CN106654286A - Flexible electrode and preparation method thereof - Google Patents
Flexible electrode and preparation method thereof Download PDFInfo
- Publication number
- CN106654286A CN106654286A CN201611033633.8A CN201611033633A CN106654286A CN 106654286 A CN106654286 A CN 106654286A CN 201611033633 A CN201611033633 A CN 201611033633A CN 106654286 A CN106654286 A CN 106654286A
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- Prior art keywords
- conductive
- basal layer
- flexible electrode
- layer
- flexible
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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
-
- 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
-
- 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 flexible electrode which comprises a conductive base layer and an active material, wherein sunken structures are uniformly distributed on the conductive base layer; the area of the sunken structures is 20-90% of the total area of the conductive base layer; the depth of the sunken structures is 1-500 microns; the area of a single sunken structure is 1 micron<2>-25mm<2>; the surface of the conductive base layer with the sunken structures is coated with the active material; the conductive base layer is arranged as a metal foil or plastic metal coating. According to the flexible electrode provided by the invention, the easily broken active materials are separated in the micro-sunken structures, so that the flexible bending property of the flexible electrode is greatly increased and the bending radius is more than 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 technology
Because energy density is high, good reliability and environmental-protecting performance are excellent, lithium battery has become most important on 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 being increasingly miniaturized for electronic equipment, recent Wearable device is risen and is developed rapidly, while soft
Property hull cell becomes the emphasis of concern.Using traditional battery processing technology, made flexible thin-film battery bending effect
It is limited, therefore how to design the Each part in battery and become those skilled in the art's improving overall bending resistance
Research topic.
For at present, strengthening the method for cell flexible has：(1) using many baby battery connection in series-parallel, then enclosed inside, reach
Flexible demand, this technology with the watchband type batterypatent of APPLE companies as representative, itself the disadvantage is that, baby battery manufacture is difficult,
Production cost is high, it is difficult to which industrialization is realized；Many battery series-parallel connections can produce battery capacity and voltage is uneven and cause attached
Plus the problem of control circuit and generation potential safety hazard；(2) using the electrode prepared by flexible material, but it has the disadvantage flexible material
It is difficult to prepare, high cost, and performance differs and be surely protected.
For example, the Chinese patent literature of Publication No. CN104078248A disclose a kind of flexible electrode preparation method and
Its flexible electrode for preparing, the preparation method includes：A. CNT and graphene oxide are made into homodisperse mixing point
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
Situ polymerization organic macromolecule conducting material, obtains ternary flexible compound film；D. by the oxidation stone in ternary flexible compound film
Black alkene reduction, that is, obtain flexible electrode.The flexible electrode preparation method is complicated, and preparation cost is higher.
The content of the invention
The invention provides a kind of flexible electrode and preparation method thereof, the flexible electrode mainly includes being tied with fine pits
The conductive basal layer of structure and the active material layer combined closely with it, the flexible electrode has excellent machinery winding performance.
The invention discloses a kind of flexible electrode, including conductive basal layer and active material, on described conductive basal layer
Sunk structure is evenly equipped with, the area of described sunk structure accounts for the 20～90% of the conductive basal layer gross area, the depth of sunk structure
Spend for 1～500 μm, the area of single sunk structure is 1 μm2～25mm2；
Described active material be coated in conductive basal layer with dimpled texture surface；
Described conductive basal layer is metal forming or plastic-metal plated film.
In the flexible electrode of the present 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 more than 0 and less than 1mm；Adjacent recessed structure
Interior active material can also be not connected to.
Sunk structure can be for circular, oval, square, strip, triangle or other are irregularly shaped.
The active material layer that the flexible electrode of the present invention is readily able to rupture separates in small sunk structure, can carry 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 can not all effectively improve flexible electrical
The pliability of pole, preferably, the area of described sunk structure accounts for the 70～85% of the conductive basal layer gross area.
Conductive basal layer is metal forming or plastic-metal plated film, in order to ensure the mechanical strength of conductive basal layer, to conduction
The thickness of basalis has certain requirement, preferably, the thickness of conductive basal layer is 1～100 μm.The conductive base of the thickness
There is bottom higher mechanical strength to have enough pliabilities simultaneously.
It is further preferred that the thickness of described conductive basal layer is 1～50 μm；It is further preferred that described conduction
The thickness of basalis is 3～8 μm.
Described conductive basal layer is metal forming or plastic-metal plated film, with identical mechanical strength and electric conductivity
On the premise of, the thickness needed for plastic-metal plated film is thinner, can substantially reduce the mass density of flexible electrode, so as to improve it
Energy density, preferably, described conductive basal layer is plastic-metal plated film, described plastic-metal plated film includes tight successively
The flexible base layer of close combination, metallic conduction coating and conductive anti oxidation layer；
Described flexible base layer is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate
One kind in ester, dimethyl silicone polymer and polyimides, the thickness of described flexible base layer is 1～20 μm；
Described metallic conduction coating is the one kind in Cu, Al, Ni, Au and Ag, the thickness of described metallic conduction coating
For 0.1～5 μm；
Described conductive anti oxidation layer includes at least in electrically conductive graphite, Graphene, CNT and carbon nano-fiber
Kind, the thickness of described conductive anti oxidation layer is more than 0 and less than 1 μm.
The conductive basal layer adopts three-decker, and using flexible base layer the mechanical machinability of conductive basal layer is strengthened
Energy；It is close that metallic conduction coating can be greatly lowered conductive basal layer overall quality while its practical electric conductivity is not affected
Degree, its mass density be only traditional Copper Foil, the 1/10～1/5 of aluminium foil, the quality of battery can be greatly reduced, improve the energy of battery
Density；Conductive anti oxidation layer can improve the heat endurance of conductive basal layer and anti-oxidant energy, while its contact resistance can be reduced,
Improve the performance of battery fast charging and discharging.
Preferably, described flexible base layer is polyethylene terephthalate；Described metallic conduction coating is
Cu or Al.
Adhesion between polyethylene terephthalate and Cu or Al is larger, is with polyethylene terephthalate
Flexible base layer, during with Cu or Al as metallic conduction coating, the better mechanical property of flexible current-collecting body.
Preferably, the thickness of described flexible base layer is 1～5 μm；The thickness of described metallic conduction coating is 0.2
～5 μm.
The flexible base layer of the thickness reduce further flexibility while can guarantee that the mechanical strength of flexible current-collecting body
The weight of collector.The thickness of metallic conduction coating can play good catchment effect when being 0.2～5 μm, can effectively drop again
The weight of less flexible collector.
Preferably, described conductive anti oxidation layer includes Graphene or CNT, described conductive anti oxidation layer
Thickness is 80～100nm.
When conductive anti oxidation layer is Graphene or CNT, its antioxygenic property more preferably, is not affecting its non-oxidizability
On the premise of energy, the thickness of the conductive anti oxidation layer can be thinner, further reduces the weight of flexible current-collecting body.
Described flexible electrode includes negative pole and positive pole, preferably, the flexible base layer of described negative pole is to gather to benzene
Naphthalate, metallic conduction coating is Cu, and active material is graphite；The flexible base layer of described positive pole is for poly- to benzene
Naphthalate, metallic conduction coating is Al, and active material is LiFePO4.
Present invention also offers the preparation method of the flexible electrode, comprises the following steps：
(1) conductive basal layer is placed on the groove connection vacuum plant on reeded mould, on mould；
(2) mould is vacuumized, makes conductive basal layer form sunk structure corresponding with groove；
(3) slurry of active material is scratched on the surface of the conductive basal layer with sunk structure, and makes conductive base
The surfacing of bottom；
(4) after the conductive basal layer after blade coating active material slurry being dried into 1～30min at 60～150 DEG C, close true
Empty device, mold removal obtains flexible electrode.
The preparation method is simple to operate, and the yield rate of product is higher.
Preferably, in step (2), vacuumizing to mould, vacuum is 1 × 10-6～1 × 10-3Pa；Further preferably
, vacuum is 1 × 10-5～1 × 10-4Pa。
Preferably, in step (4), the conductive basal layer after blade coating active material slurry is dried into 5 at 80～120 DEG C
After～10min, vacuum plant is closed, mold removal obtains flexible electrode.
Compared with prior art, beneficial effects of the present invention are：
The active material layer that the flexible electrode of the present invention is readily able to rupture separates in small sunk structure, can carry significantly
The flexible bending performance of high flexibility electrode, its bending radius ＞ 5mm.
Description of the drawings
Fig. 1 is the structural representation of flexible electrode prepared by embodiment 1；
Fig. 2 is the profile of flexible electrode in Fig. 1；
Fig. 3 is the structural representation of flexible electrode prepared by embodiment 2；
Fig. 4 is the profile along sunk structure width of flexible electrode in Fig. 2；
Fig. 5 is the profile 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 with conductive basal layer 2
Sunk structure 1, sunk structure 1 is hemispherical, and radius is 200 μm, and depth is～50 μm, and active material 3 is filled out and 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.
Preparation method is：
Copper Foil that thickness is 8 μm is chosen as conductive basal layer, be placed on be connected with vacuum air pump with circle
On the mould of groove, aspiration pump (220V) is opened, makes Copper Foil produce uniform fine pits structure according to the appearance of circular groove,
The radius of circular groove is 200 μm, and depth is～50 μm；
Again the graphitic carbon negative electrode active slurry for having configured is coated in into the copper foil surface with fine pits structure, makes graphitic carbon
Negative electrode active slurry is filled out and covered with these fine pits structures, and the electrode being painted with is dried in 120 degrees Celsius of atmosphere, treats electrode
Active slurry again closes vacuum air pump after curing molding in these fine pits structures；
Electrode is removed, is prepared battery and is prepared and encapsulate.
Embodiment 2
Aluminium foil that thickness is 15 μm is chosen as conductive basal layer, be placed on be connected with vacuum air pump with circle
On the mould of groove, aspiration pump (220V) is opened, makes Copper Foil produce uniform fine pits structure according to the appearance of circular groove,
The radius of circular groove is 200 μm, and depth is～50 μm；
Again the iron phosphate lithium positive pole active slurry for having configured is coated in into the copper foil surface with fine pits structure, makes phosphoric acid
Iron lithium positive-active slurry is filled out and covered with these fine pits structures, and the electrode being painted with is dried in 120 degrees Celsius of atmosphere, is treated
Electrode active material slurry again closes vacuum air pump after curing molding in these fine pits structures；
Electrode is removed, is prepared battery and is prepared and encapsulate.
By embodiment 1 and both positive and negative polarity flexible electrode obtained in embodiment 2 through battery Integration Assembly And Checkout, energy density is
105Wh/kg (@0.2C), the battery for assembling is made to the flexible electrode and is folded and is bent (compound bending), and electrical property does not show
Change is write, cycle performance is unaffected, the bending number of times of test 2000 times, 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
Sunk structure 1 is furnished with, 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 is filled out and is overlying in sunk structure 1, and conductive basal layer 2 is the aluminium foil of 15 μ m-thicks, and active material is graphite.
Preparation method is：
Choose thickness be 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) as conductive basal layer, it is placed on the mould with half elliptic groove for being connected with vacuum air pump
On tool, aspiration pump (220V) is opened, make PET plating Copper Foils produce uniform fine pits knot according to the appearance of half elliptic groove
Structure, the width of half elliptic groove is 200 μm, and length is 1000 μm, and depth is～50 μm；
Again the graphitic carbon negative electrode active slurry for having configured is coated in into the plating copper foil surfaces of the PET with fine pits structure, is made
Graphitic carbon negative electrode active slurry is filled out and covered with these fine pits structures, and the electrode being painted with is dried in 120 degrees Celsius of atmosphere,
Treat that electrode active material slurry again closes vacuum air pump after curing molding in these fine pits structures；
Electrode is removed, is prepared battery and is prepared and encapsulate.
Embodiment 4
Choose thickness be 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) as conductive basal layer, it is placed on the mould with half elliptic groove for being connected with vacuum air pump
On tool, aspiration pump (220V) is opened, make PET plating Copper Foils produce uniform fine pits knot according to the appearance of half elliptic groove
Structure, the width of half elliptic groove is 200 μm, and length is 1000 μm, and depth is～50 μm；
Again the iron phosphate lithium positive pole active slurry for having configured is coated in into the plating copper foil surfaces of the PET with fine pits structure,
Make iron phosphate lithium positive pole active slurry fill out cover with these fine pits structures, by the electrode being painted with 120 degrees Celsius of atmosphere
It is dried, treats that electrode active material slurry again closes vacuum air pump after curing molding in these fine pits structures；
Electrode is removed, is prepared battery and is prepared and encapsulate.
By embodiment 3 and both positive and negative polarity flexible electrode obtained in embodiment 4 through battery Integration Assembly And Checkout, energy density is
110Wh/kg (@0.2C), the battery for assembling is made to the flexible electrode and is folded and is 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 times of test 2000 times, loop test 1000
It is secondary.
Embodiment described above has been described in detail to technical scheme and beneficial effect, it should be understood that
The specific embodiment of the present invention is the foregoing is only, the present invention is not limited to, it is all to be done in the spirit of the present invention
Any modification, supplement and equivalent etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of flexible electrode, including conductive basal layer and active material, it is characterised in that uniform on described conductive basal layer
There is sunk structure, the area of described 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；
Described active material be coated in conductive basal layer with dimpled texture surface；
Described conductive basal layer is metal forming or plastic-metal plated film.
2. flexible electrode according to claim 1, it is characterised in that the area of described sunk structure accounts for conductive basal layer
The 70～85% of the gross area.
3. flexible electrode according to claim 1, it is characterised in that the thickness of conductive basal layer is 1～100 μm.
4. flexible electrode according to claim 1, it is characterised in that described conductive basal layer is plastic-metal plated film,
Described plastic-metal plated film includes flexible base layer, metallic conduction coating and the conductive anti oxidation layer combined closely successively；
Described flexible base layer is polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, poly-
One kind in dimethyl siloxane and polyimides, the thickness of described flexible base layer is 1～20 μm；
Described metallic conduction coating is the one kind in Cu, Al, Ni, Au and Ag, and the thickness of described metallic conduction coating is 0.1
～5 μm；
Described conductive anti oxidation layer includes at least one in electrically conductive graphite, Graphene, CNT and carbon nano-fiber, institute
The thickness of the conductive anti oxidation layer stated is more than 0 and less than 1 μm.
5. flexible electrode according to claim 4, it is characterised in that described flexible base layer is poly terephthalic acid second
Diol ester；Described metallic conduction coating is Cu or Al.
6. flexible electrode according to claim 5, it is characterised in that the thickness of described flexible base layer is 1～5 μm；
The thickness of described metallic conduction coating is 0.2～5 μm.
7. flexible electrode according to claim 4, it is characterised in that described conductive anti oxidation layer includes Graphene or carbon
Nanotube, the thickness of described conductive anti oxidation layer is 80～100nm.
8. the preparation method of the flexible electrode according to any one of claim 1～7, it is characterised in that comprise the following steps：
(1) conductive basal layer is placed on the groove connection vacuum plant on reeded mould, on mould；
(2) mould is vacuumized, makes conductive basal layer form sunk structure corresponding with groove；
(3) slurry of active material is scratched on the surface of the conductive basal layer with sunk structure, and makes conductive basal layer
Surfacing；
(4) after the conductive basal layer after blade coating active material slurry being dried into 1～30min at 60～150 DEG C, vacuum holding is closed
Put, mold removal obtains flexible electrode.
9. preparation method according to claim 8, it is characterised in that in step (2), mould is vacuumized, vacuum is 1
×10-6～1 × 10-3Pa。
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| Application Number | Priority Date | Filing Date | Title |
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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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611033633.8A CN106654286B (en) | 2016-11-18 | 2016-11-18 | A kind of flexible electrode and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN106654286A true CN106654286A (en) | 2017-05-10 |
| CN106654286B CN106654286B (en) | 2019-06-11 |
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| CN201611033633.8A Active CN106654286B (en) | 2016-11-18 | 2016-11-18 | A kind of flexible electrode and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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