CN106898729A - Flexible current-collecting body, electrode and battery comprising the flexible current-collecting body - Google Patents
Flexible current-collecting body, electrode and battery comprising the flexible current-collecting body Download PDFInfo
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- CN106898729A CN106898729A CN201710189749.9A CN201710189749A CN106898729A CN 106898729 A CN106898729 A CN 106898729A CN 201710189749 A CN201710189749 A CN 201710189749A CN 106898729 A CN106898729 A CN 106898729A
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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
- H01M4/661—Metal or alloys, e.g. alloy 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of 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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Abstract
The invention discloses a kind of flexible current-collecting body, electrode and battery comprising the flexible current-collecting body, wherein flexible current-collecting body includes textile substrate and metallic conduction coating, and metallic conduction coating is coated on the fiber of textile substrate；The thickness of the metallic conduction coating is 200nm~5 μm.Electrode comprising the flexible current-collecting body, its electrode active material is carried in the surface of described flexible current-collecting body and/or hole.The battery prepared using electrode of the invention, can effectively reduce the interface internal resistance of battery, reduce unit area electrode quality, improve its mass energy density；Because flexible current-collecting body of the invention has more preferable machining property relative to conventional metals paper tinsel, this can also improve the production efficiency of battery, reduce production cost；Collector substrate of the invention is macromolecular material, and fusing can be shunk in high temperature, improves the security performance of battery.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of flexible current-collecting body, the electrode comprising the flexible current-collecting body
And battery.
Background technology
Because energy density is high, good reliability and environmental-protecting performance are excellent, it is most important that lithium battery has become in the market
One of energy storage device, is widely used in the portable type electronic products such as digital camera, mobile phone and notebook computer.With electronic in the recent period
The rise of car and develop rapidly, the energy density and stability of lithium ion battery have been got back further lifting and improvement.Collection
Fluid has vital as connection electrode and the part of external circuit in lithium battery to the performance of battery performance
Influence.Collector effect be exactly will collect its surface positive pole or anode active material layer each several part low current and formed compared with
It is big to extrinsic current.
At present, lithium battery electrode plate is mainly using the level stacking pattern of electrode coated material on metal foil collector.Gold
Category paper tinsel collector and electrode material layer are separated completely, and two interlayer contacts form larger interface resistance.Improve it with electrode material
The surface contact of the bed of material turns into one of key issue for making high specific energy batteries.
Traditional plus plate current-collecting body uses aluminium foil, and at 15~20 μm, the Copper Foil that negative current collector is used, thickness exists thickness
8~12 μm.Metal foil has good electric conductivity, but in above-mentioned thickness, machining property is poor, shows as entirety
More crisp, toughness is not enough, once being subject to external impacts or external force metamorphosis, can produce irreversible vestige even hole, causes
There is leakage current in battery plus-negative plate, not only influences the effectiveness of performance of whole battery, it could even be possible to there is serious safety problem.
Additionally, the mass area ratio of metal foil is larger, traditional Copper Foil and aluminium foil accounts for the 15~20% of whole battery quality, be except
The most heavy part of the outer battery of positive and negative electrode material.Therefore, external leading colleague is pursuing thinner lighter current collector material
Or structure, its quality is reduced, so that the energy density for effectively improving.
The content of the invention
For collector mass area ratio in the prior art it is big, interface resistance is big not between collector and electrode material
Foot, the invention provides a kind of flexible collector, electrode and battery comprising the flexible current-collecting body, the collector unit area
Quality is small, and interface resistance is small between collector and electrode material in the electrode comprising the flexible current-collecting body.
A kind of flexible current-collecting body, including textile substrate and metallic conduction coating, metallic conduction coating are coated on yarn fabric
On the fiber of substrate；
The thickness of the metallic conduction coating is 200nm~5 μm.
Flexible current-collecting body of the invention, as substrate, is plated using yarn fabric by fibres for fabrics outsourcing coated with metal conductive
Layer forms three-dimensional conductive structure, and the flexible current-collecting body mass area ratio is small, can substantially reduce the quality of overall electrode, and compare
Surface area is big, can optimize contact of the electrode material with collector, reduces interface resistance between collector and electrode material.
In order to ensure the mechanical strength and electric conductivity of flexible current-collecting body, the thickness and yarn fabric of textile substrate are should ensure that
The diameter of fiber in substrate, preferably, the number of plies of described textile substrate is 2~5；The fiber of described textile substrate
A diameter of 1 μm~30 μm.
It is further preferred that the thickness of described flexible current-collecting body is 5 μm~80 μm；It is furthermore preferred that described flexible collection
The thickness of fluid is 10 μm~50 μm.
Preferably, the thickness of described metallic conduction coating is 200nm~5 μm；It is further preferred that described metal
The thickness of conductive coating is 500nm~3 μm.Both can guarantee that flexible current-collecting body had preferable mechanical strength and electric conductivity, and
Can guarantee that the mass area ratio of flexible current-collecting body is small, the energy density of battery can be effectively improved.
In order to increase the specific surface area of flexible current-collecting body, optimize contact of the electrode material with collector, reduce collector with
Interface resistance between electrode material, answers the braiding structure of optimization design textile substrate, it is ensured that textile substrate has suitable
Porosity and pore size.Preferably, the porosity of described flexible current-collecting body is 20%~85%；It is further preferred that
The porosity of described flexible current-collecting body is 25%~50%.
Flexible current-collecting body under the technical scheme has preferable mechanical strength, meanwhile, its specific surface area is larger, can be significantly
Reduce interface resistance between collector and electrode material.
Preferably, the mass area ratio of described flexible current-collecting body is 5g/m2~300g/m2；It is further preferred that
The mass area ratio of described flexible current-collecting body is 10g/m2~50g/m2。
The material of described textile substrate be polyester fiber, Fypro, polyacrylonitrile fibre, polyolefine fiber,
One kind or several in vinal, polyurethane fiber, viscose fiber, CUP, acetate fiber, cotton, fiber crops, wool, silk
Kind.
The substrate of flexible current-collecting body is macromolecular material, by high temperature after-contraction fusing, high temperature exothermic is produced in the battery
When (150 DEG C or so), physics open circuit can be carried out to battery in advance, form new one protection system.
The material of described metallic conduction coating is one or more in Cu, Al, Ni, Au, Ag, Zn, Fe.
Preferably, described metallic conduction coating includes copper coating and nickel coating successively from inside to outside；
The thickness of the copper coating is 100nm~3 μm；
The thickness of the nickel coating is 100nm~2 μm.
The flexible current-collecting body and can be used as plus plate current-collecting body, again can be used as negative current collector.The copper coating of internal layer can ensure
The electric conductivity of flexible current-collecting body.
Copper has electric conductivity higher, and nickel has preferable anticorrosive antioxygenic property, using such nickel copper-clad
Composite construction can protect copper not oxidized, be conducive to production application, while reducing the oxidation by air in transfer is produced and dropping
The possibility of low electric conductivity.
It is further preferred that the thickness of the copper coating is 400nm~2 μm；The thickness of the nickel coating is 100nm~1 μ
m。
Flexible current-collecting body of the invention can be prepared by following technique：
(1) after being respectively washed textile substrate cloth acetone, alcohol, its surface is activated with UV plasmas；
(2) preliminary gold is carried out on textile substrate cloth two sides with metallic conduction coating target using the method for vacuum sputtering
Category plated film, thickness is between 50nm~200nm；
(3) electrophoretic techniques is utilized, the enterprising row metal plating of the metal coating on textile substrate surface.
Flexible current-collecting body of the invention has advantages below：(1) with preferable pliability and machining property, with curved
Bilge radius are its resistance variations ＜ 1% after 1em bends 180 ° more than 20000 times；(2) with good heat endurance, 120
After being toasted 5 hours at DEG C, its percent thermal shrinkage ＜ 3%, resistance variations ＜ 1%；(3) with good electric conductivity, its sheet resistance is
1m Ω~50m Ω.
Present invention also offers a kind of electrode, including flexible current-collecting body as described above and electrode active material；Described
Electrode active material is carried in the surface of described flexible current-collecting body and/or hole.
Electrode of the invention, the specific surface area of flexible current-collecting body is larger, electrode active material not only load compliant collector
Surface, moreover it is possible to occupy in its internal void, improve unit area flexible current-collecting body upper electrode material load capacity；It is simultaneously electric
Pole active material is fully contacted with the surface of flexible current-collecting body, the contact performance of lifting electrode material and conductive network, reduces electricity
Interface internal resistance between extremely interior electrode active material and flexible current-collecting body.
Present invention also offers the preparation method of above-mentioned electrode, including：
Electrode active material is made electrode slurry, is coated on the flexible current-collecting body that thickness is 5 μm~80 μm, at 80 DEG C
After being dried in~120 DEG C of vacuum drying oven, described electrode is obtained；
Electrode slurry coating thickness is 30 μm~350 μm.
The preparation method of anode pole piece is：Electrode active material is dissolved in 1-METHYLPYRROLIDONE electrode slurry is obtained,
By weight percentage, described electrode active material includes：Tertiary cathode material 87~95%, Kynoar 3~7% with
And acetylene black 2~6%；
Electrode slurry is coated on the flexible current-collecting body that thickness is 5 μm~80 μm, in 80 DEG C~120 DEG C of vacuum drying oven
After middle drying, anode pole piece is obtained.
The preparation method of cathode pole piece is：Electrode active material is dissolved in 1-METHYLPYRROLIDONE electrode slurry is obtained,
By weight percentage, described electrode active material includes：Graphite material 87~93%, Kynoar 5~8% and second
Acetylene black 2~5%；
Electrode slurry is coated on the flexible current-collecting body that thickness is 5 μm~80 μm, in 80 DEG C~120 DEG C of vacuum drying oven
After middle drying, cathode pole piece is obtained.
Present invention also offers a kind of battery comprising above-mentioned electrode.
Compared with prior art, beneficial effects of the present invention are：
The battery prepared using electrode of the invention, can effectively reduce the interface internal resistance of battery, reduce unit area electrode
Quality, improves its mass energy density；Because flexible current-collecting body of the invention has preferably machinery to add relative to conventional metals paper tinsel
Work performance, this can also improve the production efficiency of battery, reduce production cost；Collector substrate of the invention is macromolecular material,
Fusing can be shunk in high temperature, the security performance of battery is improve.
Brief description of the drawings
Fig. 1 is the cross section structure schematic diagram of flexible current-collecting body of the invention；
Fig. 2 is the structural representation of single fiber in flexible current-collecting body of the invention；
Fig. 3 is the cross section structure schematic diagram of electrode of the invention.
Wherein：1st, flexible current-collecting body；2nd, conductive fiber；3rd, textile substrate fiber；4th, metallic conduction coating；5th, electrode active
Property material.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
As shown in figure 1, flexible current-collecting body of the invention 1 is formed by the braiding of conductive fiber 2, as shown in Fig. 2 conductive fiber 2
Including textile substrate fiber 3 and the metallic conduction coating 4 being coated on textile substrate fiber 3.
As shown in figure 3, electrode of the invention includes flexible current-collecting body 1 and is supported on the surface and/or hole of flexible current-collecting body 1
Electrode active material 5 in gap.
Flexible current-collecting body of the invention can be prepared by following technique：
(1) after being respectively washed textile substrate cloth acetone, alcohol, its surface is activated with UV plasmas；
(2) preliminary metal coating, nickel film are carried out on textile substrate cloth two sides with target using the method for vacuum sputtering
Thick 50nm~200nm；
(3) electrophoretic techniques is utilized, using the method copper facing plating successively of metal plating on the copper film on textile substrate surface
Film and nickel plated film.
Embodiment 1
The gross thickness of the flexible current-collecting body for preparing is 35 μm, and its textile substrate has 4 layers, and material is terylene, terylene
A diameter of 7~10 μm of fiber, the material of metallic conduction coating is copper-nickel, and gross thickness is 2 μm.
After measured, the mass area ratio of flexible current-collecting body is 37g/m2, sheet resistivity is~35m Ω；
5 hours baking percent thermal shrinkage ＜ 1%, resistance variations ＜ 2% at 120 DEG C；180 ° are bent by 1em of bending radius
More than 20000 times, resistance variations ＜ 2%.
Embodiment 2
The gross thickness of the flexible current-collecting body for preparing is 45 μm, and its textile substrate is of five storeys, and material is terylene, terylene
A diameter of 7~10 μm of fiber, the material of metallic conduction coating is copper, and gross thickness is 2 μm.
After measured, the mass area ratio of flexible current-collecting body is 50g/m2, sheet resistivity is~25m Ω；
5 hours baking percent thermal shrinkage ＜ 1%, resistance variations ＜ 2% at 120 DEG C；180 ° are bent by 1cm of bending radius
More than 20000 times, resistance variations ＜ 2%.
Embodiment 3
The gross thickness of the flexible current-collecting body for preparing is 35 μm, and its textile substrate has 4 layers, and material is terylene, terylene
A diameter of 7~10 μm of fiber, the material of metallic conduction coating is aluminium, and gross thickness is 3 μm.
After measured, the mass area ratio of flexible current-collecting body is 23g/m2, sheet resistivity is~45m Ω；
5 hours baking percent thermal shrinkage ＜ 1%, resistance variations ＜ 2% at 120 DEG C；180 ° are bent by 1cm of bending radius
More than 20000 times, resistance variations ＜ 2%.
Embodiment 4
Ternary material NCM is chosen as positive electrode, is dissolved in 1-METHYLPYRROLIDONE after mixing with PVDF and acetylene black,
Prepare anode sizing agent；By weight percentage, in the mixture of ternary material NCM, PVDF and acetylene black, ternary material NCM
It is that 94%, PVDF is 3%, acetylene black is 3%；
Then anode sizing agent is coated on flexible current-collecting body prepared by embodiment 1, coating thickness is 0.15mm, 120
It is dried in DEG C vacuum drying oven and obtains anode pole piece.
Similarly, negative material is done with graphite, is dissolved in 1-METHYLPYRROLIDONE after mixing with PVDF and acetylene black, prepared
Cathode size；By weight percentage, in the mixture of graphite, PVDF and acetylene black, graphite is that 94%, PVDF is 3%, acetylene
Black is 3%；
Then cathode size is coated on flexible current-collecting body prepared by embodiment 1, coats thickness 0.08mm, it is true at 100 DEG C
It is dried in empty baking oven and obtains cathode pole piece.
Above-mentioned anode pole piece, cathode pole piece and membrane layer poststack are encapsulated with aluminum plastic film, electrolysis is injected in glove box
Liquid post heat-seal, obtains final lithium ion battery.
Battery testing obtained by more than, its energy density is 180Wh/kg (@2C), loop test 1000 times, its appearance
Amount is maintained at more than 85%.
Embodiment 5
Ternary material NCM is chosen as positive electrode, is dissolved in 1-METHYLPYRROLIDONE after mixing with PVDF and acetylene black,
Prepare anode sizing agent；By weight percentage, in the mixture of ternary material NCM, PVDF and acetylene black, ternary material NCM
It is that 94%, PVDF is 3%, acetylene black is 3%；
Then anode sizing agent is coated on the aluminium foil of 20 μ m-thicks, coating thickness is 0.15mm, is entered in 120 DEG C of vacuum drying ovens
Row is dried to obtain anode pole piece.
Similarly, negative material is done with graphite, is dissolved in 1-METHYLPYRROLIDONE after mixing with PVDF and acetylene black, prepared
Cathode size；By weight percentage, in the mixture of graphite, PVDF and acetylene black, graphite is that 94%, PVDF is 3%, acetylene
Black is 3%；
Then cathode size is coated on flexible current-collecting body prepared by embodiment 1, coats thickness 0.08mm, it is true at 100 DEG C
It is dried in empty baking oven and obtains cathode pole piece.
Above-mentioned anode pole piece, cathode pole piece and membrane layer poststack are encapsulated with aluminum plastic film, electrolysis is injected in glove box
Liquid post heat-seal, obtains final lithium ion battery.
Battery testing obtained by more than, its energy density is 170Wh/kg (@2C), loop test 1000 times, its appearance
Amount is maintained at more than 85%.
Embodiment 6
Ternary material NCM is chosen as positive electrode, is dissolved in 1-METHYLPYRROLIDONE after mixing with PVDF and acetylene black,
Prepare anode sizing agent；By weight percentage, in the mixture of ternary material NCM, PVDF and acetylene black, ternary material NCM
It is that 94%, PVDF is 3%, acetylene black is 3%；
Then anode sizing agent is coated on flexible current-collecting body prepared by embodiment 1, coating thickness is 0.15mm, 120
It is dried in DEG C vacuum drying oven and obtains anode pole piece.
Similarly, negative material is done with graphite, is dissolved in 1-METHYLPYRROLIDONE after mixing with PVDF and acetylene black, prepared
Cathode size；By weight percentage, in the mixture of graphite, PVDF and acetylene black, graphite is that 94%, PVDF is 3%, acetylene
Black is 3%；
Then cathode size is coated on the Copper Foil of 10 μ m-thicks, coats thickness 0.08mm, carried out in 100 DEG C of vacuum drying ovens
It is dried to obtain cathode pole piece.
Above-mentioned anode pole piece, cathode pole piece and membrane layer poststack are encapsulated with aluminum plastic film, electrolysis is injected in glove box
Liquid post heat-seal, obtains final lithium ion battery.
Battery testing obtained by more than, its energy density is 155Wh/kg (@2C), loop test 1000 times, its appearance
Amount is maintained at more than 85%.
Claims (10)
1. a kind of flexible current-collecting body, it is characterised in that including textile substrate and metallic conduction coating, metallic conduction coating cladding
On the fiber of textile substrate；
The thickness of the metallic conduction coating is 200nm~5 μm.
2. flexible current-collecting body according to claim 1, it is characterised in that the number of plies of described textile substrate is 2~5；
A diameter of 1 μm~30 μm of the fiber.
3. flexible current-collecting body according to claim 1, it is characterised in that the thickness of described flexible current-collecting body is 5 μm~
80μm。
4. flexible current-collecting body according to claim 1, it is characterised in that the porosity of described flexible current-collecting body is 20%
~85%.
5. flexible current-collecting body according to claim 1, it is characterised in that described metallic conduction coating is from inside to outside successively
Including copper coating and nickel coating；
The thickness of the copper coating is 100nm~3 μm；
The thickness of the nickel coating is 100nm~2 μm.
6. a kind of electrode, including collector and electrode active material, it is characterised in that described collector is such as claim 1
Flexible current-collecting body described in~5 any one；
Described electrode active material is carried in the surface of described flexible current-collecting body and/or hole.
7. a kind of preparation method of electrode as claimed in claim 6, it is characterised in that including：
Electrode active material is made electrode slurry, is coated on the flexible current-collecting body that thickness is 5 μm~80 μm, 80 DEG C~
After being dried in 120 DEG C of vacuum drying oven, described electrode is obtained；
Electrode slurry coating thickness is 30 μm~350 μm.
8. the preparation method of electrode according to claim 7, it is characterised in that electrode active material is dissolved in N- methyl pyrroles
Electrode slurry is obtained in pyrrolidone, by weight percentage, described electrode active material includes：Tertiary cathode material 87~
95%th, Kynoar 3~7% and acetylene black 2~6%.
9. the preparation method of electrode according to claim 7, it is characterised in that electrode active material is dissolved in N- methyl pyrroles
Electrode slurry is obtained in pyrrolidone, by weight percentage, described electrode active material includes：Graphite material 87~93%,
Kynoar 5~8% and acetylene black 2~5%.
10. a kind of battery, it is characterised in that including electrode as claimed in claim 6.
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| CN201710189749.9A CN106898729A (en) | 2017-03-27 | 2017-03-27 | Flexible current-collecting body, electrode and battery comprising the flexible current-collecting body |
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Application publication date: 20170627 |