CN107681159A - A kind of metal foil collector of battery - Google Patents
A kind of metal foil collector of battery Download PDFInfo
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- CN107681159A CN107681159A CN201710707580.1A CN201710707580A CN107681159A CN 107681159 A CN107681159 A CN 107681159A CN 201710707580 A CN201710707580 A CN 201710707580A CN 107681159 A CN107681159 A CN 107681159A
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- battery
- graphene
- metal foil
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- carbon nanotube
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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
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
-
- 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
A kind of metal foil collector of battery, belongs to electrochemical technology field.The technical characterstic of the present invention is that metal foil collection liquid surface has nano-sized carbon coat, and the coating contains the graphene/carbon nanotube hybrid thing prepared by high temperature chemical vapor deposition method.Because graphene is connected with CNT by covalent bond form in graphene/carbon nanotube hybrid thing, there is excellent intrinsic conductivity and mechanical self-dispersing characteristic, avoid the microcosmic coalescence of carbon structural nano.In the assembling and running of battery, the nano-sized carbon coat of metal foil collection liquid surface can effectively improve the imbibition characteristic of collector and the direct mechanical bond of positive electrode active materials particle, conductive interconnections and intensified electrolysis liquid in the present invention；Impedance operator to reducing battery, the high rate during charging-discharging and cyclical stability for lifting battery have important value.
Description
Invention field
The present invention relates to a kind of battery current collector material, more particularly to a kind of aluminum foil current collector having, and belongs to electrification
Learn technical field.
Background technology
With the continuous development of society, the performance requirement of electrochemical storage device is also improved constantly.On the one hand, battery
Energy density demand is constantly lifted, to meet long continuation of the journey demand；On the other hand, the power-performance of battery is in occasions such as electrokinetic cells
Also there is important practical value.During the assembling of battery is practical, the current collector material of battery as one of core component,
Carry the mechanics carrier as active particle material and the effect of electron transfer passage is provided.At present prepared by lithium ion battery
In technique, more using aluminium foil as plus plate current-collecting body, copper foil as negative current collector, and the painting of electrode material is carried out on its surface
Cover to form the assembling that positive and negative electrode piece is used for battery.In pole piece preparation method traditional at present, still have in the presence of some technical problems.
First, it is that a point contacts between rigid active material particle and rigid aluminium foil or copper foil current collector, interface resistance is larger,
Power density is limited in running, while battery heat production is big, and cycle life is limited；Second, collector foil and active material
Mechanical Contact is realized by a point contact between particle, because of the generation of active material volume deformation, collector in cyclic process
It is easily peeling-off with electrode material, cause electrode failure, have a strong impact on the cycle life and security performance of battery.
Based on these considerations, it is a kind of effective technical measures in metal foil collection liquid surface coating carbon-coating, relates generally to
Coating material include carbon black, carbon nano-fiber, CNT, graphite oxide, reduction-oxidation graphite etc..Based on these materials
There is technical problem in coating layer segment, but still be difficult to the preparation for fully achieving efficient collector more than improving, and be based primarily upon at 2 points
Reason.First, the nano material intrinsic conductivity deficiency of coat is largely used to, is difficult to after carbon-coating is formed as efficent electronic
Turning on network reduces the internal resistance of cell, such as oxidized graphite flake layer etc.；Second, above material does not have three dimensional skeletal structure, machinery
Stability deficiency, such as the material such as reduction-oxidation graphite, CNT are easily laminated or assembled, it is difficult to complete supported active
Grain, keeps its structural stability.If improve the coating layer material of current collection liquid surface, using with three-dimensional structure and with
The nano-carbon material of high conductivity carries out the surface coating of metal foil collector, it will help lifting battery performance.
The content of the invention
It is an object of the invention to provide a kind of metal foil afflux of battery, to realize battery in preparing to electrode slice table
The reinforcing of face conductive interconnections, mechanical stability, imbibition characteristic.So as to improve the cyclical stability of battery and power characteristic.
Technical scheme is as follows：
The metal foil afflux of a kind of battery, it is characterised in that metal foil collection liquid surface coat, which contains, passes through high temperature
Learn graphene/carbon nanotube hybrid thing prepared by vapour deposition process, wherein graphene and CNT by covalent key connection, its
Specific surface area is between 500 to 3000 square metres every gram.
The metal foil collector includes aluminium foil, copper foil.
The nano-sized carbon coat thickness is between 0.01 micron to 100 microns.
The content of graphene/carbon nanotube hybrid thing is between 10% to 95% in the nano-sized carbon coat.
The present invention compared with prior art, has the following advantages that and high-lighting effect：The present invention utilizes chemical vapour deposition technique
The graphene/carbon nanotube hybrid thing of preparation is as the coating of conductive and mechanics functional layer and metal foil collection liquid surface.Graphene carbon
Graphene is connected with CNT by covalent bond form in nanotube hybrid, has excellent intrinsic conductivity and machinery certainly
Dispersing characteristic, avoid the microcosmic coalescence of carbon structural nano.In the assembling and running of battery, graphene/carbon nanotube hybrid thing
The aluminum foil current collector of coating can effectively improve collector and the direct mechanical bond of positive electrode active materials particle, conductive interconnections, simultaneously
The imbibition characteristic of intensified electrolysis liquid.Impedance operator to reducing battery, high rate during charging-discharging and the circulation for lifting battery are steady
It is qualitative that there is important value.
Embodiment
The present invention provides a kind of metal foil afflux of battery, and base material is used as containing metal foil (aluminium foil or copper foil), and
Nano-sized carbon coat；Wherein it is miscellaneous to contain the graphene carbon nanotube prepared by high temperature chemical vapor deposition method for nano-sized carbon coat
Compound, wherein graphene are with CNT by covalent key connection, and its specific surface area is between 500 to 3000 square metres every gram.
Nano-sized carbon coat thickness between 0.01 micron to 100 microns, wherein the content of graphene/carbon nanotube hybrid thing be
Between 10% to 95%.Specifically, graphene/carbon nanotube hybrid thing is prepared by the method for high temperature chemical vapor deposition,
Using magnesia as catalyst carrier, the method supported ferric catalyst impregnated using iron nitrate solution.Catalyst granules is sent
In fluidized bed reactor, typical reaction condition is：Under 950 DEG C of reaction temperatures, the gaseous mixture of methane, hydrogen, argon gas is passed through
Body, carbon atom, hydrogen molecule, the mol ratio of argon molecules are 1:2:5.Magnesia is sloughed by pickling after the completion of reaction and iron is urged
Agent, obtain pure graphene/carbon nanotube hybrid thing material.Its specific surface area is different with reaction condition, at 500-3000 squares
Between every gram of rice.Graphene/carbon nanotube hybrid thing is mixed in a solvent with other conductive agents such as binding agent, carbon blacks, obtains stone
Black olefinic carbon nanotube hybrid slurry.Using serialization high accuracy coating machine, realize that graphene/carbon nanotube hybrid thing slurry exists
The coating and drying of metal foil surface, obtain a kind of gold of battery containing graphene/carbon nanotube hybrid thing nanometer carbon coating
Belong to paper tinsel afflux.
The present invention is further appreciated that by following examples, but the present invention is not limited solely to embodiment.
Embodiment 1：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 500m2/g.The hybrid is disperseed in aqueous systems, and added
LA132 acrylic adhesives are divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.Obtained by being coated in aluminium foil surface
Metal foil collector with nano-sized carbon coat, the wherein content of graphene/carbon nanotube hybrid thing are 95%, thickness 2.0
Micron.Iron phosphate lithium electrode material coating is coated in the metal foil collection liquid surface, after battery is assembled into, electricity can be significantly improved
Pond high rate during charging-discharging, the full battery of LiFePO4 battery capacity under 1C discharging conditions are carried compared with using the battery of normal aluminium foil
It is high by 3%.
Embodiment 2：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 2500m2/g.By the hybrid in 1-METHYLPYRROLIDONE organism
Disperse in system, and add polyvinylidene fluoride alkenes binding agent and be divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By in aluminium
The coating of paper tinsel surface obtains the metal foil collector with nano-sized carbon coat, and the content of wherein graphene/carbon nanotube hybrid thing is
20%, thickness is 20 microns.In the metal foil collection liquid surface cobalt-coating acid lithium electrode material coating, after battery is assembled into,
Battery high rate during charging-discharging can be significantly improved, the full battery of cobalt acid lithium battery capacity under 1C discharging conditions relatively uses conventional aluminium
The battery of paper tinsel improves 2%.
Embodiment 3：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 1000m2/g.The hybrid is disperseed in aqueous systems, and added poly-
Tetrafluoroethylene binding agent is divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By being had in aluminium foil surface coating
There is the metal foil collector of nano-sized carbon coat, the wherein content of graphene/carbon nanotube hybrid thing is 75%, and thickness is 100 micro-
Rice.In the metal foil collection liquid surface cobalt-coating acid lithium electrode material coating, after battery is assembled into, it is big battery can be significantly improved
Current charge-discharge electrical property, the full battery of cobalt acid lithium battery capacity under 1C discharging conditions improve 8% compared with using the battery of normal aluminium foil.
Embodiment 4：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 600m2/g.By the hybrid in 1-METHYLPYRROLIDONE organic system
In disperse, and add polyvinylidene fluoride alkenes binding agent be divided into it is scattered, formed graphene/carbon nanotube hybrid thing slurry.By in aluminium foil
Surface coating obtains the metal foil collector with nano-sized carbon coat, and the content of wherein graphene/carbon nanotube hybrid thing is
10%, thickness is 40 microns.Iron phosphate lithium electrode material coating is coated in the metal foil collection liquid surface, is being assembled into battery
Afterwards, battery high rate during charging-discharging can be significantly improved, the full battery of LiFePO4 battery capacity under 1C discharging conditions relatively uses
The battery of normal aluminium foil improves 7%.
Embodiment 5：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 1000m2/g.The hybrid is disperseed in aqueous systems, and adds sea
Mosanom class binding agent is divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By being had in copper foil surface coating
The metal foil collector of nano-sized carbon coat, the wherein content of graphene/carbon nanotube hybrid thing are 60%, and thickness is 50 microns.
Silicium cathode material coating is coated in the metal foil collection liquid surface, after battery is assembled into, battery high current can be significantly improved and filled
Discharge performance, the full battery of silicium cathode battery capacity under 1C discharging conditions improve 6% compared with using the battery of common copper foil.
Embodiment 6：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 2000m2/g.By the hybrid in 1-METHYLPYRROLIDONE organism
Disperse in system, and add polyvinylidene fluoride alkenes binding agent and be divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By in aluminium
The coating of paper tinsel surface obtains the metal foil collector with nano-sized carbon coat, and the content of wherein graphene/carbon nanotube hybrid thing is
35%, thickness is 10.0 microns.Iron phosphate lithium electrode material coating is coated in the metal foil collection liquid surface, is being assembled into battery
Afterwards, battery high rate during charging-discharging can be significantly improved, the full battery of LiFePO4 battery capacity under 1C discharging conditions relatively uses
The battery of normal aluminium foil improves 3%.
Embodiment 7：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 500m2/g.By the hybrid in 1-METHYLPYRROLIDONE organic system
In disperse, and add polyvinylidene fluoride alkenes binding agent be divided into it is scattered, formed graphene/carbon nanotube hybrid thing slurry.By in aluminium foil
Surface coating obtains the metal foil collector with nano-sized carbon coat, and the content of wherein graphene/carbon nanotube hybrid thing is
70%, thickness is 3.0 microns.Iron phosphate lithium electrode material coating is coated in the metal foil collection liquid surface, is being assembled into battery
Afterwards, battery high rate during charging-discharging can be significantly improved, the full battery of LiFePO4 battery capacity under 1C discharging conditions relatively uses
The battery of normal aluminium foil improves 8%.
Embodiment 8：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 900m2/g.The hybrid is disperseed in aqueous systems, and adds fourth
Benzene rubber, sodium carboxymethylcellulose pyce class binding agent are divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By in copper foil surface
Coating obtains the metal foil collector with nano-sized carbon coat, and the wherein content of graphene/carbon nanotube hybrid thing is 85%,
Thickness is 0.1 micron.In graphite cathode material coating of the metal foil collection liquid surface coating containing 10% silicon materials, it is being assembled into
After battery, battery high rate during charging-discharging can be significantly improved, the full battery of the graphite cathode material containing 10% silicon materials is put in 1C
Battery capacity improves 4% compared with using the battery of common copper foil under the conditions of electricity.
Embodiment 9：By high temperature chemical vapor deposition method obtain graphene/carbon nanotube hybrid thing, wherein graphene with
For CNT by covalent key connection, its specific surface area is 1800m2/g.By the hybrid in 1-METHYLPYRROLIDONE organism
Disperse in system, and add polyvinylidene fluoride alkenes binding agent and be divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By in aluminium
The coating of paper tinsel surface obtains the metal foil collector with nano-sized carbon coat, and the content of wherein graphene/carbon nanotube hybrid thing is
40%, thickness is 5.0 microns.Manganic acid lithium electrode material coating is coated in the metal foil collection liquid surface, after battery is assembled into,
Battery high rate during charging-discharging can be significantly improved, the full battery of LiMn2O4 battery capacity under 1C discharging conditions relatively uses conventional aluminium
The battery of paper tinsel improves 4%.
Embodiment 10：Graphene/carbon nanotube hybrid thing, wherein graphene are obtained by high temperature chemical vapor deposition method
With CNT by covalent key connection, its specific surface area is 1200m2/g.The hybrid is disperseed in aqueous systems, and added
Polyvinyl alcohol binding agent is divided into scattered, formation graphene/carbon nanotube hybrid thing slurry.By being had in aluminium foil surface coating
There is the metal foil collector of nano-sized carbon coat, the wherein content of graphene/carbon nanotube hybrid thing is 55%, and thickness is 1.0 micro-
Rice.Tertiary cathode material coating is coated in the metal foil collection liquid surface, after battery is assembled into, the big electricity of battery can be significantly improved
Charge-discharge performance is flowed, the full battery of tertiary cathode material battery capacity under 1C discharging conditions is improved compared with using the battery of normal aluminium foil
5%.
Claims (4)
- A kind of 1. metal foil collector of battery, it is characterised in that：Metal foil collection liquid surface has nano-sized carbon coat, should Nano-sized carbon coat contains the graphene/carbon nanotube hybrid thing prepared by high temperature chemical vapor deposition method, graphene therein With CNT by covalent key connection, its specific surface area is between 500 to 3000 square metres every gram.
- 2. according to a kind of metal foil collector of battery described in claim 1, it is characterised in that：The metal foil collector Including aluminum foil current collector and copper foil current collector.
- 3. according to a kind of metal foil collector of battery described in claim 1 or 2, it is characterised in that：The nano-sized carbon applies Coating thickness is between 0.01 micron to 100 microns.
- 4. according to a kind of metal foil collector of battery described in claim 1 or 2, it is characterised in that：The nano-sized carbon applies The weight/mass percentage composition of graphene/carbon nanotube hybrid thing is between 10% to 95% in coating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710707580.1A CN107681159B (en) | 2017-08-17 | 2017-08-17 | Metal foil current collector for battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710707580.1A CN107681159B (en) | 2017-08-17 | 2017-08-17 | Metal foil current collector for battery |
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| CN107681159A true CN107681159A (en) | 2018-02-09 |
| CN107681159B CN107681159B (en) | 2020-06-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138627A (en) * | 2020-01-09 | 2020-05-12 | 新疆宏宇志祥工程咨询有限公司 | Graphene oxide/carbon nanotube high-strength polyurethane insulation board and preparation method thereof |
| CN112751075A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能***有限公司 | Lithium ion battery and preparation method thereof |
| CN114270560A (en) * | 2021-03-22 | 2022-04-01 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017011052A2 (en) * | 2015-04-23 | 2017-01-19 | William Marsh Rice University | Vertically aligned carbon nanotube arrays as electrodes |
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2017
- 2017-08-17 CN CN201710707580.1A patent/CN107681159B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017011052A2 (en) * | 2015-04-23 | 2017-01-19 | William Marsh Rice University | Vertically aligned carbon nanotube arrays as electrodes |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112751075A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能***有限公司 | Lithium ion battery and preparation method thereof |
| CN111138627A (en) * | 2020-01-09 | 2020-05-12 | 新疆宏宇志祥工程咨询有限公司 | Graphene oxide/carbon nanotube high-strength polyurethane insulation board and preparation method thereof |
| CN111138627B (en) * | 2020-01-09 | 2022-04-22 | 新疆亿元达光电科技有限公司 | Graphene oxide/carbon nanotube high-strength polyurethane insulation board and preparation method thereof |
| CN114270560A (en) * | 2021-03-22 | 2022-04-01 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| WO2022198403A1 (en) * | 2021-03-22 | 2022-09-29 | 宁德新能源科技有限公司 | Electrochemical apparatus and electronic apparatus |
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| CN107681159B (en) | 2020-06-12 |
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