CN110311141A - A kind of cathode of lithium device of simplified battery assembly and preparation method thereof - Google Patents
A kind of cathode of lithium device of simplified battery assembly and preparation method thereof Download PDFInfo
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- CN110311141A CN110311141A CN201910706457.7A CN201910706457A CN110311141A CN 110311141 A CN110311141 A CN 110311141A CN 201910706457 A CN201910706457 A CN 201910706457A CN 110311141 A CN110311141 A CN 110311141A
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- lithium
- cathode
- foil
- solid electrolyte
- copper foil
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
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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 present invention provides cathode of lithium devices of a kind of simplified battery assembly and preparation method thereof, belong to technical field of lithium batteries, the present invention first respectively places piece of metal lithium foil in copper foil two sides, it is wrapped up and is pressed with composite solid electrolyte film again, obtain " sandwich " structure, composite solid electrolyte film is wrapped in lithium foil to the present invention and copper foil presses, solve the problems, such as lithium an- ode and negative lug welding, simultaneously, lithium on epilamellar solid electrolyte and lithium foil will form three-dimensional network conductive structure, lithium ion uniform deposition can be made on the surface of lithium metal, it prevents Li dendrite growth from piercing through basement membrane and causes battery short circuit, the generation of lithium metal Yu electrolyte side reaction can be prevented simultaneously, reduce the consumption of lithium.This cathode of lithium device can be applied in traditional lithium battery, can be matched with traditional anode, simple process, and can obtain high-energy density, while the cycle performance and security performance of lithium battery can be improved.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of cathode of lithium devices of simplified battery assembly, further relate to
A kind of preparation method of the cathode of lithium device of simplified battery assembly.
Background technique
Lithium an- ode is due to its theoretical specific capacity (3860mAh/g) and minimum oxidation-reduction potential with superelevation
(- 3.04V) is considered to be one of ideal negative electrode material of lithium ion battery of high-energy density.But due to cyclic process
In, cathode lithium dendrite growth easily pierces through diaphragm and short circuit is caused to cause safety problem, meanwhile, lithium metal also has very high anti-
Activity is answered, can react with electrolyte and generate consumption, cause cycle efficieny lower.Therefore it needs to carry out lithium an- ode
It protects to improve the performance of battery.On the other hand, since lithium metal matter is soft, it is easy to deform, damaged and fracture, therefore use single
The tab of lithium anode draws operation and needs the very little heart.One side negative lug is easy brother's lithium metal when being shaken or falling and fall
It falls off or disconnects on foil, another aspect lithium metal tab is easily deformed and anode pole piece contact short circuit when being squeezed or impacting.
So how on lithium anode soldering polar ear is lithium metal as lithium metal secondary battery negative pole and must face and solve
Problem.
The lithium gold for preparing lithium-sulfur rechargeable battery is disclosed in the Chinese invention patent application of Publication No. CN104241598A
Belong to the method for cathode, but the lithium ion conducting particle on its diaphragm can only mechanically prevent lithium dendrite growth, it can not be in lithium
Metal surface forms effective protective layer.
Therefore, it is necessary to seek the new technology of one kind to solve the above problems.
Summary of the invention
The purpose of the present invention is: in view of the above deficiencies, provide cathode of lithium device and its preparation of a kind of simplified battery assembly
Method is prepared for a kind of " sandwich " structure using the basement membrane and metal negative electrode that are coated with solid electrolyte coating in the present invention
Composite construction, increases the weldability of battery cathode ear, and improves the cycle performance and security performance of battery.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of cathode of lithium device of simplified battery assembly, including cathode ontology, composite solid electrolyte film and negative electrode lug,
The cathode ontology includes copper foil and the metallic lithium foil that copper foil two sides are arranged in, and the copper foil at least one side edge is equipped with not golden
Belong to the bonding pad of lithium foil covering, the negative electrode lug is set to bonding pad, and the composite solid electrolyte film includes basement membrane and setting
Solid electrolyte coating in one side surface of basement membrane, the composite solid electrolyte film are provided with the side of solid electrolyte coating
Coat other regions of cathode ontology in addition to bonding pad.Solid electrolyte coating and the lithium foil of cathode ontology directly connect after cladding
Touching.
The metallic lithium foil is with a thickness of 20-50 μm.
The solid electrolyte coating be include Li-La-Ti oxygen (LLTO), titanium phosphate aluminium lithium (LATP), lithium lanthanum zirconium oxygen
(LLZO), one of tantalum elements doped lithium lanthanum zirconium oxygen (LLZTO), gallium elements doped lithium lanthanum zirconium oxygen (Ga-LLZO), phosphoric acid germanium aluminium lithium (LAGP)
Or several mixed coatings.
Another side surface of basement membrane is equipped with ceramic coating, and the ceramic coating is Al2O3, boehmite coating.
The solid electrolyte coating layer thickness is 2-4 μm.
The basement membrane is one of polypropylene (PP), polyethylene (PE), non-woven fabrics.
The copper thickness is 6-20 μm.
The negative electrode lug is connect by way of welding or gluing with the bonding pad.
The negative electrode lug is one of nickel tab, copper polar ear or copper nickel plating tab；
A kind of preparation method of the cathode of lithium device of simplified battery assembly, comprising the following steps:
Step 1: piece of metal lithium foil is respectively placed in copper foil both side surface, the metallic lithium foil is set to the copper foil table
Behind face, at least one edge of the copper foil is the bonding pad not covered by lithium foil, is put two sides with composite solid electrolyte film
The copper foil for being equipped with lithium foil is wrapped up with " u "-shaped, and package region does not cover bonding pad, and is pressed by way of roll-in or lamination
It closes, copper foil, metallic lithium foil and composite solid electrolyte membrane pressure is made to close to obtain " sandwich " structure；
Step 2: cutting " sandwich " structure of step 1, and after welding or glued negative electrode lug to bonding pad
To the cathode of lithium device for simplifying battery assembly.
Beneficial effects of the present invention: 1, the tab that the copper foil material of the bonding pad of cathode ontology improves cathode of lithium can weld
Property；2, the solid electrolyte coating on composite solid electrolyte film and the lithium of metallic lithium foil will form three-dimensional network at the two interface
Conductive structure makes lithium ion uniform deposition on the surface of lithium metal, prevents Li dendrite growth from piercing through basement membrane and causes battery short circuit, and three
Dimension network structure protects lithium metal, avoids the generation of the further side reaction of electrolyte in lithium metal and battery, reduces lithium
Consumption；3, this cathode of lithium device can be applied in traditional lithium battery, can be matched with traditional anode, simple process,
And high-energy density can be obtained, improve the cycle performance and security performance of lithium battery.
Detailed description of the invention
Fig. 1 is the cathode of lithium schematic device of " sandwich " structure, wherein 1 is copper foil, 2 be metallic lithium foil, and 3 be composite solid
State dielectric film.
Fig. 2 is the charge-discharge performance schematic diagram that cathode of lithium device prepared by embodiment 1 is assembled into soft-package battery.
Specific embodiment
Below by specific embodiment the technical scheme of the present invention will be further described explanation, but the present invention is not limited to
Following embodiment.
Embodiment one:
The metallic lithium foil 2 with a thickness of 50 μm is added in 1 two sides of copper foil with a thickness of 6 μm, copper foil 1 reserves copper polar ear welding
Then LLTO/PP/Al is used in position2O3Composite solid electrolyte film 3 wraps up metallic lithium foil 2 and copper foil 1, wherein LLTO mono-
Against metallic lithium foil 2, LLTO coating layer thickness is 2 μm, and roll-in is carried out on roll squeezer for side, makes metallic lithium foil 2 and copper foil 1 and compound
The pressing of solid electrolyte membrane 3 integrally obtains " sandwich " structure, is die-cut to the size needed and to weld lithium that copper polar ear obtains negative
Pole device, can directly with positive lamination assembling soft-package battery.
Embodiment two:
The metallic lithium foil 2 with a thickness of 30 μm is added in 1 two sides of copper foil with a thickness of 8 μm, copper foil 1 reserves nickel tab welding
Then LLZO-LATP/PP/Al is used in position2O3Composite solid electrolyte film 3 wraps up metallic lithium foil 2 and copper foil 1, wherein
Against metallic lithium foil 2, LLZO-LATP coating layer thickness is 2 μm for the side LLZO-LATP, and roll-in is carried out on roll squeezer, makes lithium metal
Foil 2 and the pressing of copper foil 1 and composite solid electrolyte film 3 integrally obtain " sandwich " structure, are die-cut to the size needed and welding
The cathode of lithium device that nickel tab obtains, can directly with positive lamination assembling soft-package battery.
Embodiment three:
The metallic lithium foil 2 with a thickness of 40 μm is added in 1 two sides of porous copper foil with a thickness of 6 μm, copper foil 1 reserves the weldering of nickel tab
The position connect, then uses LATP/PP/Al2O3Composite solid electrolyte film 3 wraps up metallic lithium foil 2 and copper foil 1, wherein
Against metallic lithium foil 2, LATP coating layer thickness is 4 μm for the side LATP, and roll-in is carried out on roll squeezer, makes metallic lithium foil 2 and copper foil 1
" sandwich " structure is integrally obtained with the pressing of composite solid electrolyte film 3, the size needed is die-cut to and welds nickel tab and obtain
Cathode of lithium device, can directly with positive lamination assembling soft-package battery.
Example IV:
The metallic lithium foil 2 with a thickness of 50 μm is added in 1 two sides of copper foil with a thickness of 6 μm, copper foil 1 reserves copper polar ear welding
Then LLZTO/PE/Al is used in position2O3Composite solid electrolyte film 3 wraps up metallic lithium foil 2 and copper foil 1, wherein LLZTO
Against metallic lithium foil 2, LLZTO coating layer thickness is 2 μm, and roll-in is carried out on roll squeezer for side, make metallic lithium foil 2 and copper foil 1 and
The pressing of composite solid electrolyte film 3 integrally obtains " sandwich " structure, is die-cut to the size needed and welds what copper polar ear obtained
Cathode of lithium device, can directly with positive lamination assembling soft-package battery.
Embodiment five:
The metallic lithium foil 2 with a thickness of 20 μm is added in 1 two sides of copper foil with a thickness of 8 μm, copper foil 1 reserves the weldering of copper nickel plating tab
Then the position connect is wrapped up metallic lithium foil 2 and copper foil 1 with LLTO/PE/ boehmite composite solid electrolyte film 3, wherein
Against metallic lithium foil 2, LLTO coating layer thickness is 4 μm for the side LLTO, and roll-in is carried out on roll squeezer, makes metallic lithium foil 2 and copper foil 1
" sandwich " structure is integrally obtained with the pressing of composite solid electrolyte film 3, the size needed is die-cut to and welds copper nickel plating tab
Obtained cathode of lithium device, can directly with positive lamination assembling soft-package battery.
Embodiment six:
The metallic lithium foil 2 with a thickness of 20 μm is added in 1 two sides of copper foil with a thickness of 12 μm, copper foil 1 reserves copper nickel plating tab
Then the position of welding is wrapped up metallic lithium foil 2 and copper foil 1 with LLZTO/PE composite solid electrolyte film 3, wherein
Against metallic lithium foil 2, LLZTO coating layer thickness is 3 μm for the side LLZTO, and roll-in is carried out on roll squeezer, makes metallic lithium foil 2 and copper
Foil 1 and the pressing of composite solid electrolyte film 3 integrally obtain " sandwich " structure, are die-cut to the size needed and weld copper nickel plating pole
The cathode of lithium device that ear obtains, can directly with positive lamination assembling soft-package battery.
In the above-mentioned technical solutions, the beneficial effect obtained is: 1, the copper foil material of the bonding pad of cathode ontology improves
The tab weldability of cathode of lithium；2, the solid electrolyte coating on composite solid electrolyte film and the lithium of metallic lithium foil are in the two
Interface will form three-dimensional network conductive structure, makes lithium ion uniform deposition on the surface of lithium metal, prevents Li dendrite growth from piercing through
Basement membrane causes battery short circuit, and three-dimensional net structure protects lithium metal, avoids lithium metal and electrolyte in battery further
The generation of side reaction reduces the consumption of lithium；3, this cathode of lithium device can be applied in traditional lithium battery, can with it is traditional just
Pole matches, simple process, and can obtain high-energy density, improves the cycle performance and security performance of lithium battery.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of cathode of lithium device of simplified battery assembly, it is characterised in that: including cathode ontology, composite solid electrolyte film with
And negative electrode lug, the cathode ontology include copper foil and the metallic lithium foil that copper foil two sides are arranged in, the copper foil at least one side edge
Equipped with the bonding pad not covered by metallic lithium foil, the negative electrode lug is set to bonding pad, and the composite solid electrolyte film includes
Basement membrane and the solid electrolyte coating that one side surface of basement membrane is arranged in, the composite solid electrolyte film are provided with solid electrolyte
Other regions of the side cladding cathode ontology of coating in addition to bonding pad.
2. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the lithium metal
Foil is with a thickness of 20-50 μm.
3. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the solid-state electricity
Solving matter coating to be includes Li-La-Ti oxygen (LLTO), titanium phosphate aluminium lithium (LATP), lithium lanthanum zirconium oxygen (LLZO), tantalum elements doped lithium lanthanum zirconium oxygen
(LLZTO), the mixed coating of one or more of gallium elements doped lithium lanthanum zirconium oxygen (Ga-LLZO), phosphoric acid germanium aluminium lithium (LAGP).
4. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the basement membrane is another
Side surface is equipped with ceramic coating, and the ceramic coating is Al2O3, boehmite coating.
5. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the solid-state electricity
Solving matter coating layer thickness is 2-4 μm.
6. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the basement membrane is
One of polypropylene (PP), polyethylene (PE), non-woven fabrics.
7. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the negative electrode lug with
The bonding pad is connected by way of welding or gluing.
8. a kind of cathode of lithium device of simplified battery assembly according to claim 1, it is characterised in that: the negative electrode lug is
One of nickel tab, copper polar ear or copper nickel plating tab.
9. preparation a kind of preparation method of the cathode of lithium device of simplified battery assembly, feature as described in claim 1-8 is any
It is: the following steps are included:
Step 1: respectively placing piece of metal lithium foil in copper foil both side surface, after the metallic lithium foil is set to the copper foil surface,
At least one edge of the copper foil is the bonding pad not covered by lithium foil, and two sides are placed with lithium with composite solid electrolyte film
The copper foil of foil is wrapped up with " u "-shaped, and package region does not cover bonding pad, and is pressed by way of roll-in or lamination, makes copper
Foil, metallic lithium foil and composite solid electrolyte membrane pressure close to obtain " sandwich " structure；
Step 2: cutting " sandwich " structure of step 1, and obtains lithium after welding or glued negative electrode lug to bonding pad
Cathode device.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883823A (en) * | 2020-06-10 | 2020-11-03 | 华南理工大学 | Composite polymer solid electrolyte material and preparation method and application thereof |
| CN112467258A (en) * | 2020-11-25 | 2021-03-09 | 北京航空航天大学 | Preparation method of lithium-air battery based on gel electrolyte-lithium cathode integrated structure |
| CN114899351A (en) * | 2022-04-29 | 2022-08-12 | 蜂巢能源科技股份有限公司 | Composite lithium metal cathode, solid-state battery and preparation method of composite lithium metal cathode |
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