CN115189012A - Solid-state battery cell with mutually embedded structure and preparation method thereof - Google Patents
Solid-state battery cell with mutually embedded structure and preparation method thereof Download PDFInfo
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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
- H01M10/052—Li-accumulators
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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
- H01M10/058—Construction or manufacture
-
- 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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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a solid-state battery cell with a mutual embedded structure, which comprises a positive electrode, a negative electrode and a solid-state electrolyte layer, wherein the positive electrode comprises a positive electrode current collector and a positive electrode material loaded on the positive electrode current collector, and the surface of the positive electrode material is provided with at least one pit; the solid electrolyte layer is attached to the entire surface of the pit; the negative electrode comprises at least one negative electrode area and a negative electrode current collector electrically connected with the negative electrode area, wherein the negative electrode area is formed by a negative electrode material filled with pits attached with the solid electrolyte layer, and the negative electrode current collector is arranged on the surface of the negative electrode area and is electrically connected with the negative electrode area. The invention also provides a preparation method of the solid-state battery cell with the mutually embedded structure. The invention also provides a solid-state battery cell with a series structure, which is formed by connecting at least two battery cell units in series through the connecting terminal. The solid-state battery cell has the characteristics of large contact area between the electrode and the solid electrolyte and difficult short circuit.
Description
Technical Field
The invention belongs to the technical field of energy storage. In particular, the present invention relates to a solid-state battery cell having a mutual insertion structure and a method for preparing the same.
Background
Solid-state batteries are widely recognized as the next generation battery technology due to their high safety and high specific energy characteristics. Because the solid electrolyte in the solid battery replaces the electrolyte of the lithium ion battery, the anode material and the electrolyte are connected by a solid-solid interface. When the positive and negative electrode materials with high volume effect are used, the low solid-solid interface contact area and the interface separation directly influence the exertion of the electrical performance of the battery.
Meanwhile, in the assembly process of the battery, due to the compact compression process, a permeation process is easy to generate in a solid-solid interface, so that the low Young modulus materials such as electrolyte and the like are deformed. In a simple parallel structure solid-state battery, such a large planar ultra-thin electrolyte layer structure is highly likely to cause internal short circuits in the battery.
At present, a cell structure which has a large contact area between an electrode and a solid electrolyte, is not easy to short circuit in a battery and can be freely combined in series and parallel is urgently needed.
Disclosure of Invention
The invention aims to provide a solid-state battery cell with a mutual embedding structure, which can overcome the problem of insufficient contact area between an electrode and a solid electrolyte caused by a parallel structure in the conventional solid-state battery packaging and can also overcome the problem of structural damage caused by the volume effect of the electrode after circulation. The solid-state battery cell provided by the invention divides the cell into a huge number of tiny units, can eliminate a small number of defective units during manufacturing, and can be freely combined for series-parallel connection according to the requirement of design voltage. The invention also aims to provide a method for preparing the solid-state battery cell with the embedded structure.
The above object of the present invention is achieved by the following means.
In a first aspect, the present invention provides a solid-state battery cell with an inter-embedded structure comprising a positive electrode, a negative electrode and a solid-state electrolyte layer, wherein,
the positive electrode comprises a positive electrode current collector and a positive electrode material loaded on the positive electrode current collector, wherein the surface of the positive electrode material is provided with at least one pit;
the solid electrolyte layer is attached to the entire surface of the pit
The negative pole include at least one negative pole district and with the negative pole current collector that the negative pole district electricity is connected, wherein, the negative pole district is formed by being full of the negative pole material who is full of the pit that adheres to solid electrolyte layer, the negative pole current collector set up in on the surface in negative pole district and with the negative pole district forms the electricity and connects.
Preferably, in the solid-state battery cell with an embedded structure according to the present invention, an electrically insulating material layer is disposed on a surface of the positive electrode material, so as to electrically insulate the positive electrode material from the negative electrode current collector. In the present invention, the electrically insulating material layer is provided on the surface of the positive electrode material, which means that the electrically insulating material layer covers the surface of the positive electrode material or covers and extends beyond the surface of the positive electrode material.
Preferably, in the solid-state battery cell with an embedded structure according to the present invention, the electrically insulating material layer has a through hole at a position corresponding to the negative electrode region, and the negative electrode current collector has a protrusion portion matching with the through hole to be electrically connected to the negative electrode region through the electrically insulating material layer.
Preferably, in the solid-state battery cell with an embedded structure according to the present invention, the shape of the pit is cylindrical, pyramidal, frustoconical, or prismatic.
In a particular embodiment of the invention, the shape of the pits is an inverted frusto-conical shape.
Preferably, in the solid-state battery cell with an embedded structure of the invention, the pits are arranged in an array.
Preferably, in the solid-state battery cell with the embedded structure of the invention, the array-type arrangement is performed by:
the pits are arranged in individual rows along a first direction and are spaced apart within each row in a second direction, wherein the first and second directions are perpendicular to each other and a plane formed by the first and second directions is parallel to an upper surface of the cathode material.
Preferably, in the solid-state battery cell with a mutually embedded structure according to the invention, the size of the pits is 100 to 20000 μm, preferably 100 to 9000 μm.
Preferably, in the solid-state battery cell having an intercalated structure according to the present invention, the thickness of the solid electrolyte layer is 1 to 100 μm.
Preferably, in the solid-state battery cell with the embedded structure, the thickness of the negative electrode current collector is 1-50 μm, preferably 1-20 μm.
In a second aspect, the present invention provides a method for preparing a solid-state battery cell with an embedded structure, which comprises the following steps:
(1) Loading a positive electrode material on the surface of a positive electrode current collector, and forming at least one pit on the surface of the positive electrode material by pressing;
(2) Attaching a solid electrolyte layer to the entire surface of the pit;
(3) Filling the pit to which the solid electrolyte layer is attached with an anode material to form an anode region;
(4) Electrically connecting a negative current collector to the negative region;
(5) Optionally, before the step (4), forming an electrically insulating material layer on the surface of the cathode material.
In a third aspect, the present invention provides a series-structured solid-state battery cell composed of at least two cell sub-units connected in series via connection terminals (see fig. 3), the cell sub-units including the solid-state battery cells having a nested structure of the present invention.
In the embodiment of the invention, the negative electrode current collector can be in a single-layer cell structure formed by adopting layered packaging at the top, and can also be compatible with lamination to realize that all single-layer cells are connected in series with each other in the solid-state battery.
In a specific embodiment of the present invention, an insulating water-blocking and oxygen-blocking film is used to encapsulate a solid-state battery cell by hot pressing, so as to form a solid-state battery.
In a specific embodiment of the present invention, the positive electrode current collector needs to be subjected to a surface cleaning treatment before it is used.
In a specific embodiment of the present invention, the positive electrode material is supported on the surface of the positive electrode current collector with the back structure, and an array of inverted truncated cone-shaped dimples is prepared by cold press molding.
In a specific embodiment of the present invention, the liquid-phase electrolyte is attached to the inside of the pit through a mask corresponding to the pit of the inverted truncated cone shape, or the electrolyte is attached to the inside of the pit by a deposition method. The electrolyte is then shaped and heat treated using a die to form the desired solid electrolyte.
In the embodiment of the invention, the negative electrode slurry is filled in the solid electrolyte interface of the inverted truncated cone shape, the negative electrode slurry is injected by a cold rolling or melting method to form the negative electrode material, and the interface of the electrolyte and the negative electrode material can be treated or not, and is preferably modified by a metal mixed conductive layer.
In particular embodiments of the present invention, conventional methods in the art may be employed to prepare the desired negative current collector of the present invention, such as the method disclosed in reference patent application 201410440238.6.
In the specific embodiment of the invention, the negative current collector is led out by cold pressing, and the single-layer battery cores are stacked into groups to realize the lamination in the battery, thereby realizing the series connection in the battery.
In the specific embodiment of the invention, the positive and negative electrode tabs are led out from the side surface of the battery cell, and then the battery cell is transferred and thermally packaged.
The invention has the following beneficial effects:
on one hand, the solid-state battery cell has the characteristic of large contact area between the electrode and the solid electrolyte. On the other hand, the solid-state battery cell is not easy to be short-circuited, and the problem of structural damage caused by the volume effect of the electrode after circulation can be solved. In addition, the solid-state battery cell provided by the invention divides the battery cell into a huge number of tiny units, can eliminate a small number of defective units during manufacturing, and can realize series connection among the battery cell subunits by adding connecting terminals among the battery cell subunits according to the requirement of design voltage (see fig. 3). The solid-state battery cell with the embedded structure provided by the invention is actually a parallel connection between cell structures (see fig. 1). Therefore, the solid-state battery cell with the mutually embedded structure can realize free series-parallel connection of the cell structure.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a side sectional view of a solid state battery cell of an embodiment of the invention;
fig. 2 is a top cross-sectional view of a solid state battery cell without a negative current collector according to an embodiment of the present invention;
figure 3 is a cross-sectional side view of a series connection of cell sub-units according to an embodiment of the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Preparation of positive electrode
An aluminum foil with a thickness of 12 μm was used as a positive electrode current collector, and then, the positive electrode current collector was subjected to ultrasonic treatment using deionized water and ethanol, respectively, for 30min, followed by drying the positive electrode current collector in a vacuum environment at 120 ℃. Mixing LCO positive active material: LGPS sulfide electrolyte: carbon nanotube: PVDF is in a mass ratio of 5 2 After ball milling and mixing for 3 hours in an inert atmosphere, the mixture was dispersed in anhydrous NMP to form a 60wt% solid content mixture. The positive electrode precursor was formed to a thickness of 1800 μm by applying the mixed solution to one surface of a positive electrode current collector, compacted with a truncated cone-shaped metal grinder having a depth of 1250 μm under a low vacuum < 100Pa environment, and then cold-rolled using a pressure of 50MPa for 15min to form a desired positive electrode.
(2) Solid electrolyte layer preparation
LGPS and LPS sulfide solid electrolyte (1:1 weight ratio mixed) and PTFE binder were mixed at 300r/min in N 2 Ball milling and mixing for 2h under inert atmosphere, wherein the PTFE adhesive accounts for 2wt% of the total mixture. After mixing, the mixture was dispersed in anhydrous cyclohexane to form a mixture of 80% solids by mass. Covering the surface of the positive electrode with a mask plate to shield the positive electrode from being invertedAnd a truncated cone region for spraying the mixed solution into the depression to form a liquid electrolyte with a thickness of 200 μm. Then, the liquid electrolyte was compacted with a generatrix coaxial truncated cone metal grinder under a low vacuum < 100Pa environment to fit the pits of the inverted truncated cone of the positive electrode. Then cold rolling for 5min by using the pressure of 10MPa, and then starting heating and hot pressing at 200 ℃ for 5min to form a crystallized solid electrolyte layer structure.
(3) Preparation of negative electrode
A 1 μ gold plating was deposited using magnetron sputtering to the solid electrolyte interface to form a mixed ionic conduction layer. In an inert atmosphere Ar 2 And heating the metal lithium to 180 ℃ for hot melting, injecting the metal lithium into the hole by using a micro needle, and filling the negative electrode to be flush with the platform area structure of the positive electrode.
(4) Preparation of negative current collector
A flexible negative bilayer current collector was formed using a 20 μm thick composite flexible FPC film with an annular insulating layer and a Fe metal conductive layer. Then, the negative electrode double-layer current collector is placed on the top of a planar negative electrode, and cold pressing is carried out for 5min under the pressure of 10 MPa. Then, polyimide films with the thickness of 30 microns and provided with positive and negative electrode tabs are used and are respectively cold-rolled with positive and negative current collectors, and then the preparation of the single-chip solid-state battery cell is completed.
(5) Preparation of solid-state batteries
And repeating the preparation steps of the single-layer battery cell, and transferring and laminating the outer sides of the negative pole pieces to form series connection in the battery cell. And (3) aligning and superposing multiple prepared electric core layers, welding positive and negative electrode lugs at the edges of the electric core, pre-packaging by using an aluminum plastic film (edge 150 ℃), putting the prepared electric core of the solid-state battery into a sealing bag in vacuum, and hot-pressing for 30s at the pressure of 600MPa and the temperature of 170 ℃ by using a hot isostatic press to finish the preparation of the solid-state battery.
Comparative example 1
(1) Preparation of positive electrode
And (3) mixing LCO ternary cathode material: LGPS sulfide electrolyte: super P conductive carbon: the mass ratio of PTFE to graphene is 4.5:3:1.5:0.5 2 Ball-milling and mixing for 1h under inert atmosphere, and dispersing into anhydrous cyclohexane to form 60% solidMixed solution with the content mass ratio. The mixed solution was coated on the surface of a general positive electrode current collector to form a positive electrode precursor having a thickness of 120 μm, and then vacuum-dried at 120 ℃ for 6 hours. And compacting the positive electrode precursor into a planar electrode by using a flat plate grinding tool under the environment of low vacuum less than 100 Pa. Then cold pressing with 10MPa pressure for 5min, then starting hot pressing at 150 ℃ for 10min, and continuing cold pressing with isostatic press at 400MPa for 60s, then removing the pressure.
(2) Solid electrolyte layer preparation
Mixing LPS sulfide solid electrolyte with 2wt% of PTFE binder, and stirring at 300r/min in N 2 And (3) ball-milling and mixing for 1h under an inert atmosphere, and then dispersing the mixture into anhydrous cyclohexane to form a mixed solution with the solid content of 80% by mass. The mixed solution was sprayed to the surface of the prepared planar cathode by spraying to form a liquid electrolyte with a thickness of 20 μm. Then, compacting under the environment of low vacuum less than 100Pa, then cold rolling for 5min under the pressure of 10MPa, and then starting heating and hot pressing at 160 ℃ for 10min to form a solid electrolyte layer structure. And (3) rapidly heating the electrolyte area locally by using nanosecond infrared laser drying, and raising the temperature of the electrolyte to 460 ℃ to improve the crystal bloom degree.
(3) Preparation of the negative electrode
Mixing metal Li with 2wt% of Ag simple substance at 180 ℃ to form liquid metal, then uniformly coating the liquid metal on the surface of a stainless steel substrate, cooling and separating the negative electrode. And thinning the metal lithium negative electrode to 100 mu m by using a roller press. And depositing a 30nm high-mixed-conductivity amorphous carbon layer on the surface of the metal lithium with the thickness of 100 mu m by ion source sputtering to serve as a conductive layer. And contacting the prepared cathode mixed electric conduction layer with the prepared solid electrolyte layer to form a planar stacking structure.
(4) Preparation of negative current collector
A flexible negative bilayer current collector was formed using a 20 μm thick composite flexible FPC film with an annular insulating layer and a Fe metal conducting layer. Then, the negative electrode double-layer current collector is placed on the top of a planar negative electrode, and cold pressing is carried out for 5min under the pressure of 10 MPa. Then, polyimide films with the thickness of 30 micrometers and provided with positive and negative electrode tabs are used and are respectively cold-rolled with positive and negative current collectors, and then the preparation of the single solid-state battery cell is completed.
(5) Preparation of solid-state battery
And (3) aligning and superposing two prepared electric core layers, placing the prepared electric core film of the solid-state battery in a polyimide film sealing bag, and hot-pressing for 30s at 200 ℃ by a press under the pressure of 400 MPa. Then, the local excess polyimide film outside the edge tab is removed by laser to form a solid-state battery.
Example 2
The electrochemical performance of the prepared solid battery with the nested array structure and the battery with the parallel structure are tested by using a battery test system of blue-electricity electronic corporation of Wuhan, the test temperature is 60 ℃, and the test voltage is 3.0-4.3V vs Li + Li, test rates of 0.05C and 0.1C, respectively, where the nominal capacity is calculated as 145 mAh/g. The specific capacity of the whole battery is calculated according to the mass of the LCO positive active material.
Table 1 results of performance test of example 1 and comparative example 1
As can be seen from table 1 above, when the solid-state battery is manufactured by using the circular truncated cone array structure, the electrochemical performance is significantly improved because the contact area between the electrode and the solid electrolyte is very high. First, the discharge capacity at 0.05C and 0.1C is higher; second, the cycle capacity retention at 0.1C rate for 50 weeks increased from about 70% to about 96%. The main reason for achieving this performance is to greatly increase the contact area of the electrode and the solid electrolyte by the nested mode, enhancing the capacity release. Simultaneously, the material that volume expansion leads to has been alleviated to the structure of cavity formula is inefficacy, so the cycling stability promotes. The invention solves the problem of capacity attenuation caused by poor interface contact and large volume change in the solid-state battery, and has positive significance for practical application.
Claims (10)
1. A solid-state battery cell having an inter-embedded structure includes a positive electrode, a negative electrode, and a solid-state electrolyte layer, wherein,
the positive electrode comprises a positive electrode current collector and a positive electrode material loaded on the positive electrode current collector, wherein the surface of the positive electrode material is provided with at least one pit;
the solid electrolyte layer is attached to the entire surface of the pit;
the negative pole includes at least one negative pole district and with the negative pole current collector that the negative pole district electricity is connected, wherein, the negative pole district is formed by the negative pole material who is full of the pit that adheres to solid state electrolyte layer, the negative pole current collector set up in on the surface in negative pole district and with the negative pole district forms the electricity and connects.
2. The solid state battery cell of claim 1, wherein the positive electrode material has a surface with a layer of electrically insulating material disposed thereon to electrically insulate the positive electrode material from the negative electrode current collector.
3. The solid state battery cell with an interdigitated structure of claim 2, wherein the electrically insulating material layer has a through-hole at a location corresponding to the negative electrode region, and the negative electrode current collector has a protrusion matching the through-hole to electrically connect with the negative electrode region through the electrically insulating material layer.
4. The solid state battery cell of claim 1, wherein the dimple is cylindrical, pyramidal, frustoconical, or prismatic in shape.
5. The solid state battery cell with a nested structure of claim 1, wherein the dimples are arranged in an array.
6. The solid state battery cells of claim 5, wherein the array format arrangement is performed by:
the pits are arranged in individual rows along a first direction and are spaced apart within each row in a second direction, wherein the first and second directions are perpendicular to each other and a plane formed by the first and second directions is parallel to an upper surface of the cathode material.
7. The solid-state battery cell with a mutually nested structure of claim 1, wherein the size of the depressions is 100-20000 μm, preferably 100-9000 μm.
8. The solid state battery cell with an interdigitated structure of claim 1, wherein the thickness of the solid state electrolyte layer is 1-100 μ ι η;
preferably, the thickness of the negative electrode current collector is 1 to 50 μm, preferably 1 to 20 μm.
9. The method of preparing a solid-state battery cell with an interdigitated structure according to any one of claims 1 to 8, comprising the steps of:
(1) Loading a positive electrode material on the surface of a positive electrode current collector, and forming at least one pit on the surface of the positive electrode material by pressing;
(2) Attaching a solid electrolyte layer to the entire surface of the pit;
(3) Filling the pit to which the solid electrolyte layer is attached with a negative electrode material to form a negative electrode region;
(4) Electrically connecting a negative current collector to the negative region;
(5) Optionally, before the step (4), forming an electrically insulating material layer on the surface of the cathode material.
10. A series-structured solid-state battery cell constituted by at least two electric core units connected in series through a connection terminal, the electric core units comprising the solid-state battery cell having an interfitting structure as recited in any one of claims 1 to 8.
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