CN106654286B - A kind of flexible electrode and preparation method thereof - Google Patents
A kind of flexible electrode and preparation method thereof Download PDFInfo
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- CN106654286B CN106654286B CN201611033633.8A CN201611033633A CN106654286B CN 106654286 B CN106654286 B CN 106654286B CN 201611033633 A CN201611033633 A CN 201611033633A CN 106654286 B CN106654286 B CN 106654286B
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- conductive
- basal layer
- layer
- flexible
- sunk structure
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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
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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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
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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
The invention discloses a kind of flexible electrodes, including conductive basal layer and active material, sunk structure is evenly equipped on the conductive basal layer, the area of the sunk structure accounts for the 20~90% of the conductive basal layer gross area, the depth of sunk structure is 1~500 μm, and the area of single sunk structure is 1 μm2~25mm2；The active material has on dimpled texture surface coated in conductive basal layer；The conductive basal layer is metal foil or plastic-metal plated film.The active material layer that flexible electrode of the invention is readily able to fracture separates in small sunk structure, is greatly improved the flexible bending performance of flexible electrode, bending radius > 5mm.
Description
Technical field
The present invention relates to flexible technical field of energy storage more particularly to a kind of flexible electrode and preparation method thereof.
Background technique
Since energy density is high, good reliability and environmental-protecting performance are excellent, lithium battery has become most important in the market
One of energy storage device is widely used in the portable electronic products such as digital camera, mobile phone and laptop.
With being increasingly miniaturized for electronic equipment, recent wearable device obtains rise and rapid development, while soft
Property hull cell become concern emphasis.Using traditional battery processing technology, made flexible thin-film battery bending effect
It is limited, therefore the Each part in battery how is designed to improve whole bending resistance as those skilled in the art's
Research topic.
For at present, the method for enhancing cell flexible has: (1) it is using more baby batteries series-parallel, then enclosed inside, reach
Flexible demand, this technology using the watchband type batterypatent of APPLE company as representative, its shortcoming is that, baby battery manufacture is difficult,
High production cost, it is difficult to which industrialization is realized；More batteries can generate battery capacity and voltage in series and parallel unevenly to be caused to want attached
Add control circuit and leads to the problem of security risk；(2) electrode prepared by flexible material, but the disadvantage is that flexible material are used
It is not easy to prepare, it is at high cost, and performance is different is surely protected.
For example, the Chinese patent literature of Publication No. CN104078248A disclose a kind of flexible electrode preparation method and
Its flexible electrode prepared, the preparation method include: a. that evenly dispersed mixing point is made in carbon nanotube and graphene oxide
Dispersion liquid；B. the solvent in mixed dispersion liquid is removed, the film with three-dimensional conductive network is made；C. in three-dimensional conductive network thin-film
Middle in-situ polymerization organic macromolecule conducting material obtains ternary flexible compound film；D. by the oxidation stone in ternary flexible compound film
Black alkene reduction, i.e. acquisition flexible electrode.The flexible electrode preparation method is complicated, and preparation cost is higher.
Summary of the invention
The present invention provides a kind of flexible electrode and preparation method thereof, which mainly includes with fine pits knot
The conductive basal layer of structure and the active material layer combined closely with it, the flexible electrode have excellent mechanical winding performance.
The invention discloses a kind of flexible electrode, including conductive basal layer and active material, on the conductive basal layer
It is evenly equipped with sunk structure, the area of the sunk structure accounts for the 20~90% of the conductive basal layer gross area, the depth of sunk structure
Degree is 1~500 μm, and the area of single sunk structure is 1 μm2~25mm2；
The active material has on dimpled texture surface coated in conductive basal layer；
The conductive basal layer is metal foil or plastic-metal plated film.
In flexible electrode of the invention, active material is filled in conductive basal layer depression in the surface structure, adjacent recessed
Active material in structure can be connected with each other, and the thickness of junction active material is greater than 0 and is less than 1mm；Adjacent recessed structure
Interior active material can also be not connected to.
Sunk structure can be round, oval, rectangular, strip, triangle or other irregular shapes.
The active material layer that flexible electrode of the invention is readily able to fracture separates in small sunk structure, can mention significantly
The flexible bending performance of high flexibility electrode.
The ratio that the area of sunk structure accounts for the conductive basal layer gross area is excessive or too small cannot all effectively improve flexible electrical
The flexibility of pole, preferably, the area of the sunk structure accounts for the 70~85% of the conductive basal layer gross area.
Conductive basal layer is metal foil or plastic-metal plated film, in order to guarantee the mechanical strength of conductive basal layer, to conduction
The thickness of basal layer have certain requirement, preferably, conductive basal layer with a thickness of 1~100 μm.The conductive base of the thickness
Bottom mechanical strength with higher has enough flexibilities simultaneously.
It is further preferred that the conductive basal layer with a thickness of 1~50 μm；It is further preferred that the conduction
Basal layer with a thickness of 3~8 μm.
The conductive basal layer is metal foil or plastic-metal plated film, in mechanical strength having the same and electric conductivity
Under the premise of, it is thinner needed for plastic-metal plated film, the mass density of flexible electrode can be substantially reduced, to improve it
Energy density, preferably, the conductive basal layer is plastic-metal plated film, the plastic-metal plated film includes successively tight
Flexible base layer, metallic conduction coating and the conductive anti oxidation layer of close combination；
The flexible base layer is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate
One of ester, dimethyl silicone polymer and polyimides, the flexible base layer with a thickness of 1~20 μm；
The metallic conduction coating is one of Cu, Al, Ni, Au and Ag, the thickness of the metallic conduction coating
It is 0.1~5 μm；
The conductive anti oxidation layer includes at least one in electrically conductive graphite, graphene, carbon nanotube and carbon nano-fiber
Kind, the thickness of the conductive anti oxidation layer is greater than 0 and less than 1 μm.
The conductive basal layer uses three-decker, utilizes the mechanical machinability of flexible base layer enhancing conductive basal layer
Energy；The quality that conductive basal layer entirety can be greatly lowered in metallic conduction coating while not influencing its practical electric conductivity is close
Degree, the 1/10~1/5 of the only traditional copper foil of mass density, aluminium foil, the quality of battery can be greatly reduced, the energy of battery is improved
Density；Conductive anti oxidation layer can improve the thermal stability and anti-oxidant energy of conductive basal layer, while can reduce its contact resistance,
Improve the performance of battery fast charging and discharging.
Preferably, the flexible base layer is polyethylene terephthalate；The metallic conduction coating is
Cu or Al.
Binding force between polyethylene terephthalate and Cu or Al is larger, is with polyethylene terephthalate
Flexible base layer, when using Cu or Al as metallic conduction coating, the better mechanical property of flexible current-collecting body.
Preferably, the flexible base layer with a thickness of 1~5 μm；The metallic conduction coating with a thickness of 0.2
~5 μm.
The flexible base layer of the thickness further reduced flexibility while the mechanical strength that can guarantee flexible current-collecting body
The weight of collector.Metallic conduction coating with a thickness of 0.2~5 μm when can play good catchment effect and effectively drop
The weight of less flexible collector.
Preferably, the conductive anti oxidation layer includes graphene or carbon nanotube, the conductive anti oxidation layer
With a thickness of 80~100nm.
When conductive anti oxidation layer is graphene or carbon nanotube, antioxygenic property is more preferable, is not influencing its inoxidizability
Under the premise of energy, the thickness of the conduction anti oxidation layer can be thinner, further decreases the weight of flexible current-collecting body.
The flexible electrode includes cathode and anode, preferably, the flexible base layer of the cathode is poly- to benzene
Naphthalate, metallic conduction coating are Cu, and active material is graphite；The flexible base layer of the anode is poly- to benzene
Naphthalate, metallic conduction coating are Al, and active material is LiFePO4.
The present invention also provides the preparation methods of the flexible electrode, comprising the following steps:
(1) conductive basal layer is placed on on reeded mold, the groove on mold connects vacuum plant；
(2) mold is vacuumized, conductive basal layer is made to form sunk structure corresponding with groove；
(3) by the slurry blade coating of active material on the surface of the conductive basal layer with sunk structure, and make conductive base
The surfacing of bottom；
(4) conductive basal layer after blade coating active material slurry after dry 1~30min, is closed true at 60~150 DEG C
Empty device, removes mold, obtains flexible electrode.
The preparation method is easy to operate, and the yield rate of product is higher.
Preferably, vacuumizing in step (2) to mold, vacuum degree is 1 × 10-6~1 × 10-3Pa；Further preferably
, vacuum degree is 1 × 10-5~1 × 10-4Pa。
Preferably, in step (4), by the conductive basal layer after blade coating active material slurry dry 5 at 80~120 DEG C
After~10min, vacuum plant is closed, mold is removed, obtains flexible electrode.
Compared with prior art, the invention has the benefit that
The active material layer that flexible electrode of the invention is readily able to fracture separates in small sunk structure, can mention significantly
The flexible bending performance of high flexibility electrode, bending radius > 5mm.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flexible electrode prepared by embodiment 1；
Fig. 2 is the sectional view of flexible electrode in Fig. 1；
Fig. 3 is the structural schematic diagram of flexible electrode prepared by embodiment 2；
Fig. 4 is the sectional view along sunk structure width direction of flexible electrode in Fig. 2；
Fig. 5 is the sectional view along sunk structure length direction of flexible electrode in Fig. 2.
Specific embodiment
Embodiment 1
As depicted in figs. 1 and 2, flexible electrode includes conductive basal layer 2 and active material.It is evenly equipped on conductive basal layer 2
Sunk structure 1, sunk structure 1 are hemispherical, and radius is 200 μm, and depth is~50 μm, and active material 3, which is filled out, is overlying on sunk structure 1
Interior, conductive basal layer 2 is the copper foil of 8 μ m-thicks, and active material is graphite.
The preparation method comprises the following steps:
It chooses with a thickness of 8 μm of copper foil as conductive basal layer, places it in that be connected with having for vacuum pump round
It on the mold of groove, opens aspiration pump (220V), copper foil is made to generate uniform fine pits structure according to the appearance of circular groove,
The radius of circular groove is 200 μm, and depth is~50 μm；
Configured graphitic carbon negative electrode active slurry is coated in the copper foil surface with fine pits structure again, makes graphitic carbon
Negative electrode active slurry, which is filled out, to be covered in these fine pits structures, the electrode being painted with is dried in 120 degrees Celsius of atmosphere, to electrode
Active slurry again closes vacuum pump after curing molding in these fine pits structures；
Electrode is removed, battery preparation and encapsulation are prepared.
Embodiment 2
It chooses with a thickness of 15 μm of aluminium foil as conductive basal layer, places it in that be connected with having for vacuum pump round
It on the mold of groove, opens aspiration pump (220V), copper foil is made to generate uniform fine pits structure according to the appearance of circular groove,
The radius of circular groove is 200 μm, and depth is~50 μm；
Configured iron phosphate lithium positive pole active slurry is coated in the copper foil surface with fine pits structure again, makes phosphoric acid
Iron lithium positive-active slurry, which is filled out, to be covered in these fine pits structures, and the electrode being painted with is dried in 120 degrees Celsius of atmosphere, to
Electrode active material slurry again closes vacuum pump after curing molding in these fine pits structures；
Electrode is removed, battery preparation and encapsulation are prepared.
Positive and negative anodes flexible electrode made from embodiment 1 and embodiment 2 is passed through into battery assembly and test, energy density is
105Wh/kg (@0.2C), makees the battery assembled to the flexible electrode and is folded and be bent (compound bending), electrical property is not shown
Variation is write, cycle performance is unaffected, the bending number of test 2000 times, and loop test 1000 times.
Embodiment 3
As shown in Fig. 3, Fig. 4 and Fig. 5, flexible electrode includes conductive basal layer 2 and active material.On conductive basal layer 2
It is furnished with sunk structure 1, sunk structure 1 is semielliptical shape, and the width of sunk structure 1 is 200 μm, and length is 1000 μm, and depth is
~50 μm, active material, which is filled out, to be overlying in sunk structure 1, and conductive basal layer 2 is the aluminium foil of 15 μ m-thicks, and active material is graphite.
The preparation method comprises the following steps:
Choose with a thickness of 4.8 μm or so polyethylene terephthalate (PET) plating copper foil (PET film thickness be 3.8 μm,
Plated copper film is 1 μm or so) it is used as conductive basal layer, place it in the mould with half elliptic groove for being connected with vacuum pump
It on tool, opens aspiration pump (220V), PET plating copper foil is made to generate uniform fine pits knot according to the appearance of half elliptic groove
Structure, the width of half elliptic groove are 200 μm, and length is 1000 μm, and depth is~50 μm；
Configured graphitic carbon negative electrode active slurry is coated in the plating copper foil surface of the PET with fine pits structure again, is made
Graphitic carbon negative electrode active slurry, which is filled out, to be covered in these fine pits structures, and the electrode being painted with is dried in 120 degrees Celsius of atmosphere,
Vacuum pump is closed again after curing molding in these fine pits structures to electrode active material slurry；
Electrode is removed, battery preparation and encapsulation are prepared.
Embodiment 4
Choose with a thickness of 4.8 μm or so polyethylene terephthalate (PET) plating copper foil (PET film thickness be 3.8 μm,
Plated copper film is 1 μm or so) it is used as conductive basal layer, place it in the mould with half elliptic groove for being connected with vacuum pump
It on tool, opens aspiration pump (220V), PET plating copper foil is made to generate uniform fine pits knot according to the appearance of half elliptic groove
Structure, the width of half elliptic groove are 200 μm, and length is 1000 μm, and depth is~50 μm；
Configured iron phosphate lithium positive pole active slurry is coated in the plating copper foil surface of the PET with fine pits structure again,
Make iron phosphate lithium positive pole active slurry fill out cover in these fine pits structures, by the electrode being painted in 120 degrees Celsius of atmosphere
It is dry, vacuum pump is closed again after curing molding in these fine pits structures to electrode active material slurry；
Electrode is removed, battery preparation and encapsulation are prepared.
Positive and negative anodes flexible electrode made from embodiment 3 and embodiment 4 is passed through into battery assembly and test, energy density is
110Wh/kg (@0.2C) makees the battery assembled to the flexible electrode and is folded and be bent (along the length direction list of sunk structure
To bending), electrical property does not have significant changes, and cycle performance is unaffected, the bending number of test 2000 times, loop test 1000
It is secondary.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that
Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention
Any modification, supplementary, and equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of flexible electrode, including conductive basal layer and active material, which is characterized in that uniformly distributed on the conductive basal layer
There is sunk structure, the area of the sunk structure accounts for the 20~90% of the conductive basal layer gross area, and the depth of sunk structure is 1
~500 μm, the area of single sunk structure is 1 μm2~25mm2；
The active material has on dimpled texture surface coated in conductive basal layer；
The conductive basal layer is metal foil or plastic-metal plated film.
2. flexible electrode according to claim 1, which is characterized in that the area of the sunk structure accounts for conductive basal layer
The 70~85% of the gross area.
3. flexible electrode according to claim 1, which is characterized in that conductive basal layer with a thickness of 1~100 μm.
4. flexible electrode according to claim 1, which is characterized in that the conductive basal layer is plastic-metal plated film,
The plastic-metal plated film includes the flexible base layer successively combined closely, metallic conduction coating and conductive anti oxidation layer；
The flexible base layer is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, gathers
One of dimethyl siloxane and polyimides, the flexible base layer with a thickness of 1~20 μm；
The metallic conduction coating is one of Cu, Al, Ni, Au and Ag, the metallic conduction coating with a thickness of 0.1
~5 μm；
The conductive anti oxidation layer includes at least one of electrically conductive graphite, graphene, carbon nanotube and carbon nano-fiber, institute
The thickness for the conductive anti oxidation layer stated is greater than 0 and less than 1 μm.
5. flexible electrode according to claim 4, which is characterized in that the flexible base layer is poly terephthalic acid second
Diol ester；The metallic conduction coating is Cu or Al.
6. flexible electrode according to claim 5, which is characterized in that the flexible base layer with a thickness of 1~5 μm；
The metallic conduction coating with a thickness of 0.2~5 μm.
7. flexible electrode according to claim 4, which is characterized in that the conductive anti oxidation layer includes graphene or carbon
Nanotube, the conductive anti oxidation layer with a thickness of 80~100nm.
8. the preparation method of described in any item flexible electrodes according to claim 1~7, which comprises the following steps:
(1) conductive basal layer is placed on on reeded mold, the groove on mold connects vacuum plant；
(2) mold is vacuumized, conductive basal layer is made to form sunk structure corresponding with groove；
(3) by the slurry blade coating of active material on the surface of the conductive basal layer with sunk structure, and make conductive basal layer
Surfacing；
(4) conductive basal layer after blade coating active material slurry after dry 1~30min, is closed into vacuum holding at 60~150 DEG C
It sets, removes mold, obtain flexible electrode.
9. preparation method according to claim 8, which is characterized in that in step (2), vacuumized to mold, vacuum degree 1
×10-6~1 × 10-3Pa。
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| CN201611033633.8A CN106654286B (en) | 2016-11-18 | 2016-11-18 | A kind of flexible electrode and preparation method thereof |
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| CN201611033633.8A CN106654286B (en) | 2016-11-18 | 2016-11-18 | A kind of flexible electrode and preparation method thereof |
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| CN106654286B true CN106654286B (en) | 2019-06-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110197893A (en) * | 2019-06-19 | 2019-09-03 | 珠海格力电器股份有限公司 | Pole piece, battery core and battery modules |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071860A (en) * | 2007-06-08 | 2007-11-14 | 大连理工大学 | Flexible current-collecting body |
| CN202034434U (en) * | 2010-09-30 | 2011-11-09 | 东莞新能源科技有限公司 | Lithium ion battery positive plate and lithium ion battery with positive plate |
| CN102303007A (en) * | 2011-09-02 | 2012-01-04 | 深圳市格瑞普电池有限公司 | Method for coating electrode plate for lithium ion battery, electrode plate for lithium ion battery, and lithium ion battery |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN103367702A (en) * | 2013-07-18 | 2013-10-23 | 东莞新能源科技有限公司 | Lithium ion battery pole piece and lithium ion battery comprising pole piece |
-
2016
- 2016-11-18 CN CN201611033633.8A patent/CN106654286B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071860A (en) * | 2007-06-08 | 2007-11-14 | 大连理工大学 | Flexible current-collecting body |
| CN202034434U (en) * | 2010-09-30 | 2011-11-09 | 东莞新能源科技有限公司 | Lithium ion battery positive plate and lithium ion battery with positive plate |
| CN102303007A (en) * | 2011-09-02 | 2012-01-04 | 深圳市格瑞普电池有限公司 | Method for coating electrode plate for lithium ion battery, electrode plate for lithium ion battery, and lithium ion battery |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN103367702A (en) * | 2013-07-18 | 2013-10-23 | 东莞新能源科技有限公司 | Lithium ion battery pole piece and lithium ion battery comprising pole piece |
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