirit and original of the invention
Within then, made any modification, equivalent replacement or improvement etc. be should all be included in the protection scope of the present invention.
Embodiment 1:
(4 × 12 centimetres of copper foil, 3 × 10 centimetre 10 of aluminium foil of aluminium foil of copper foil package are washed with the hydrochloric ultrasonic wave that concentration is 1mol/L
Piece) 10 minutes, then successively dried up after ten minutes with argon gas with clear water, ethyl alcohol and each supersound washing of acetone again.After drying
The aluminium foil of copper foil package is placed in the three-necked flask for the 100mL of anhydrous pyridine solvent for being mounted with 80mL, and gas in bottle is set
It is changed to argon atmosphere.With the perseverance for injecting argon gas protection after the six alkynyl benzene monomers of the pyridinium dissolution 36mg of 20mL by syringe
It presses in funnel, instills and kept the temperature into the three-necked flask of 50 DEG C (preferably 50 DEG C) of the aluminium foil for filling solvent and copper foil package, 2
It is dripped off in hour；System is maintained at 50 DEG C of reaction 12h.Aluminium flake is taken out after reaction, successively uses ethyl alcohol and acetone washing copper sheet
For several times, it is finally dried at 100 DEG C of vacuum, the novel utter misery aluminium foil (Fig. 1) of graphite acetylenic protective layer can be obtained.Fig. 2's
Scanning electron microscope (SEM) photograph is the result shows that graphite alkene piles up the film for showing about 20nm or so on aluminum substrates.
Application examples 1:
Using the novel utter misery aluminium foil of 1 gained graphite acetylenic protective layer of embodiment as collector, by LiMn2O4 according to LiMn2O4:
Conductive black: polytetrafluoroethylene (PTFE)=8:1:1 ratio is deployed into slurry and is uniformly coated on novel utter misery aluminium foil as collector,
Punching is the electrode slice of diameter 1cm after drying, for the cathode as lithium ion battery, uses lithium piece as to electrode, using 1
Mol/L lithium hexafluoro phosphate (LiPF6)/(solvent is ethylene carbonate (EC): dimethyl carbonate (DMC), volume ratio 1:1, addition
The FEC that volume ratio is 5%) it is used as electrolyte, it is assembled into 2032 type button cells in the glove box full of argon gas and carries out electrochemistry
Performance test.
Comparative example 1:
Using business aluminium foil as collector, by LiMn2O4 according to LiMn2O4: conductive black: polytetrafluoroethylene (PTFE)=8:1:1 ratio tune
It is made into slurry and is uniformly coated on novel utter misery aluminium foil as collector, punching is the electrode slice of diameter 1cm after drying, for making
For the cathode of lithium ion battery, use lithium piece as to electrode, using 1 mol/L lithium hexafluoro phosphate (LiPF6)/(solvent is carbon
Vinyl acetate (EC): dimethyl carbonate (DMC), volume ratio 1:1, the FEC that addition volume ratio is 5%) it is used as electrolyte, it uses
Polypropylene diaphragm is assembled into 2032 type button cells in the glove box full of argon gas and carries out electrochemical property test.With conventional quotient
Compared with aluminium foil, the novel utter misery aluminium foil of graphite acetylenic protective layer as collector lithium ion battery in capacity (Fig. 3) and
There is a degree of promotion on self-discharge performance (Fig. 4).
Application examples 2:
The electrode slice for being diameter 1.2cm by the novel utter misery aluminium foil punching of 1 gained graphite acetylenic protective layer of embodiment, for making
For the cathode of double ion ion battery, by graphite according to graphite: polytetrafluoroethylene (PTFE)=9:1 ratio is deployed into slurry and uniformly applies
Cloth is in normal aluminium foil, the electrode slice that same punching is diameter 1cm after dry, using 4mol/L lithium hexafluoro phosphate (LiPF6)/
(solvent is methyl ethyl carbonate (EMC): vinylene carbonate (VC), volume ratio 95:5) is used as electrolyte, uses glass fibre
Diaphragm is assembled into 2032 type button cells in the glove box full of argon gas and carries out electrochemical property test.
Comparative example 2:
Business aluminium foil is made the electrode slice that punching is diameter 1.2cm to press graphite for the cathode as double ion ion battery
According to graphite: polytetrafluoroethylene (PTFE)=9:1 ratio is deployed into slurry and is uniformly coated in normal aluminium foil, after dry same punching be
The electrode slice of diameter 1cm, using 4mol/L lithium hexafluoro phosphate (LiPF6)/(solvent is methyl ethyl carbonate (EMC): carbonic acid Asia second
Enester (VC), volume ratio 95:5) it is used as electrolyte, it is assembled into the glove box full of argon gas using fibreglass diaphragm
2032 type button cells carry out electrochemical property test.Compared with conventional commercial aluminium foil, the novel utter misery of graphite acetylenic protective layer
Aluminium foil has a degree of promotion in multiplying power (Fig. 5) and cycle performance (Fig. 6) as the Dual-ion cell of collector.
Claims (8)
1. a kind of method for preparing utter misery aluminium foil, which comprises the following steps: by graphite alkene or derivative containing acetylene bond
Object monomer dissolve in organic solvent, be placed in reaction solution under certain condition using aluminium foil as substrate with copper foil make containing
Then the monomer of acetylene bond uniform deposition under copper catalysis obtains utter misery aluminium foil by cleaning drying in aluminium foil surface.
2. the preparation method of utter misery aluminium foil according to claim 1, it is characterised in that: above-mentioned reaction uses the stone containing acetylene bond
Black alkynes monomer or derivative include that other miscellaneous elements such as hydrogen, halogen, nitrogen, sulphur, phosphorus, boron replace one or more of graphite alkene.
3. the preparation method of utter misery aluminium foil according to claim 1, it is characterised in that: with pyridine, triethylamine, acetone, ethyl alcohol,
One or more of organic solvents such as tetrahydrofuran, methylene chloride, chloroform, petroleum ether, n-hexane are used as mixed solvent,
There is specific nanotopography in aluminium surface by the coupling reaction preparation of graphite alkene monomer in a solvent on reactive matrix surface
Graphite alkene protective layer.
4. the preparation method of utter misery aluminium foil according to claim 1, it is characterised in that: matrix used in above-mentioned reaction includes copper
Piece, copper foil, copper wire, copper mesh, copper powder, copper nano particles etc. contain Copper substrate, and with the aforementioned aluminium flake being used in conjunction with containing Copper substrate,
Aluminium foil, aluminum steel, aluminium net etc. contain aluminum substrate.
5. the preparation method of utter misery aluminium foil according to claim 1, it is characterised in that: above-mentioned reaction temperature is 10~120 DEG C,
Preferably 50 DEG C；Reaction time is 1~72h, preferably 12h；Above-mentioned reaction is in nitrogen, argon gas, helium, xenon, and Krypton etc. is lazy
It is carried out under property gas, preferably argon gas.
6. the preparation method of utter misery aluminium foil according to claim 1, it is characterised in that: the utter misery aluminium foil of above-mentioned reaction preparation,
Surface graphite alkene protective layer thickness is between 10nm-1 μm.
7. the application of utter misery aluminium foil according to claim 1, it is characterised in that: the energy storage device be metal ion battery or
Supercapacitor, wherein material can be used as collector or electrode material uses；Material can be used directly in energy storage device,
It is crushed or other forms uses.
8. metal ion battery according to claim 7, it is characterised in that: the metal be selected from lithium, sodium, potassium, aluminium, magnesium,
One of calcium, zinc, cadmium, nickel, cobalt.
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| CN201810523367.XA CN109004232A (en) | 2018-05-28 | 2018-05-28 | A kind of chemical preparation method of novel utter misery aluminium foil and its application |
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| CN201810523367.XA CN109004232A (en) | 2018-05-28 | 2018-05-28 | A kind of chemical preparation method of novel utter misery aluminium foil and its application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114142041A (en) * | 2021-11-26 | 2022-03-04 | 傲普(上海)新能源有限公司 | Carbon-coated aluminum foil and preparation method thereof |
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2018
- 2018-05-28 CN CN201810523367.XA patent/CN109004232A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114142041A (en) * | 2021-11-26 | 2022-03-04 | 傲普(上海)新能源有限公司 | Carbon-coated aluminum foil and preparation method thereof |
| CN114142041B (en) * | 2021-11-26 | 2023-07-18 | 傲普(上海)新能源有限公司 | Carbon-coated aluminum foil and preparation method thereof |
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Application publication date: 20181214 |