CN111342106A - Stacked all-solid-state thin film battery and preparation method thereof - Google Patents
Stacked all-solid-state thin film battery and preparation method thereof Download PDFInfo
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- CN111342106A CN111342106A CN202010165574.XA CN202010165574A CN111342106A CN 111342106 A CN111342106 A CN 111342106A CN 202010165574 A CN202010165574 A CN 202010165574A CN 111342106 A CN111342106 A CN 111342106A
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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
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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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
Abstract
The invention provides a stacked all-solid-state thin film battery and a method for preparing the stacked all-solid-state thin film battery, wherein the stacked all-solid-state thin film battery comprises the following components: a support body; the all-solid-state thin-film battery units are arranged above the support body in a stacked mode, a substrate is arranged between every two all-solid-state thin-film battery units, and the all-solid-state thin-film battery units are connected; and the packaging layer is attached to the top surface and the side surface of the stacked all-solid-state thin film battery cells, extends to the support body, and is matched with the support body to form a packaging structure. According to the technical scheme, all-solid-state thin film monomers are stacked in series or/and in parallel in the same packaging layer to form the stacked all-solid-state thin film battery with a compact internal structure and a small size, so that the output voltage or current is improved, the capacity is increased, the energy density of the battery is greatly improved, the endurance time is prolonged, and the stacked all-solid-state thin film battery can be used for built-in power supplies of various high-end electronic products, such as implantable medical devices, various sensors and the like.
Description
Technical Field
The invention relates to the technical field of all-solid-state batteries, in particular to a stacked all-solid-state thin film battery and a preparation method thereof.
Background
An all-solid-state thin-film battery is an all-solid-state battery, and the thickness of the all-solid-state thin-film battery is generally only a few micrometers. Compared with the traditional lithium battery, the lithium battery has the advantages of good safety, super-strong cycle life, extremely low self-discharge rate, extremely high discharge rate, higher energy density, wireless charging and the like, so that the lithium battery becomes a technology which is acknowledged by the industry and has the most application potential and industrialization prospect.
High-end electronic products require a built-in power supply having characteristics of small volume, high capacity, and reflow soldering. However, the all-solid-state thin film battery in the prior art has a low voltage, generally only 4v, and a small capacity, generally not exceeding 5mAh, which greatly limits its application in high-end electronic equipment.
Therefore, how to develop an all-solid-state thin film battery with high voltage and large capacity in a limited volume becomes a technical problem to be solved urgently.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, the invention aims to provide a stacked all-solid-state thin film battery and a stacked all-solid-state thin film battery preparation method, wherein an all-solid-state thin film battery monomer is deposited on a support body, a layer of thin film is plated on the all-solid-state thin film battery monomer to be used as a substrate to continuously manufacture the next all-solid-state thin film battery monomer, and by analogy, a plurality of all-solid-state thin film battery monomers are stacked to form a stacked all-solid-state thin film battery structure, the whole stacked thin film battery structure is packaged to form the stacked all-solid-state thin film battery with large capacity, the energy density of the battery is greatly improved, the endurance time is prolonged, and the stacked all-solid-state thin film battery can be used for built-in power supplies of various high-end.
In order to achieve the above object, an aspect of the present invention provides a stacked all-solid-state thin film battery including: a support body; the all-solid-state thin-film battery units are arranged above the support body in a stacked mode, a substrate is arranged between every two all-solid-state thin-film battery units, and the all-solid-state thin-film battery units are connected; and the packaging layer is attached to the top surface and the side surface of the stacked all-solid-state thin film battery cells, extends to the support body, and is matched with the support body to form a packaging structure.
In the scheme, a plurality of all-solid-state thin film battery monomers are stacked in series and/or in parallel in the same packaging layer to form an all-solid-state thin film battery stacking structure with a compact internal structure and a smaller volume, so that the output voltage is improved to a certain extent, the battery capacity is increased, the requirement of high-end electronic products on a built-in power supply can be met, the whole stacked all-solid-state thin film battery is supported by the support body, the stability and the firmness of the battery during placement are favorably improved, the stacked all-solid-state thin film battery provided by the invention packages a large number of all-solid-state thin film battery monomers in a smaller volume, so that the energy density of the battery is improved, the endurance time is prolonged, the stacked all-solid-state thin film battery can be formed at one time, the stacked all-solid-state thin film battery does not need to be integrated after being packaged, and the volume of the packaging layer, when the number of all-solid-state thin-film battery monomers is 3, the occupied volume of the stacked all-solid-state thin-film battery provided by the invention can be reduced by 20% and the unit energy density can be improved by 25% compared with a battery which is packaged and then integrated. When the number of all solid-state thin-film battery monomers is 3, the battery capacity can reach 15mAh at most, and the output voltage can reach 11.7V after the batteries are connected in series.
It should be noted that the number of stacked all-solid-state thin-film battery cells can be set according to different voltage or capacity requirements.
Preferably, the combination mode of all-solid-state thin-film battery cells is in series connection or parallel connection.
In this scheme, can select the free compound mode of all solid state thin film battery according to the demand of different voltage or capacity, further promote the application scope of the all solid state thin film battery of heap, can satisfy high-end electronic product to built-in power supply's little volume, high-voltage, the demand of large capacity.
The number of all-solid-state thin film battery monomers in the stacked all-solid-state thin film battery is more than 2, and the connection mode can be parallel connection, series connection or combination of the two modes. The parallel-serial connection mode among all-solid-state thin-film battery cells can be changed by changing the polarity direction of all-solid-state thin-film battery cells.
Preferably, the substrate is an insulating film, and the all-solid-state thin film battery cell includes: the cathode current collector layer and the anode current collector layer are deposited on the support body or the substrate at intervals, the cathode current collector layer is opposite to the anode current collector layer, the cathode current collector layers of the all-solid-state thin film battery monomers are connected into a whole, and the anode current collector layers of the all-solid-state thin film batteries are connected into a whole; the cathode layer covers the partial area of the cathode current collector layer close to the anode, and is isolated from the anode current collector layer; the electrolyte layer is arranged on the cathode layer, two ends of the electrolyte layer respectively extend to the positions above the boundary position of the cathode current collector layer and the cathode layer and the isolation positions between the anode current collector layer and the cathode layer as well as the cathode current collector layer, and the surface area of the electrolyte layer is larger than that of the cathode layer; and the anode layer is arranged on the electrolyte layer and is lapped with the anode current collector layer.
In this scheme, the negative pole current collector layer, the positive pole current collector layer, the cathode layer, the electrolyte layer, the positive pole layer constitutes all solid state thin film battery monomer, all solid state thin film battery monomer's volume is less, battery capacity is higher, higher energy density has, the surface area on electrolyte layer is greater than the surface area of cathode layer, the risk of electrode short circuit has been reduced, it is even as an organic whole through the free negative pole current collector layer of a plurality of all solid state thin film battery, the free positive pole current collector layer of a plurality of all solid state thin film battery links as an organic whole, the free parallel connection of a plurality of all solid state thin film battery has been realized, thereby output current has been improved, battery capacity and unit energy density, and the integrated into one piece of the all solid state thin film battery of heap has been realized.
Every all solid-state film battery monomer in the full solid-state film battery of heap is kept apart through the base, and the base is inorganic non-metallic insulation barrier film, and this base is gone through the preparation of coating film mode, and is not existing inorganic non-metallic insulating piece, and all solid-state film battery monomer in the full solid-state film battery of heap is one shot forming, is an overall structure after the shaping, and is not the simple connection of a plurality of good batteries of encapsulation moreover. The substrate is made of mica, glass, ceramic, polyurethane, silicon-based material, PET, PI, SiO2、MgO、SrTiO3、NdGaO3As a main material, one or two of them.
In addition, the direction of two ends of two adjacent all-solid-state thin-film battery monomers is reversed to realize the series connection of a plurality of all-solid-state thin-film battery monomers, taking three all-solid-state thin-film battery monomers as an example, the cathode current collector layer of the first all-solid-state thin-film battery monomer on the support body extends out from the end side to be used as a cathode output end, the anode current collector layer of the first all-solid-state thin-film battery monomer is connected with the cathode current collector layer of the second thin-film battery, the cathode current collector layer of the first all-solid-state thin-film battery monomer is separated from the anode current collector layer of the second thin-film battery through substrate insulation, similarly, the anode current collector layer of the second all-solid-state thin-film battery monomer is connected with the cathode current collector layer of the third all-solid-state thin-film battery monomer, the anode current collector layer of the third all-solid-state, The cathode current collector layer and the anode current collector layer of the second all-solid-state thin-film battery cell and the cathode current collector layer of the third all-solid-state thin-film battery cell are arranged in the packaging layer.
Preferably, the substrate is a conductive metal thin film, and the stacked all-solid-state thin film battery further includes: a cathode current collector layer deposited on the support; the all-solid-state thin film battery cell includes: a cathode layer covering the upper part of the region of the cathode current collector layer; an electrolyte layer disposed on the cathode layer; the anode layer is arranged on the electrolyte layer, and the stacked all-solid-state thin film battery further comprises: anode current collector layer, the bottom deposit on the supporter of anode current collector layer, with the deposit have the cathode current collector layer adjacent setting of cathode layer, the top deposit on anode current collector layer is in the free top of the highest all solid state thin film battery, the lateral part on anode current collector layer is located the free one end of all solid state thin film battery, link as an organic whole with anode current collector layer, be equipped with the insulating layer between the lateral part on anode current collector layer and the free terminal side face of all solid state thin film battery and the terminal side face on cathode current collector layer, the top and the lateral part on anode current collector layer are located the encapsulated layer. In this scheme, the cathode layer, the electrolyte layer, the positive pole layer constitutes all solid state film battery monomer, all solid state film battery monomer's volume is less, battery capacity is higher, higher energy density has, the single series connection of a plurality of all solid state film battery has been realized for conductive metal film through the base, thereby output voltage and unit energy density have been improved, and the integrated into one piece of the all solid state film battery of heap has been realized, the volume has further been reduced, be equipped with the insulating layer between the lateral part of positive pole current collector layer and all solid state film battery monomer's the terminal side face and the terminal side face of negative pole current collector layer, the emergence of the inside electric leakage phenomenon of battery has effectively been prevented.
The parallel connection and series connection modes of all-solid-state thin film battery monomers in the same stacked all-solid-state thin film battery can be combined to meet the requirements of a built-in power supply of a high-end electronic product on output voltage and battery capacity under the condition of smaller battery volume.
Preferably, the support is an insulating structure, and the support is made of mica, glass, ceramic, polyurethane, silicon-based material, PET, PI, SiO2、MgO、SrTiO3、NdGaO3As a main material, one or two of them.
In the scheme, the support body is made of mica, glass, ceramic, polyurethane, silicon-based material, PET, PI and SiO2、MgO、SrTiO3、NdGaO3One or two of the stacked all-solid-state thin-film batteries are used as main materials, the insulation performance is good, the sealing performance is strong, the whole stacked all-solid-state thin-film battery is attached to the supporting body, the thickness of the supporting body can be selected according to actual needs, the supporting firmness is guaranteed, and meanwhile the occupied volume is reduced.
Preferably, the anode current collector layer is one or more of Al, Ni, Cr, Ti; the anode layer is made of lithium metal alloy or LiFePO4、LiCoO2、LiNiO5MnO4、TiS2、WO3、MoO3、V2O5、LiMn2O4One or two of the anode layers, the thickness of the anode layer is 25 nm-250 mu m; the electrolyte layer is LiPOxNy、Li7La3Zr2O12、LiBO3、LiPO4、Li3OXThe electrolyte layer is composed of 1-50 electrolyte films, and the single electrolyte filmThe thickness is 25 nm-200 nm; the cathode layer is Li, LiAl or LiCoOx、TiO2、Si、Sn、Li2SiS3、Si37C63、SiCu、Li4Ti5O12、SnO、SnO2、Sn3N4、Co3O4One or two, the thickness of the cathode layer is 25 nm-250 μm; the cathode current collector layer is one or more of Cu, Ag, Pt and Au.
In the scheme, the cathode current collector layer, the anode current collector layer, the electrolyte layer, the anode layer and the cathode layer are wide in material selection range, the thickness of the electrolyte layer is reasonable in design, and the small-size, high-capacity-density and other performances of the all-solid-state thin-film battery monomer are favorably realized.
Preferably, the packaging layer is any one of polytetrafluoroethylene, epoxy resin, polyisobutylene, acrylate, polyisobutylene and polyurethane, the thickness of the packaging layer is 1-30 μm,
the water vapor transmission rate of the packaging layer is less than 10-5gm-2d-1The water vapor transmission rate of the support body is not more than 10- 3gm-2d-1。
In this scheme, regard as the encapsulation layer with arbitrary one in polytetrafluoroethylene, epoxy, polyisobutylene, acrylic ester, polyisobutylene, polyurethane, the cover is on the top surface of the all solid state thin film battery of heap, side and supporter, constitute packaging structure jointly with the supporter, can be to vapor, oxygen is isolated, play to block and guard action to the battery, the all solid state thin film battery of whole heap only has one deck encapsulated layer, when effectively protecting the battery, the volume of battery has also been reduced, the unit energy density of battery has been improved.
It should be noted that the encapsulation layer cannot cover the electrodes, that is, the cathode current collector layer and the anode current collector layer at both ends of the support.
The technical scheme of the invention also provides a preparation method of the stacked all-solid-state thin film battery, which comprises the following steps: cleaning the support body by adopting a plasma etching method, a high-temperature heat treatment method and/or a wet chemical cleaning method to remove residual dirt on the support body; preparing a first all-solid-state thin film battery cell on a support; preparing a substrate on the first all-solid-state thin-film battery monomer by adopting a magnetron sputtering deposition method, a vacuum evaporation deposition method or a radio frequency sputtering method; preparing a second all-solid-state thin film battery monomer on a substrate, wherein a current collector layer of the second all-solid-state thin film battery monomer and a current collector layer of the first all-solid-state thin film battery monomer which are positioned on the same side of a support body are deposited into a whole, and the current collector layer comprises a cathode current collector layer and an anode current collector layer; repeatedly stacking upwards to prepare a substrate and a second all-solid-state thin film battery monomer; when the number of the stacked first all-solid-state thin film battery monomers and the number of the stacked second all-solid-state thin film battery monomers reach a specified number, annealing to obtain corresponding crystal structures; and covering a packaging layer on the top surface of the last stacked second all-solid-state film monomer and the side surfaces of all the first all-solid-state film monomers and the second all-solid-state film monomers by adopting a spin-coating method, a dip-coating method or a spraying method, wherein the packaging layer and the support body jointly form a battery packaging structure.
In the scheme, the support body is cleaned by adopting a plasma etching method, a high-temperature heat treatment method or a wet chemical cleaning method, residual dirt on the support body can be removed, bulk cleaning can be carried out, laser cutting is carried out according to requirements, so that the efficiency is improved, a substrate is prepared in a film coating mode after a first all-solid-state thin film battery monomer is prepared on the support body, a second all-solid-state thin film battery monomer is prepared on the substrate, stacking is carried out according to the substrate, the integrated forming of the stacked all-solid-state thin film battery is favorably realized, the connection of the all-solid-state thin film monomers is realized by depositing a current collector layer positioned on the same side of the support body into a whole, the all-solid-state thin film monomers can be selected to be connected in series or in parallel or combined according to requirements, and finally a packaging layer is covered, the stacked, the stacked all-solid-state thin-film battery has compact internal structure and small volume, improves output voltage and current to a certain extent, increases battery capacity, and can meet the requirement of high-end electronic products on a built-in power supply, the stacked all-solid-state thin-film battery preparation method provided by the invention can package a large number of all-solid-state thin-film battery monomers in small volume, thereby improving the energy density of the battery, increasing the endurance time, the stacked all-solid-state thin film battery can be formed at one time without being integrated after being packaged, the volume of the packaging layer in the all-solid-state thin film battery is about 30 percent of the total volume of the battery, when the number of all-solid-state thin-film battery monomers is 3, the occupied volume of the stacked all-solid-state thin-film battery provided by the invention can be reduced by 20% and the unit energy density can be improved by 25% compared with a battery which is packaged and then integrated. When the number of all solid-state thin-film battery monomers is 3, the battery capacity can reach 15mAh at most, and the output voltage can reach 11.7V after the batteries are connected in series.
It should be noted that, generally, after 3 to 5 all-solid-state thin-film battery cells are stacked, annealing treatment is performed to remove stress in time, and if more all-solid-state thin-film battery cells need to be stacked, annealing treatment may be performed once every 3 to 5 all-solid-state thin-film battery cells are stacked, and then stacking is continued, and so on.
Preferably, the preparing the first all-solid-state thin film battery cell or the second all-solid-state thin film battery cell specifically includes: depositing and preparing a cathode current collector film on a support or a designated area of a substrate by adopting an atomic layer deposition method, a chemical vapor deposition method, a plasma deposition method or a plasma enhanced chemical vapor deposition method to form a cathode current collector layer; preparing a cathode film in a designated area on the cathode current collector layer by adopting a lithography method or a radio frequency sputtering method to form a cathode layer; preparing an electrolyte film on the cathode layer by adopting a magnetron sputtering deposition method, a vacuum evaporation method or a PECVD method to form an electrolyte layer, wherein the surface area of the electrolyte layer is larger than that of the cathode layer; preparing an anode film on the electrolyte layer by adopting a lithography method or a radio frequency sputtering method to form an anode layer; and depositing the anode current collector film on a support or a designated area on the substrate by adopting an atomic layer deposition method, a chemical vapor deposition method, a plasma deposition method or a plasma enhanced chemical vapor deposition method to form an anode current collector layer.
In the scheme, the preparation methods of the cathode current collector film, the cathode film, the electrolyte film, the anode film and the anode current collector film are mature and efficient, the yield and the quality are high, and the realizability is high.
Preferably, the annealing treatment is a heat treatment at 300 ℃ to 800 ℃.
In the scheme, the annealing treatment is heat treatment at 300-800 ℃, so that a required crystal structure can be obtained, the preparation success rate is high, and the quality is high.
It should be noted that, the deposition of each layer of thin film of the stacked all-solid-state thin film battery requires a dedicated mold, the mold has corresponding holes, and the first layer of thin film is formed at one time when the thin film is formed in the corresponding holes, for example, when the first layer of thin film is prepared, the mold is etched with spaces of a cathode current collector, a part of electrolyte and an anode current collector. When preparing the second film, the second mould is replaced, and the second mould is provided with a space with partial electrolyte, cathode and anode current collectors to form the second film at one time. By analogy, the mold needs to be replaced each time the film properties change. Finally, the required battery combination is formed, the whole battery combination is a whole, and generally, the die is provided with carved holes of different layers on the same horizontal plane for mass production.
Through the technical scheme, an all-solid-state thin-film battery monomer is deposited on a support body, a layer of thin film is plated on the all-solid-state thin-film battery monomer to serve as a substrate to continuously manufacture the next all-solid-state thin-film battery monomer, and by analogy, a plurality of all-solid-state thin-film battery monomers are stacked to form a stacked all-solid-state thin-film battery structure, the whole stacked thin-film battery structure is packaged to form a stacked all-solid-state thin-film battery with large capacity, the stacked all-solid-state thin-film batteries with compact internal structure and small size are formed by stacking the all-solid-state thin-film monomers in series or/and in parallel in the same packaging layer, the output voltage and the current are improved, the capacity is increased, the energy density of the batteries is greatly improved, the endurance time is increased, and the stacked all-, Various sensors and the like.
The stacked all-solid-state thin film battery can be formed in one step without being packaged and then integrated, the volume of a packaging layer in the all-solid-state thin film battery is about 30% of the total volume of the battery, when the number of all-solid-state thin film battery monomers is 3, the occupied volume of the stacked all-solid-state thin film battery can be reduced by 20% compared with the packaged and re-integrated battery, and the unit energy density can be improved by 25%. When the number of all solid-state thin-film battery monomers is 3, the battery capacity can reach 15mAh at most, and the output voltage can reach 11.7V after the batteries are connected in series.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 shows a schematic structural view of a stacked all-solid-state thin film battery according to an embodiment of the present invention;
fig. 2 shows a schematic front view of the all-solid-state thin film battery cell of fig. 1;
fig. 3 shows a schematic top view of the all-solid-state thin film battery cell of fig. 1;
fig. 4 shows a schematic structural view of a stacked all-solid-state thin film battery according to another embodiment of the present invention;
figure 5 shows a schematic flow diagram of a stacked all-solid-state thin film battery fabrication method according to one embodiment of the present invention,
wherein, the corresponding relationship between the reference numbers and the components in fig. 1 to fig. 4 is:
102 a support, 104 an all-solid-state thin film battery cell, 1042 a cathode current collector layer, 1044 an anode current collector layer, 1046 a cathode layer, 1048 an electrolyte layer, 1050 an anode layer, 106 a substrate, 108 an encapsulation layer, 110 an insulating layer.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
As shown in fig. 1 to 3, a stacked all-solid-state thin film battery according to an embodiment of the present invention includes: a support body 102; the all-solid-state thin-film battery cells 104 are arranged above the support body 102 in a stacked mode, a substrate 106 is arranged between every two all-solid-state thin-film battery cells 104, and the all-solid-state thin-film battery cells 104 are connected; and the packaging layer 108 is attached to the top surface and the side surface of the stacked all-solid-state thin film battery cells 104, extends to the support body 102, and is matched with the support body 102 to form a packaging structure.
In this embodiment, a plurality of all-solid-state thin-film battery cells 104 are stacked in series and/or in parallel in the same packaging layer 108 to form an all-solid-state thin-film battery stacking structure with a compact internal structure and a small volume, thereby improving output voltage to a certain extent, increasing battery capacity, and meeting the requirement of high-end electronic products on a built-in power supply, and the support body 102 supports the whole stacked all-solid-state thin-film battery, which is beneficial to improving stability and firmness when the battery is placed, the stacked all-solid-state thin-film battery provided by the invention packages a large number of all-solid-state thin-film battery cells 104 in a small volume, thereby improving energy density of the battery, increasing endurance time, and the stacked all-solid-state thin-film battery can be formed at one time without being packaged and then integrated, and the volume of the packaging layer 108 in the all-solid-state thin-film battery accounts for about 30%, when the number of all-solid-state thin-film battery cells 104 is 3, the occupied volume of the stacked all-solid-state thin-film battery provided by the invention can be reduced by 20% and the unit energy density can be improved by 25% compared with the battery which is packaged and then integrated. When the number of all-solid-state thin-film battery cells 104 is 3, the battery capacity can reach 15mAh at most, and the output voltage can reach 11.7V after series connection.
It should be noted that the number of stacked all-solid-state thin-film battery cells 104 can be set according to different voltage or capacity requirements.
The combination mode of all-solid-state thin-film battery cells 104 is series connection or parallel connection.
In this embodiment, the combination mode of the all-solid-state thin-film battery cells 104 can be selected according to the requirements of different voltages or capacities, so that the application range of the stacked all-solid-state thin-film battery is further expanded, and the requirements of high-end electronic products on small volume, high voltage and large capacity of the built-in power supply can be met.
The number of all-solid-state thin-film battery cells 104 in the stacked all-solid-state thin-film battery is greater than 2, and the connection mode can be parallel connection, series connection or combination of the two modes. The parallel-serial connection mode between all-solid-state thin-film battery cells 104 can be changed by changing the polarity direction of all-solid-state thin-film battery cells 104.
As shown in fig. 1 to 3, the substrate 106 is an insulating film, and the all-solid-state thin-film battery cell 104 includes: the cathode current collector layer 1042 and the anode current collector layer 1044 are deposited on the support 102 or the substrate 106 at intervals, the cathode current collector layer 1042 is opposite to the anode current collector layer 1044, the cathode current collector layers 1042 of the plurality of all-solid-state thin-film battery cells 104 are connected into a whole, and the anode current collector layers 1044 of the plurality of all-solid-state thin-film battery cells are connected into a whole; a cathode layer 1046 covering a portion of the cathode current collector layer 1042 near the anode, the cathode layer 1046 being isolated from the anode current collector layer 1044; an electrolyte layer 1048 disposed on the cathode layer 1046, wherein two ends of the electrolyte layer 1048 extend to positions above a boundary between the cathode current collector layer 1042 and the cathode layer 1046 and at an isolation position between the anode current collector layer 1044 and the cathode layer 1046 and the cathode current collector layer 1042, respectively, and a surface area of the electrolyte layer 1048 is greater than a surface area of the cathode layer 1046; an anode layer 1050 is disposed on the electrolyte layer 1048, and overlaps with the anode current collector layer 1044.
In this embodiment, the cathode current collector layer 1042, the anode current collector layer 1044, the cathode layer 1046, the electrolyte layer 1048, and the anode layer 1050 form the all-solid-state thin film battery cell 104, the all-solid-state thin film battery cell 104 has a smaller volume, a higher battery capacity, and a higher energy density, the surface area of the electrolyte layer 1048 is greater than the surface area of the cathode layer 1046, thereby reducing the risk of electrode short circuit, the cathode current collector layers 1042 of the all-solid-state thin film battery cells 104 are connected into a whole, the anode current collector layers 1044 of the all-solid-state thin film battery cells are connected into a whole, and the parallel connection of the all-solid-state thin film battery cells 104 is realized, thereby improving the output current, the battery capacity and the unit energy density, and realizing the integral molding of the stacked all-solid-state thin film.
Each all-solid-state thin-film battery monomer 104 in the stacked all-solid-state thin-film battery is isolated through a substrate 106, the substrate 106 is an inorganic non-metal insulating isolation film, the substrate is prepared in a coating mode, the substrate is not an existing inorganic non-metal insulating sheet, all-solid-state thin-film battery monomers 104 in the stacked all-solid-state thin-film battery are formed in one step, the formed substrate is of an integral structure, and the connection of a plurality of packaged batteries is not simple. The substrate 106 is made of mica, glass, ceramic, polyurethane, silicon-based material, PET, PI, or SiO2、MgO、SrTiO3、NdGaO3As a main material, one or two of them.
In addition, the direction of two ends of two adjacent all-solid-state thin-film battery monomers is reversed to realize the series connection of a plurality of all-solid-state thin-film battery monomers, taking three all-solid-state thin-film battery monomers as an example, the cathode current collector layer of the first all-solid-state thin-film battery monomer on the support body extends out from the end side to be used as a cathode output end, the anode current collector layer of the first all-solid-state thin-film battery monomer is connected with the cathode current collector layer of the second thin-film battery, the cathode current collector layer of the first all-solid-state thin-film battery monomer is separated from the anode current collector layer of the second thin-film battery through substrate insulation, similarly, the anode current collector layer of the second all-solid-state thin-film battery monomer is connected with the cathode current collector layer of the third all-solid-state thin-film battery monomer, the anode current collector layer of the third all-solid-state, The cathode current collector layer and the anode current collector layer of the second all-solid-state thin-film battery cell and the cathode current collector layer of the third all-solid-state thin-film battery cell are arranged in the packaging layer.
Alternatively, as shown in fig. 4, the substrate 106 is a conductive metal thin film, and the stacked all-solid-state thin film battery further includes: a cathode current collector layer 1042 deposited on the support; the all-solid-state thin film battery cell includes: a cathode layer 1046 covering the region of the cathode current collector layer 1042; an electrolyte layer 1048 disposed on the cathode layer 1046; an anode layer 1050 disposed on the electrolyte layer 1048, the stacked all-solid-state thin film battery further comprising: the anode current collector layer 1044 is deposited on the support body at the bottom of the anode current collector layer 1044, and is disposed adjacent to the cathode current collector layer 1042 on which the cathode layer 1046 is deposited, the top of the anode current collector layer 1044 is deposited above the highest all-solid-state thin-film battery cell, the side of the anode current collector layer 1044 is located at one end of the all-solid-state thin-film battery cell, the anode current collector layer 1044 is connected into a whole, an insulating layer 110 is disposed between the side of the anode current collector layer 1044 and the end side of the all-solid-state thin-film battery cell and the end side of the cathode current collector layer 1042, and the top and the side of the anode current collector layer 1044 are located in the encapsulation layer 108. In this embodiment, the cathode layer 1046, the electrolyte layer 1048, and the anode layer 1050 form the all-solid-state thin-film battery cell 104, the all-solid-state thin-film battery cell 104 has a smaller volume, a higher battery capacity, and a higher energy density, and the substrate 106 is used as a conductive metal film to realize the series connection of the plurality of all-solid-state thin-film battery cells 104, thereby improving the output voltage and the unit energy density, and realizing the integral formation of the stacked all-solid-state thin-film battery, further reducing the volume, the insulating layer 110 is arranged between the side portion of the anode current collector layer 1044 and the end side surfaces of the all-solid-state thin-film battery cells 104 and the end side surface of the cathode current collector layer 1042, and effectively preventing the.
The parallel connection and series connection modes of all-solid-state thin film battery cells 104 in the same stacked all-solid-state thin film battery can be combined to meet the requirements of a built-in power supply of a high-end electronic product on output voltage and battery capacity under the condition of a smaller battery volume.
The support 102 is an insulating structure, and the support 102 is made of mica, glass, ceramic, or polymerUrethane, silicon-based material, PET, PI, SiO2、MgO、SrTiO3、NdGaO3As a main material, one or two of them.
The support 102 is made of mica, glass, ceramic, polyurethane, silicon-based material, PET, PI, SiO2、MgO、SrTiO3、NdGaO3One or two of the materials are used as main materials, the insulation property is good, the sealing property is strong, the whole stacked all-solid-state thin-film battery is attached to the support body 102, the thickness of the support body 102 can be selected according to actual needs, the supporting firmness is guaranteed, and the occupied volume is reduced.
The anode current collector layer 1044 is one or more of Al, Cu, Ni, Cr and Ti; the anode layer 1050 is made of lithium metal alloy or LiFePO4、LiCoO2、LiNiO5MnO4、TiS2、WO3、MoO3、V2O5、LiMn2O4One or two of them, the thickness of the anode layer 1050 is 25 nm-250 μm; electrolyte layer 1048 is LiPOxNy、Li7La3Zr2O12、LiBO3、LiPO4、Li3OX The electrolyte layer 1048 is composed of 1-50 electrolyte thin films, and the thickness of a single electrolyte thin film is 25 nm-200 nm; cathode layer 1046 is Li, LiAl, LiCoOx、TiO2、Si、Sn、Li2SiS3、Si37C63、SiCu、Li4Ti5O12、SnO、SnO2、Sn3N4、Co3O4One or two, the thickness of the cathode layer 1046 is 25nm to 250 μm; the cathode current collector layer 1042 is one or more of Cu, Ag, Pt, Au.
The cathode current collector layer 1042, the anode current collector layer 1044, the electrolyte layer 1048, the anode layer 1050 and the cathode layer 1046 are wide in material selection range, the thickness of the electrolyte layer 1048 is reasonable in design, and the all-solid-state thin film battery cell 104 is beneficial to achieving the performances of small volume, high capacity density and the like.
The packaging layer 108 is any one of polytetrafluoroethylene, epoxy resin, polyisobutylene, acrylate, polyisobutylene and polyurethane, the thickness of the packaging layer 108 is 1-30 μm,
the encapsulation layer 108 has a water vapor transmission rate of less than 10-5gm-2d-1The water vapor transmission rate of the support 102 is not more than 10-3gm-2d-1。
Any one of polytetrafluoroethylene, epoxy resin, polyisobutylene, acrylate, polyisobutylene and polyurethane is taken as a packaging layer 108, covers on the top surface, the side surface and the supporting body 102 of the stacked all-solid-state thin-film battery, and forms a packaging structure together with the supporting body 102, so that water vapor and oxygen can be isolated, the battery is blocked and protected, the whole stacked all-solid-state thin-film battery only has one packaging layer 108, the battery is effectively protected, the size of the battery is reduced, and the unit energy density of the battery is improved.
It should be noted that the encapsulation layer 108 cannot cover the electrode, that is, the cathode current collector layer 1042 and the anode current collector layer 1044 at two ends of the support 102.
As shown in fig. 5, a method for manufacturing a stacked all-solid-state thin film battery according to an embodiment of the present invention includes:
s502, cleaning the support body by adopting a plasma etching method, a high-temperature heat treatment method or a wet chemical cleaning method to remove residual dirt on the support body;
s504, preparing a first all-solid-state thin film battery monomer on a support body;
s506, preparing a substrate on the first all-solid-state thin-film battery monomer by adopting a magnetron sputtering deposition method, a vacuum evaporation deposition method or a radio frequency sputtering method;
s508, preparing a second all-solid-state thin film battery monomer on the substrate, wherein a current collector layer of the second all-solid-state thin film battery monomer and a current collector layer of the first all-solid-state thin film battery monomer, which are positioned on the same side of the support, are deposited into a whole, and the current collector layers comprise a cathode current collector layer and an anode current collector layer;
s510, repeatedly stacking upwards to prepare a substrate and a second all-solid-state thin film battery monomer;
s512, when the number of the stacked first all-solid-state thin film battery monomers and the number of the stacked second all-solid-state thin film battery monomers reach a specified number, annealing to obtain corresponding crystal structures;
and S514, covering a packaging layer on the top surface of the last stacked second all-solid-state thin film monomer and the side surfaces of all the first all-solid-state thin film monomers and the second all-solid-state thin film monomers by adopting a spin coating method, a dip coating method or a spraying method, wherein the packaging layer and the support body jointly form a battery packaging structure.
In the embodiment, the support body is cleaned by adopting a plasma etching method, a high-temperature heat treatment method or a wet chemical cleaning method, residual dirt on the support body can be removed, bulk cleaning can be carried out, laser cutting is carried out according to requirements, so that the efficiency is improved, a substrate is prepared in a film coating mode after a first all-solid-state thin film battery monomer is prepared on the support body, a second all-solid-state thin film battery monomer is prepared on the substrate, stacking is carried out according to the substrate, the integrated forming of the stacked all-solid-state thin film battery is favorably realized, the connection of the all-solid-state thin film monomers is realized by depositing a current collector layer positioned on the same side of the support body into a whole, the all-solid-state thin film monomers can be selected to be connected in series or in parallel or combined according to requirements, and finally a packaging layer is covered, the stacked, the stacked all-solid-state thin-film battery has compact internal structure and small volume, improves output voltage and current to a certain extent, increases battery capacity, and can meet the requirement of high-end electronic products on a built-in power supply, the stacked all-solid-state thin-film battery preparation method provided by the invention can package a large number of all-solid-state thin-film battery monomers in small volume, thereby improving the energy density of the battery, increasing the endurance time, the stacked all-solid-state thin film battery can be formed at one time without being integrated after being packaged, the volume of the packaging layer in the all-solid-state thin film battery is about 30 percent of the total volume of the battery, when the number of all-solid-state thin-film battery monomers is 3, the occupied volume of the stacked all-solid-state thin-film battery provided by the invention can be reduced by 20% and the unit energy density can be improved by 25% compared with a battery which is packaged and then integrated. When the number of all solid-state thin-film battery monomers is 3, the battery capacity can reach 15mAh at most, and the output voltage can reach 11.7V after the batteries are connected in series.
It should be noted that, generally, after 3 to 5 all-solid-state thin-film battery cells are stacked, annealing treatment is performed to remove stress in time, and if more all-solid-state thin-film battery cells need to be stacked, annealing treatment may be performed once every 3 to 5 all-solid-state thin-film battery cells are stacked, and then stacking is continued, and so on.
The preparation of the first all-solid-state thin film battery cell or the second all-solid-state thin film battery cell specifically includes: depositing and preparing a cathode current collector film on a support or a designated area of a substrate by adopting an atomic layer deposition method, a chemical vapor deposition method, a plasma deposition method or a plasma enhanced chemical vapor deposition method to form a cathode current collector layer; preparing a cathode film in a designated area on the cathode current collector layer by adopting a lithography method or a radio frequency sputtering method to form a cathode layer; preparing an electrolyte film on the cathode layer by adopting a magnetron sputtering deposition method or a vacuum evaporation method and/or a PECVD method to form an electrolyte layer, wherein the surface area of the electrolyte layer is larger than that of the cathode layer; preparing an anode film on the electrolyte layer by a lithography method and/or a radio frequency sputtering method to form an anode layer; and depositing the anode current collector film on a support or a designated area on the substrate by adopting an atomic layer deposition method and/or a chemical vapor deposition method or a plasma enhanced chemical vapor deposition method to form an anode current collector layer.
In the embodiment, the preparation methods of the cathode current collector film, the cathode film, the electrolyte film, the anode film and the anode current collector film are mature and efficient, the qualification rate and the quality are high, and the realizability is high.
The annealing treatment is heat treatment at 300-800 ℃.
The annealing treatment is heat treatment at 300-800 ℃, so that the required crystal structure can be obtained, the preparation success rate is high, and the quality is high.
It should be noted that, the deposition of each layer of thin film of the stacked all-solid-state thin film battery requires a dedicated mold, the mold has corresponding holes, and the first layer of thin film is formed at one time when the thin film is formed in the corresponding holes, for example, when the first layer of thin film is prepared, the mold is etched with spaces of a cathode current collector, a part of electrolyte and an anode current collector. When preparing the second film, the second mould is replaced, and the second mould is provided with a space with partial electrolyte, cathode and anode current collectors to form the second film at one time. By analogy, the mold needs to be replaced each time the film properties change. Finally, the required battery combination is formed, the whole battery combination is a whole, and generally, the die is provided with carved holes of different layers on the same horizontal plane for mass production.
Example 1
The stacked all-solid-state thin-film battery comprises three all-solid-state thin-film battery monomers, the three all-solid-state thin-film battery monomers are in a parallel structure, the volume is 2cm x 4cm x 26 mu m, the output voltage of the battery can reach 3.9v, and the capacity of the battery can reach 12 mAh; when the discharge depth is 80% at 25 ℃, the cycle life of the battery is more than 1000 times; the working temperature is-20 ℃ to 70 ℃; the self-discharge rate under standard conditions (20 ℃ C., one atmosphere) was less than 2%/year. The stacked all-solid-state thin-film battery has the advantages of compact internal structure, small volume, improved output voltage to a certain extent and increased battery capacity.
The preparation method of the stacked all-solid-state thin film battery comprises the following steps:
the method comprises the following steps: treating the support body by using an RCA cleaning machine to remove surface stains, heavy metals and other particles;
step two: placing the support body in a coating device, covering the support body with a special mold, wherein the mold is provided with corresponding carved holes, and the film grows in the corresponding carved holes to deposit each film of the all-solid-state film battery monomer, wherein the cathode current collector film is a metal copper film, and the thickness of the film is 0.8 mu m; the anode current-collecting film is a metal aluminum film, and the thickness of the film is 1.1 mu m; the cathode film is LiCoO3A film having a film thickness of 2.3 μm; the electrolyte film is a LiPNO film, and the thickness of the electrolyte film is 1.6 mu m; an anode thin film LiTi alloy film, wherein the mass ratio of li to Ti is 9: 1, the thickness of the anode film is 2.3 mu m;
step three: placing the sample prepared in the second step into coating equipment, covering the sample by using a substrate mould, and depositing SiO2The film is used as a substrate, and the thickness of the substrate is 1 mu m;
step four: repeating the second step, continuously depositing each film of the all-solid-state thin film battery monomer on the substrate prepared in the third step, and depositing the all-solid-state thin film battery monomer and the current collector of the all-solid-state thin film battery monomer in the second step into a whole;
step five: repeating the third step and the fourth step once;
step six: putting the sample prepared in the fifth step into an annealing furnace for annealing, and carrying out heat treatment at 300-800 ℃;
step seven: and putting the sample prepared in the sixth step into an automatic dip-coating machine for packaging, wherein the dip-coating material is polytetrafluoroethylene and the thickness is 3 microns.
Example 2
The stacked all-solid-state thin-film battery comprises three all-solid-state thin-film battery monomers, the three all-solid-state thin-film battery monomers are in a parallel structure, the volume is 1mm x 4.5 mu m, the output voltage can reach 3.9v, and the total battery capacity can reach 1.6 mu Ah. The stacked all-solid-state thin-film battery has the advantages of compact internal structure, small volume, improved output voltage to a certain extent and increased battery capacity.
The preparation method of the stacked all-solid-state thin film battery is the same as that of the embodiment 1, wherein the cathode current collector thin film in the all-solid-state thin film battery monomer is a metal copper film, and the thickness of the thin film is 60 nm; the anode current collector film is a metal aluminum film, and the thickness of the film is 115 nm; the cathode film is LiCoO3The film thickness is 320 nm; the electrolyte film is a LiPNO film, and the thickness of the electrolyte film is 180 nm; the anode film is a LiTi alloy film, and the mass ratio of li to Ti is 9: 1, the film thickness is 320 nm. The substrate is SiO2A film, the film thickness being 500 n; the thickness of the packaging layer is 1 μm, and the material is polytetrafluoroethylene.
Example 3
The stacked all-solid-state thin-film battery comprises three all-solid-state thin-film battery monomers, the three all-solid-state thin-film battery monomers are in a parallel structure, the volume is 1cm x 4.5 mu m, the output voltage can reach 3.9v, and the total battery capacity can reach 160 mu Ah. The stacked all-solid-state thin-film battery has the advantages of compact internal structure, small volume, improved output voltage to a certain extent and increased battery capacity.
The preparation method of the stacked all-solid-state thin film battery is the same as that of the embodiment 1, wherein the cathode current collector thin film in the all-solid-state thin film battery monomer is a metal copper film, and the thickness of the thin film is 60 nm; the anode current collector film is a metal aluminum film, and the thickness of the film is 115 nm; the cathode film is LiCoO3The film thickness is 320 nm; the electrolyte film is a LiPNO film, and the thickness of the electrolyte film is 180 nm; the anode film is a LiTi alloy film, and the mass ratio of li to Ti is 9: 1, the film thickness is 320 nm. The substrate is SiO2A film, the film thickness being 500 n; the thickness of the packaging layer is 1 μm, and the material is polytetrafluoroethylene.
The technical scheme of the invention is described in detail by combining the drawings, and the invention provides a stacked all-solid-state thin-film battery and a method for preparing the stacked all-solid-state thin-film battery.
The stacked all-solid-state thin film battery can be formed in one step without being packaged and then integrated, the volume of a packaging layer in the all-solid-state thin film battery is about 30% of the total volume of the battery, when the number of all-solid-state thin film battery monomers is 3, the occupied volume of the stacked all-solid-state thin film battery can be reduced by 20% compared with the packaged and re-integrated battery, and the unit energy density can be improved by 25%. When the number of all solid-state thin-film battery monomers is 3, the battery capacity can reach 15mAh at most, and the output voltage can reach 11.7V after the batteries are connected in series.
In the present invention, the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more unless expressly limited otherwise. The terms "mounted," "connected," "fixed," and the like are to be construed broadly, and for example, "connected" may be a fixed connection, a removable connection, or an integral connection; "coupled" may be direct or indirect through an intermediary. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "left", "right", "front", "rear", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or unit must have a specific direction, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A stacked all-solid-state thin film battery, comprising:
a support body;
the all-solid-state thin film battery units are arranged above the support body in a stacked mode, a substrate is arranged between every two all-solid-state thin film battery units, and the all-solid-state thin film battery units are connected;
and the packaging layer is attached to the top surface and the side surface of the stacked all-solid-state thin film battery cells, extends to the support body, and is matched with the support body to form a packaging structure.
2. The stacked all-solid-state thin film battery according to claim 1,
the combination mode of all solid-state thin-film battery cells is in series connection or in parallel connection.
3. The stacked all-solid thin film battery according to claim 1, wherein the substrate is an insulating thin film, and the all-solid thin film battery cell comprises:
a cathode current collector layer and an anode current collector layer which are deposited on the support or the substrate at intervals, wherein the cathode current collector layer is opposite to the anode current collector layer, the cathode current collector layers of the all-solid-state thin film battery cells are connected into a whole, and the anode current collector layers of the all-solid-state thin film cells are connected into a whole;
the cathode layer covers the partial area of the cathode current collector layer close to the anode current collector layer, and is isolated from the anode current collector layer;
the electrolyte layer is arranged on the cathode layer, two ends of the electrolyte layer respectively extend to the positions above the boundary position of the cathode current collector layer and the cathode layer and the isolation positions between the anode current collector layer and the cathode layer as well as the cathode current collector layer, and the surface area of the electrolyte layer is larger than that of the cathode layer;
and the anode layer is arranged on the electrolyte layer and is lapped with the anode current collector layer.
4. The stacked all-solid thin film battery according to claim 1, wherein the substrate is a conductive metal thin film, the stacked all-solid thin film battery further comprising: a cathode current collector layer deposited on the support;
the all-solid-state thin film battery cell includes:
a cathode layer covering the region of the cathode current collector layer;
an electrolyte layer disposed on the cathode layer;
an anode layer disposed on the electrolyte layer,
the stacked all-solid-state thin film battery further includes: anode current collector layer, anode current collector layer's bottom deposit in on the supporter, have with the deposit the cathode layer the adjacent setting of cathode current collector layer, anode current collector layer's top deposit is highest the free top of full solid state thin film battery, anode current collector layer's lateral part is located the free one end of full solid state thin film battery, will anode current collector layer even is as an organic whole, anode current collector layer's lateral part with the free terminal side of full solid state thin film battery and be equipped with the insulating layer between the terminal side of cathode current collector layer, anode current collector layer's top and lateral part are located in the encapsulated layer.
5. The stacked all-solid thin film battery according to claim 3 or 4,
the support body is of an insulating structure and is made of mica, glass, ceramic, polyurethane, silicon-based material, PET, PI and SiO2、MgO、SrTiO3、NdGaO3As a main material, one or two of them.
6. The stacked all-solid-state thin film battery according to claim 5,
the anode current collector layer is one or more of Al, Ni, Cr and Ti;
the anode layer is made of lithium metal alloy or LiFePO4、LiCoO2、LiNiO5MnO4、TiS2、WO3、MoO3、V2O5、LiMn2O4One or two of the anode layers, wherein the thickness of the anode layer is 25 nm-250 mu m;
the electrolyte layer is LiPOxNy、Li7La3Zr2O12、LiBO3、LiPO4、Li3OXThe electrolyte layer consists of 1-50 electrolyte films, and the thickness of a single electrolyte film is 25-200 nm;
the cathode layer is Li, LiAl or LiCoOx、TiO2、Si、Sn、Li2SiS3、Si37C63、SiCu、Li4Ti5O12、SnO、SnO2、Sn3N4、Co3O4One or two, the thickness of the cathode layer is 25 nm-250 μm;
the cathode current collector layer is one or more of Cu, Ag, Pt and Au.
7. The stacked all-solid-state thin film battery according to claim 6,
the packaging layer is any one of polytetrafluoroethylene, epoxy resin, polyisobutylene, acrylate, polyisobutylene and polyurethane, the thickness of the packaging layer is 1-30 μm,
the packaging layer has a water vapor transmission rate of less than 10-5gm-2d-1The water vapor transmission rate of the support body is not more than 10-3gm-2d-1。
8. A method for preparing a stacked all-solid-state thin film battery is characterized by comprising the following steps:
cleaning the support body by adopting a plasma etching method, a high-temperature heat treatment method or a wet chemical cleaning method to remove residual dirt on the support body;
preparing a first all-solid-state thin film battery cell on the support;
preparing a substrate on the first all-solid-state thin-film battery monomer by adopting a magnetron sputtering deposition method, a vacuum evaporation deposition method or a radio frequency sputtering method;
preparing a second all-solid-state thin film battery monomer on the substrate, wherein a current collector layer of the second all-solid-state thin film battery monomer and a current collector layer of the first all-solid-state thin film battery monomer which are positioned on the same side of the support body are deposited into a whole, and the current collector layers comprise a cathode current collector layer and an anode current collector layer;
repeatedly stacking upwards to prepare the substrate and the second all-solid-state thin film battery cell;
when the number of the stacked first all-solid-state thin-film battery cells and the number of the stacked second all-solid-state thin-film battery cells reach a specified number, annealing to obtain corresponding crystal structures;
and covering a packaging layer on the top surface of the last stacked second all-solid-state film monomer and the side surfaces of all the first all-solid-state film monomer and the second all-solid-state film monomer by adopting a spin-coating method, a dip-coating method or a spraying method, wherein the packaging layer and the support body jointly form a battery packaging structure.
9. The method for manufacturing a stacked all-solid-state thin film battery according to claim 8, wherein the manufacturing of the first all-solid-state thin film battery cell or the second all-solid-state thin film battery cell specifically comprises:
depositing and preparing a cathode current collector film on the support or the appointed area of the substrate by adopting an atomic layer deposition method or a chemical vapor deposition method or a plasma enhanced chemical vapor deposition method to form a cathode current collector layer;
preparing a cathode film in a designated area on the cathode current collector layer by adopting a lithography method or a radio frequency sputtering method to form a cathode layer;
preparing an electrolyte film on the cathode layer by adopting a magnetron sputtering deposition method, a vacuum evaporation method or a PECVD method to form an electrolyte layer, wherein the surface area of the electrolyte layer is larger than that of the cathode layer;
preparing an anode film on the electrolyte layer by using the lithography method or the radio frequency sputtering method to form an anode layer;
and depositing and preparing an anode current collector film on the support or the designated area on the substrate by adopting the atomic layer deposition method or the chemical vapor deposition method or the plasma enhanced chemical vapor deposition method to form an anode current collector layer.
10. The method of manufacturing a stacked all-solid-state thin film battery according to claim 9,
the annealing treatment is heat treatment at 300-800 ℃.
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| CN110870127A (en) * | 2017-08-10 | 2020-03-06 | 国际商业机器公司 | Stacked battery structure |
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| CN112054159A (en) * | 2020-09-23 | 2020-12-08 | 兰州大学 | Preparation method of integrated all-solid-state lithium ion battery |
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