CN114759266B - Prefabricated module of solid-state battery, solid-state battery and preparation method of solid-state battery - Google Patents

Prefabricated module of solid-state battery, solid-state battery and preparation method of solid-state battery Download PDF

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CN114759266B
CN114759266B CN202210670266.1A CN202210670266A CN114759266B CN 114759266 B CN114759266 B CN 114759266B CN 202210670266 A CN202210670266 A CN 202210670266A CN 114759266 B CN114759266 B CN 114759266B
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active material
material layer
electrode active
solid
positive electrode
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CN114759266A (en
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杨晓光
张文珂
杨立鹏
关豪元
张祥
孙逢春
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Shenzhen Automotive Research Institute of Beijing University of Technology
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
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    • 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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
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    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane

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Abstract

A prefabricated module of a solid-state battery, a solid-state battery and a method for manufacturing the same, wherein the prefabricated module comprises: the positive electrode composite unit and the negative electrode composite unit are arranged in a stacked mode; the positive electrode composite unit includes: the bipolar plate comprises a bipolar plate and a positive active material layer, wherein the positive active material layer is compounded on one surface of the bipolar plate and has a preset compaction density; the anode composite unit includes: a solid electrolyte layer and an anode active material layer, the anode active material layer being combined on one surface of the solid electrolyte layer; the negative electrode active material layer in a molten state is bonded to the other surface of the bipolar plate. The positive electrode composite unit and the negative electrode composite unit are prepared separately, and the positive electrode active material layer can have a preset compaction density under a large rolling force so as to increase the capacity of a finished solid battery and avoid the problem that the solid electrolyte layer cannot realize a large compaction density due to the consideration of mechanical strength.

Description

Prefabricated module of solid-state battery, solid-state battery and preparation method of solid-state battery
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a prefabricated module of a solid-state battery, the solid-state battery and a preparation method of the solid-state battery.
Background
The traditional lithium ion battery is composed of a positive current collector, a positive active substance, a diaphragm, a negative active substance, a negative current collector and an electrolyte, wherein the positive active substance is coated on two sides of the positive current collector, the negative active substance is coated on two sides of the negative current collector, the positive active substance and the negative active substance are separated by the diaphragm, the electrolyte generally adopts an organic liquid electrolyte, the liquid electrolyte is filled in gaps and apertures of the positive active substance and the negative active substance and the diaphragm, the liquid electrolyte is volatile and flammable, the potential safety hazard of explosion and fire is large, and under a high-capacity and high-energy density system, the lithium ion battery has the risks of gas expansion, liquid leakage and thermal runaway caused by internal short circuit.
The solid electrolyte material has intrinsic safety, and the solid electrolyte is adopted to replace the liquid electrolyte to form the solid battery, so that the potential safety hazard of the battery is hopefully solved, and therefore, the solid battery is a currently accepted mainstream technical route of a future power battery. Because the solid-state battery does not contain flowable liquid electrolyte, the solid-state battery can adopt a series structure formed by stacking a plurality of battery units consisting of positive electrodes, electrolyte and negative electrodes, and adopts a metal bipolar plate to replace positive and negative electrode current collectors of the traditional liquid-state battery, namely, one side of the bipolar plate is the positive electrode material of one battery unit, and the other side of the bipolar plate is the negative electrode material of the adjacent battery unit. Compared with the traditional lithium ion battery with liquid electrolyte, which needs different current collectors for the positive electrode and the negative electrode, the solid-state battery based on the bipolar plate has higher grouping efficiency.
The existing solid electrolytes are generally classified into three types, i.e., oxide, sulfide and polymer, wherein the oxide solid electrolyte has the best safety, stability and high voltage resistance, and is widely concerned by the industry. However, as a ceramic material, the oxide solid-state battery has common problems that an electrolyte sheet is easy to break, large-size preparation is difficult, electrode-electrolyte interface contact is poor, impedance is high and the like.
One of the major challenges of oxide solid state batteries is the contradiction between the compacted density of the electrode sheets and the brittle fracture of the oxide solid electrolyte sheets. The electrode plate is formed by coating mixed slurry consisting of active substances, solid electrolyte particles, a binder, a conductive additive and the like on a metal current collector in a dry method or a wet method. In order to improve the energy density of the battery, the surface loading of active materials needs to be improved, and meanwhile, the coated electrode plate needs to be subjected to rolling force through a rolling machine so as to improve the compaction density of the electrode plate. However, the stack assembly of electrode sheets with oxide solid electrolyte sheets is a problem facing current solid-state battery production: on the one hand, the oxide solid electrolyte sheet has strong brittleness and is easily broken even by applying a small pressure; on the other hand, if no pressure is applied, high interfacial resistance exists between the electrode sheet and the solid electrolyte sheet, which seriously affects the battery performance.
Disclosure of Invention
The invention mainly solves the technical problem of providing a prefabricated module for preparing a solid-state battery in a bonding mode, the solid-state battery and a preparation method thereof.
According to a first aspect of the present application, there is provided a prefabricated module of a solid-state battery, comprising: a positive electrode composite unit and a negative electrode composite unit which are arranged in a stacked manner; the positive electrode composite unit includes: the bipolar plate comprises a bipolar plate and a positive electrode active material layer, wherein the positive electrode active material layer is compounded on one surface of the bipolar plate and has a preset compaction density; the anode composite unit includes: a solid electrolyte layer and an anode active material layer, the anode active material layer being combined on one surface of the solid electrolyte layer; the negative electrode active material layer in a molten state is bonded to the other surface of the bipolar plate.
In one embodiment, the predetermined compacted density is greater than or equal to 2.8 g/cm 3 。
According to a second aspect of the present application, there is provided a solid-state battery comprising: at least two of said prefabricated modules arranged in a stack, and an ion conductor adhesive layer arranged between two adjacent prefabricated modules; the ion conductor bonding layer is used for bonding the other surface of the solid electrolyte layer of the previous prefabricated module in the two adjacent prefabricated modules with the surface of the positive electrode active material layer of the next prefabricated module and conducting ions.
In one embodiment, the material of the ion conductor adhesive layer is an organic polymer or an organic-inorganic composite material having ion conduction.
In one embodiment, the organic polymer comprises: one or more of perfluorosulfonic acids, polyionic liquid, PEO, PEG, PAA, sulfonated polyurethane or sulfonated polyether ether ketone.
In one embodiment, the organic-inorganic composite material is a composite material of an organic material and an inorganic material, the organic material including: one or more combinations of perfluorosulfonic acids, polyionic liquids, PEO, PEG, PAA, sulfonated polyurethane, sulfonated polyetheretherketone, PVDF, PTFE, CMC, or SBR, and the inorganic material comprises one or more combinations of perovskite, NASICON, LISICON, and garnet solid electrolytes.
According to a third aspect of the present application, there is provided a method for manufacturing a solid-state battery, comprising the steps of:
compounding the positive active material slurry on one surface of the bipolar plate to form a positive active material layer, and rolling to obtain a positive composite unit consisting of the positive active material layer with preset compaction density and the bipolar plate;
compounding a negative electrode active material on one surface of the solid electrolyte layer to form a negative electrode active material layer, and obtaining a negative electrode composite unit consisting of the negative electrode active material layer and the solid electrolyte layer;
the negative electrode active material layer is in a molten state, the positive electrode composite unit is stacked above the negative electrode composite unit, the other surface of the bipolar plate faces the molten negative electrode active material layer, the other surface of the bipolar plate is bonded with the molten negative electrode active material layer, and the prefabricated module is obtained after the molten negative electrode active material layer is solidified;
and laminating at least two prefabricated modules, arranging an ion conductor bonding layer between every two adjacent prefabricated modules, bonding the other surface of the solid electrolyte layer of the previous prefabricated module with the surface of the anode active material layer of the next prefabricated module in the two adjacent prefabricated modules, and curing the ion conductor bonding layer to obtain the solid-state battery.
In one embodiment, in the step of combining the positive active material slurry on one surface of the bipolar plate to form the positive active material layer to obtain the positive composite unit composed of the positive active material layer and the bipolar plate, after the positive active material slurry is combined on one surface of the bipolar plate, the positive active material layer with the preset compaction density is formed after the positive active material slurry is solidified and rolled.
In one embodiment, the solid electrolyte layer is heated to a temperature equal to or higher than the melting point of the negative electrode active material layer, and the negative electrode active material is combined with one surface of the solid electrolyte layer to form the negative electrode active material layer, thereby obtaining a molten negative electrode active material layer.
According to the prefabricated module of the solid-state battery, the solid-state battery and the preparation method thereof in the above embodiments, the positive electrode composite unit and the negative electrode composite unit are separately prepared, and the positive electrode active material layer can have the preset compaction density under the rolling of a large rolling force, so as to increase the capacity of the finished solid-state battery and avoid the problem that the solid-state electrolyte layer cannot realize a large compaction density due to the consideration of mechanical strength. In the preparation process of the solid-state battery, the prefabricated modules are bonded through the ion conductor bonding layer, so that the solid-state electrolyte layer can be prevented from being subjected to brittle fracture due to compaction splicing, and the contradiction between the compaction density of the positive electrode active material layer in the solid-state battery and the brittle fracture of the solid-state electrolyte layer is avoided. The molten negative electrode active material layer is formed by heating, so that the capacity loss caused by rolling of the negative electrode composite unit can be avoided, and meanwhile, the solid-state battery is prepared by bonding a plurality of prefabricated modules through the ion conductor bonding layers, so that the preparation efficiency can be effectively improved.
Drawings
Fig. 1 is a schematic structural diagram of a prefabricated module of a solid-state battery provided herein;
fig. 2 is a schematic diagram illustrating the preparation of a positive electrode composite unit in a prefabricated module of a solid-state battery provided in the present application;
fig. 3 is a schematic diagram illustrating the preparation of a negative electrode composite unit in a prefabricated module of a solid-state battery provided herein;
fig. 4 is a composite schematic diagram of a prefabricated module of a solid-state battery provided herein;
fig. 5 is a composite schematic view of a solid-state battery provided herein;
fig. 6 is a schematic structural diagram of a solid-state battery provided in the present application;
fig. 7 is a flow chart of a method for manufacturing a solid-state battery provided in the present application.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. Wherein like elements in different embodiments are numbered with like associated elements. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, one skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances. In some instances, certain operations related to the present application have not been shown or described in this specification in order not to obscure the core of the present application with unnecessary detail, and it is not necessary for those skilled in the art to describe these operations in detail, so that they may be fully understood from the description in the specification and the general knowledge in the art.
Furthermore, the described features, operations, or characteristics may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification and drawings are for the purpose of describing certain embodiments only and are not intended to imply a required sequence unless otherwise indicated where such sequence must be followed.
The numbering of the components as such, e.g., "first", "second", etc., is used herein only to distinguish the objects as described, and does not have any sequential or technical meaning. The term "connected" and "coupled" when used in this application, unless otherwise indicated, includes both direct and indirect connections (couplings).
The application provides a prefabricated module of a solid-state battery, the solid-state battery and a preparation method of the solid-state battery, wherein the solid-state battery is formed by sequentially stacking at least two prefabricated modules, and an ion conductor bonding layer is arranged between every two adjacent prefabricated modules, so that on one hand, an ion conduction effect is achieved, on the other hand, the two adjacent prefabricated modules are bonded and connected in series, and the interface resistance of a positive electrode and a solid electrolyte layer is reduced. The prefabricated module is formed by laminating a positive electrode composite unit and a negative electrode composite unit, the positive electrode composite unit is composed of a bipolar plate and a positive electrode active material layer compounded on one surface of the bipolar plate, and the positive electrode active material layer has a preset compaction density after the positive electrode composite unit is rolled and pressed so as to meet the use requirement of high capacity of the battery. The negative electrode composite unit consists of a solid electrolyte layer and a negative electrode active substance layer compounded on one surface of the solid electrolyte layer, the negative electrode active substance layer is bonded with the other surface of the bipolar plate in a molten state, and after solidification, the positive electrode composite unit and the negative electrode composite unit are compounded into a prefabricated module, so that the problem of fracture caused by rolling and pressing the solid electrolyte layer is avoided, the service life of a finished solid battery is prolonged, and the quality of the finished solid battery is improved.
In this application, solid-state battery mainly is the group battery of using in the aspect of the new forms of energy, for example, uses the group battery on electric automobile, can effectively improve its security and life.
The first embodiment,
The present embodiment provides a prefabricated module of a solid-state battery, as shown in fig. 1, the prefabricated module 100 including: the positive electrode composite unit 10 and the negative electrode composite unit 20 are stacked and disposed on the negative electrode composite unit 20 to obtain a prefabricated module 100.
The positive electrode composite unit 10 includes: the bipolar plate comprises a bipolar plate 11 and a positive electrode active material layer 12, wherein the positive electrode active material layer 12 is compounded on one surface of the bipolar plate 11, and the positive electrode active material layer 12 has a preset compaction density.
Specifically, after the positive electrode active material slurry 120 with a preset thickness is coated on one surface of the bipolar plate 11, the positive electrode active material slurry 120 is dried, cured, rolled and compacted to form the positive electrode active material layer 12 with a preset compaction density, the positive electrode active material slurry 120 usually contains lithium ions, and the preset compaction density enables the positive electrode active material layer 12 to have a certain compactness, so that the energy density of the finished solid-state battery can be improved, and the battery capacity can be improved.
In this embodiment, the predetermined compaction density of the positive electrode active material layer 12 is 2.8 g/cm or more 3 For example, the preset compaction density may be 2.8 g/cm 3 、3.0g/cm 3 、3.2 g/cm 3 、3.4 g/cm 3 And the like, of course, the preset compaction density of the positive electrode active material layer 12 may also be selected according to the actual situation.
In one embodiment, the thickness of the positive electrode active material layer 12 is 1 μm to 500 μm, and may be, for example, 1 μm,2 μm,3 μm, 8230498 μm,499 μm,500 μm. By setting different thicknesses of the positive electrode active material layer 12, the positive electrode active material layer 12 can have a corresponding preset compaction density, the thickness and the preset compaction density are in a proportional relation, and the thinner the thickness is, the higher the preset compaction density is. Therefore, the thickness of the positive electrode active material layer 12 can also be selected according to the actual situation.
In this embodiment, the positive electrode active material slurry 120 is generally formed by mixing and stirring positive electrode active material powder, a conductive agent, a binder, solid electrolyte particles, and a solvent, and the solvent generally includes but is not limited to: one or a combination of at least two of water, N-methylpyrrolidone and ethanol.
The positive electrode active material includes LiCoO 2 、LiMnO 2 、LiNi 1-x-y Co x Mn y O 2 (wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5), liFePO 4 And one or more combinations of sulfur-containing positive electrode active materials, wherein the sulfur-containing positive electrode active material mainly comprises Li 2 S and the like. The conductive agent comprises one or more of carbon black conductive agent (SP), graphite conductive agent and graphene conductive agent. The binder comprises one or more of polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and Styrene Butadiene Rubber (SBR).
Referring to fig. 2, fig. 2 shows a manufacturing apparatus for manufacturing the positive electrode composite unit 10, the manufacturing apparatus including: a mixer 13, a first extrusion die 14, a bipolar plate discharge assembly 15, a drying assembly 16, and a rolling assembly 17. The positive electrode active material, the conductive agent, the binder, the solid electrolyte particles, and the solvent are added to the mixer 13, and mixed and stirred by the mixer 13 to form the positive electrode active material slurry 120. The first extrusion die 14 communicates with the mixer 13, and the uniformly stirred positive electrode active material slurry 120 is fed to the first extrusion die 14. The bipolar plate discharging assembly 15 is used for discharging a bipolar plate coil 110, the first extrusion die head 14 uniformly coats the positive active material slurry 120 on one side of the bipolar plate coil 110, and the width of the die opening of the first extrusion die head 14 is adjusted to adjust the thickness of the positive active material slurry 120 coated on one side of the bipolar plate coil 110 to be a preset thickness, in a preferred embodiment, the preset thickness of the coated positive active material slurry 120 is 1 μm to 500 μm, for example: can be 1 μm,2 μm,3 μm, 823030498 μm,499 μm and 500 μm, and is selected according to actual needs. In this embodiment, the cathode active material slurry 120 is coated to a predetermined thickness of 200 μm. The bipolar plate coiled material 110 coated with the positive active material slurry 120 is heated and dried by the drying component 16, so that the positive active material slurry 120 is cured, the cured positive active material slurry 120 and the bipolar plate coiled material 110 are rolled by the rolling component 17, so that the cured positive active material slurry 120 is plastically deformed to form a positive active material layer 12 with a preset compaction density, so that the positive active material layer 12 is compounded on one surface of the bipolar plate coiled material 110, and then the positive composite unit 10 is formed by cutting at a fixed length.
In this embodiment, the bipolar plate roll 110 discharged from the bipolar plate discharging assembly 15 is guided by the guide roller 18 so that the bipolar plate roll 110 is in a horizontal state to ensure uniformity of the thickness of the coating layer applied with the positive active material slurry 120. The drying assembly 16 generally employs an oven, inside which a supporting roller 161 is further provided to support and convey the bipolar plate roll 110 coated with the positive active material slurry 120.
The rolling assembly 17 is composed of an upper roller 171 and a lower roller 172, the upper roller 171 may be a steel roller or a rubber roller, and correspondingly, the lower roller 172 may be a rubber roller or a steel roller, of course, the upper roller 171 and the lower roller 172 may both be steel rollers, or both may be rubber rollers, and is specifically selected according to actual needs. The upper and lower rolls 171 and 172 apply a linear load t, which is expressed by the formula t = F, to the bipolar plate coil 110 coated with the positive electrode active material slurry 120 by rolling N /W c Calculation of in the formula F N A rolling force, W, acting on the bipolar plate coil 110 coated with the positive electrode active material slurry 120 c Is the width of the coated cathode active material slurry 120, wherein the rolling force is the pressure between the upper and lower rolls 171 and 172, that is, the force that plastically deforms the cathode active material slurry 120.
The bipolar plate 11 is coated with electrode active materials with different polarities on two side surfaces thereof, so that the amount of inactive materials can be reduced to improve the energy density of the finished battery. The material of the bipolar plate 11 is usually metal foil such as Al, cu, ni, ti, etc., or stainless steel SUS, etc., and the thickness is usually 5 μm to 30 μm, for example, the thickness of the bipolar plate 11 may be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, and is selected according to actual needs. In this embodiment, stainless steel SUS is used for the bipolar plate 11.
In another embodiment, the positive electrode composite unit may be formed by directly bonding and pulverizing the positive electrode active material powder, the conductive agent, the binder, and the solid electrolyte particles without using a solvent, extruding the resultant mixture by an extruder to form a sheet-like positive electrode active material in the form of a film, covering the sheet-like positive electrode active material layer on the bipolar plate, and sufficiently bonding the sheet-like positive electrode active material to the bipolar plate by roll pressing.
The anode composite unit 20 includes: a solid electrolyte layer 21 and an anode active material layer 22, the anode active material layer 22 being combined on one side of the solid electrolyte layer 21, and the anode active material layer 22 in a molten state being bonded to the other side of the bipolar plate 11, thereby forming a prefabricated module.
The material of the anode active material layer 22 includes, but is not limited to, metals such as lithium, sodium, potassium, or an alloy composed of a plurality of these metals.
The preparation method of the negative electrode composite unit comprises the following steps: the solid electrolyte layer 21 is first heated by heating to a temperature exceeding and maintained at the melting point of the anode active material layer 22 or higher. For example, if metallic lithium is used as the negative electrode active material, since the melting point of metallic lithium is 180 ℃, the hot stage temperature may be 200 ℃. Further, the negative electrode active material 220 in a molten state may be coated on one side of the solid electrolyte layer 21 to form the negative electrode composite unit 20 (refer to the following examples). The thickness of the anode active material layer 22 is usually 1 μm to 50 μm, and may be, for example, 1 μm,2 μm,3 μm, 823048 μm,49 μm, or 50 μm, although the thickness of the anode active material layer 22 may be selected according to the actual circumstances.
Another way to prepare the anode composite unit 20 is: the anode active material layer 22 having a size equivalent to that of the solid electrolyte layer 21 is separately prepared, and the separately prepared anode active material layer 22 is usually a metal foil such as a lithium foil, a sodium foil, or the like. The anode active material layer 22 is then placed over the solid electrolyte layer 21. Before the anode active material layer 22 is placed over the solid electrolyte layer 21, the solid electrolyte layer 21 is heated by heating and kept at the melting point of the anode active material layer 22 or more, and the anode active material layer 22 becomes molten.
The material of the solid electrolyte layer 21 is of perovskite type (e.g., li) 0.33 La 0.56 TiO 3 LLTO), NASICON type (e.g. Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 LATP), LISICON (e.g. Li) 10 GeP 2 S 12 LGPS) and garnet type (e.g. Li) 7 La 3 Zr 2 O 12 LLZO) solid electrolyte.
The preparation method of the prefabricated module comprises the following steps: the anode composite unit 20 is formed, the anode composite unit 20 is heated to make the anode active material layer 22 in a molten state, and the cathode composite unit 10 is placed over the anode composite unit 20 with one surface of the bipolar plate 11 bonded and fixed to the molten anode active material layer 22. Alternatively, the solid electrolyte layer 21 is heated to a temperature higher than or equal to the melting point of the anode active material layer 22, the anode active material 220 is combined with one surface of the solid electrolyte layer 21 to form the molten anode active material layer 22, and the cathode composite unit 10 is placed on the anode composite unit 20, and one surface of the bipolar plate 11 is bonded and fixed to the molten anode active material layer 22.
Referring to fig. 3, fig. 3 illustrates a manufacturing apparatus for manufacturing the negative electrode composite unit 20 according to an embodiment, the manufacturing apparatus including: a storage bin 23, a second extrusion die head 24, and a heating assembly 25, wherein the storage bin 23 has a heating function and is used for storing the molten negative active material 220, and the storage bin 23 is communicated with the second extrusion die head 24 and can convey the molten negative active material 220 to the second extrusion die head 24. The heating unit 25 is configured to heat the solid electrolyte layer 21 to a temperature higher than a melting point of the negative electrode active material 220, and coat the molten negative electrode active material 220 on one surface of the solid electrolyte layer 21 through the second extrusion die 24, wherein the thickness of the negative electrode active material 220 coated on one surface of the solid electrolyte layer 21 is generally 1 μm to 50 μm, and may be, for example, 1 μm,2 μm,3 μm \823048μ m,49 μm, or 50 μm. The specific coating thickness can be adjusted by adjusting the width of the die opening of the second extrusion die 24. After the negative electrode active material 220 in a molten state is coated on one side of the solid electrolyte layer 21, the negative electrode active material 220 and the solid electrolyte layer 21 can be tightly combined, and the negative electrode active material layer 22 is kept in a molten state for a certain time.
In the above embodiment, the anode active material layer 22 is formed by closely bonding the molten anode active material 220 to the solid electrolyte layer 21, so that the loss of lithium and the contamination of impurities in the anode active material layer 22 can be effectively prevented and the capacity of the finished solid-state battery can be further improved, as compared with the conventional roll-pressing method.
In this embodiment, the positive electrode composite unit 10 is placed above the molten negative electrode active material layer 22, and the other surface of the bipolar plate 11 faces the molten negative electrode active material layer 22, and after the molten negative electrode active material layer 22 is solidified, the prefabricated module 100 composed of the positive electrode active material layer, the bipolar plate, the negative electrode active material layer, and the solid electrolyte layer is finally formed.
Specifically, the solid electrolyte layer 21 is heated by the heating assembly 25 to a temperature higher than the melting point of the negative electrode active material layer 22, the molten negative electrode active material 220 is coated on one surface of the solid electrolyte layer 21 by the second extrusion die 24, the negative electrode active material 220 is kept in a molten state by the action of the heating assembly 25, the heating assembly 25 is kept to heat the solid electrolyte layer 21 all the time, the positive electrode composite unit 10 is placed above the molten negative electrode active material 220, the other surface of the bipolar plate 11 faces the molten negative electrode active material 220, and after the molten negative electrode active material 220 is solidified, the prefabricated module 100 composed of the positive electrode active material layer, the bipolar plate, the negative electrode active material layer and the solid electrolyte layer is finally formed.
In the above embodiment, the heating member 25 is kept heating the solid electrolyte layer 21 until the cathode composite unit 10 is placed above the negative electrode active material 220 in a molten state.
In this embodiment, the heating temperature of the heating member 25 to the solid electrolyte layer 21 is 200 ℃ or more, that is, the melting point of the anode active material layer 22 is less than 200 ℃, for example, the melting point of the anode active material layer 22 is 180 ℃ or 190 ℃.
In other embodiments, instead of extrusion coating the anode active material 220 in a molten state, the anode active material layer 22 having a size corresponding to that of the solid electrolyte sheet may be separately prepared, and the anode active material layer 22 may be separately prepared, where the anode active material layer 22 is usually a metal foil, such as lithium foil, sodium foil, and the like. Then, the anode active material layer 22 is placed on the solid electrolyte layer 21, and since the solid electrolyte layer 21 is positioned on the heating member 25 and the temperature of the heating member 25 is higher than the melting point of the anode active material, the anode active material layer 22 becomes molten.
In other embodiments, the anode composite unit 20 is formed after the anode active material layer 22 in a molten state is solidified. Referring to fig. 4, fig. 4 shows another embodiment of a manner of preparing a prefabricated module, heating the anode composite unit 20 by the heating assembly 25 to a temperature above the melting point of the anode active material layer 22 so that the anode active material layer 22 solidified on one side of the solid electrolyte layer 21 is molten, placing the cathode composite unit 10 on the molten anode active material layer 22 and facing the other side of the bipolar plate 11 to the molten anode active material layer 22, and forming the prefabricated module 100 after the molten anode active material layer 22 is solidified.
It is noted that the process for preparing the anode composite unit 20 is performed in a nitrogen or inert gas (e.g., argon, helium, neon, etc.) environment or at least in a drying room.
Example II,
The present embodiment provides a solid-state battery composed of at least two prefabricated modules and an ion conductor adhesive layer disposed between the adjacent two prefabricated modules.
Referring to fig. 5, the present embodiment provides a solid-state battery 300 including: at least two prefabricated modules 100 arranged one above the other, and an ion conductor adhesive layer 200 arranged between two adjacent prefabricated modules 100. In fig. 5, two prefabricated modules 100 and one ion conductor adhesive layer 200 are taken as an example for illustration, and the prefabricated module 100 is a prefabricated module in the first embodiment, wherein all functions and features of the prefabricated module 100 have been described in detail in the first embodiment, and are not described again here. The prefabricated modules 100 are arranged one on another, and the ion conductor adhesive layer 200 has an ion conduction and adhesion function, and the ion conductor adhesive layer 200 serves to adhere the other surface of the solid electrolyte layer 21 of the last prefabricated module 100 of the adjacent two prefabricated modules 100 to the surface of the positive electrode active material layer 12 of the next prefabricated module 100 and conduct ions between the positive electrode active material and the solid electrolyte, thereby forming the solid-state battery 300.
In this embodiment, the ion conductor adhesive slurry may be combined on the surface of the positive electrode active material layer 12 to form the ion conductor adhesive layer 200.
It is understood that solid-state battery 300 may be formed from a plurality of prefabricated modules 100 stacked one on top of the other, and ion conductor adhesive layer 200 may not be provided on the uppermost prefabricated module.
The ion conductor adhesive layer 200 material is an organic polymer or organic-inorganic composite material with ion conduction, wherein the organic ion conductor polymer comprises: one or more of perfluorosulfonic acids, polyionic liquids, PEO (Polyethylene oxide), PEG (Polyethylene glycol), PAA (Polyacrylic acid), sulfonated polyurethane, or sulfonated polyetheretherketone.
The organic-inorganic composite material is a composite material of an organic material and an inorganic material, wherein the organic material comprises: one or more of perfluorosulfonic acids, polyionic liquids, PEO (Polyethylene oxide), PEG (Polyethylene glycol), PAA (Polyacrylic acid), sulfonated polyurethane, sulfonated polyetheretherketone, PVDF (Polyvinylidene difluoride), PTFE (polytetrafluoroethylene), CMC (Carboxymethyl Cellulose) or SBR (Polymerized Styrene Butadiene Rubber) and perovskite type (e.g. Li, styrene Butadiene Rubber) 0.33 La 0.56 TiO 3 LLTO), NASICON type (e.g. Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 LATP), LISICON type (e.g. Li) 10 GeP 2 S 12 LGPS) and garnet type (e.g. Li) 7 La 3 Zr 2 O 12 LLZO) solid electrolyte.
In this embodiment, the ion conductor adhesive layer 200 is made of PVDF-perfluorosulfonic acid-LATP material, and is specifically selected according to actual needs, by lithiating perfluorosulfonic acid (Nafion) to obtain Li-Nafion, dissolving Li-Nafion in organic solvent DMF (with a solid content of 10%), adding PVDF and 10% LATP in equal proportions, stirring to form a uniform slurry, coating the uniform slurry on the surface of the positive electrode active material layer 12, and heating to perform in-situ polymerization and curing, so that the thickness of the positive electrode active material layer 12 is 1 μm to 10 μm, for example, 1 μm,2 μm,3 μm \8230, 8 μm, 9 μm, and 10 μm.
Referring to fig. 6, fig. 6 illustrates the manner in which a plurality of prefabricated modules 100 form a solid-state battery 300.
In this embodiment, the ion conductor adhesive layer 200 is used to tightly adhere the other surface of the solid electrolyte layer 21 of the previous prefabricated module 100 of the two adjacent prefabricated modules 100 to the surface of the positive electrode active material layer 12 of the next prefabricated module 100, so that the impedance between the solid electrolyte layer 21 of the previous prefabricated module 100 and the positive electrode active material layer 12 of the next prefabricated module 100 can be effectively reduced, and the preparation efficiency of the solid-state battery can be improved.
Example III,
In this embodiment, a method for manufacturing a solid-state battery based on the second embodiment is provided, and referring to fig. 7, the method for manufacturing a solid-state battery provided in this embodiment includes the following steps: the method comprises a positive electrode composite unit forming step S100, a negative electrode composite unit forming step S200, a prefabricated module forming step S300 and a solid-state battery forming step S400.
A positive electrode composite unit forming step S100 of forming a positive electrode composite unit 10 by combining the positive electrode active material slurry 120 on one surface of the bipolar plate 11 to form the positive electrode active material layer 12, the positive electrode composite unit being composed of the positive electrode active material layer 12 and the bipolar plate 11 having a predetermined density.
In this example, the positive electrode was repeatedIn the step S100 of forming the combined unit, after the positive electrode active material slurry 120 is combined on one side of the bipolar plate 11, the positive electrode active material layer 12 is formed after the positive electrode active material slurry 120 is solidified and rolled, in a manner that the positive electrode active material layer 12 has a predetermined compacted density, in a preferred embodiment, the predetermined compacted density of the positive electrode active material layer 12 is greater than or equal to 2.8 g/cm 3 For example, the preset compaction density may be 2.8 g/cm 3 、3.0g/cm 3 、3.2 g/cm 3 、3.4 g/cm 3 And the like, of course, the predetermined compaction density of the positive electrode active material layer 12 may also be selected according to actual circumstances.
In one embodiment, the thickness of the positive electrode active material layer 12 is 1 μm to 500 μm, and may be, for example, 1 μm,2 μm,3 μm, 8230498 μm,499 μm,500 μm. Of course, the thickness of the positive electrode active material layer 12 can be selected according to the actual situation.
Specifically, after the positive electrode active material slurry 120 with a preset thickness is coated on one surface of the bipolar plate 11, the positive electrode active material slurry 120 is dried, cured, rolled and compacted to form the positive electrode active material layer 12 with a preset compaction density, and the preset compaction density enables the positive electrode active material layer 12 to have certain compactness, so that the energy density of the finished solid-state battery can be improved, and the battery capacity can be improved.
The positive electrode active material slurry 120 is generally formed by mixing and stirring positive electrode active material powder, a conductive agent, a binder, solid electrolyte particles, and a solvent, which generally includes but is not limited to: one or a combination of at least two of water, N-methylpyrrolidone and ethanol. The positive electrode active material comprises LiCoO 2 、LiMnO 2 、LiNi 1-x-y Co x Mn y O 2 (wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5), liFePO 4 And Li 2 S and the like, and one or more of sulfur-containing positive electrode active materials. The conductive agent comprises one or more of carbon black conductive agent (SP), graphite conductive agent and graphene conductive agent. The binder comprises one or more of polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and Styrene Butadiene Rubber (SBR).
As shown in fig. 2, fig. 2 shows a manufacturing apparatus for manufacturing the positive electrode composite unit 10, the manufacturing apparatus including: a mixer 13, a first extrusion die 14, a bipolar plate discharge assembly 15, a drying assembly 16, and a rolling assembly 17. The positive electrode active material, the conductive agent, the binder, the solid electrolyte particles, and the slurry solvent are added to the mixer 13, and mixed and stirred by the mixer 13 to form the positive electrode active material slurry 120. The first extrusion die 14 communicates with the mixer 13, and the uniformly stirred positive electrode active material slurry 120 is fed to the first extrusion die 14. The bipolar plate discharging assembly 15 is used for discharging the bipolar plate coiled material 110, the first extrusion die head 14 uniformly coats the positive active material slurry 120 on one side of the bipolar plate coiled material 110, and the thickness of the positive active material slurry 120 coated on one side of the bipolar plate coiled material 110 is adjusted to be a preset thickness by adjusting the width of the die opening of the first extrusion die head 14, in a preferred embodiment, the preset thickness of the coated positive active material slurry 120 is 1 μm to 500 μm, for example: can be 1 μm,2 μm,3 μm, 823030498 μm,499 μm and 500 μm, and is selected according to actual needs. In this embodiment, the cathode active material slurry 120 is coated to a predetermined thickness of 200 μm. The bipolar plate roll 110 coated with the positive active material slurry 120 is heated and dried by the drying component 16 to solidify the positive active material slurry 120, the solidified positive active material slurry 120 and the bipolar plate roll 110 are rolled by the rolling component 17, so that the solidified positive active material slurry 120 generates plastic deformation to form a positive active material layer 12 with a preset compaction density, the positive active material layer 12 is compounded on one surface of the bipolar plate roll 110, and the positive composite unit 10 is formed by cutting at a fixed length.
In this embodiment, the bipolar plate roll 110 discharged from the bipolar plate discharging assembly 15 is guided by the guide roller 18 so that the bipolar plate roll 110 is in a horizontal state to ensure uniformity of the thickness of the coating layer applied with the positive active material slurry 120. The drying assembly 16 generally employs an oven, inside which a supporting roller 161 is further provided to support and convey the bipolar plate roll 110 coated with the positive active material slurry 120.
The rolling assembly 17 consists of an upper roll171 and a lower roller 172, wherein the upper roller 171 can be a steel roller or a rubber roller, and correspondingly, the lower roller 172 can be a rubber roller or a steel roller, of course, both the upper roller 171 and the lower roller 172 can be steel rollers, or both can be rubber rollers, and the selection is specifically carried out according to actual needs. The upper and lower rolls 171 and 172 apply a linear load t, which is expressed by the formula t = F, to the bipolar plate coil 110 coated with the positive electrode active material slurry 120 by rolling N /W c Calculation of in the formula F N A rolling force, W, acting on the bipolar plate coil 110 coated with the positive electrode active material slurry 120 c Is the width of the coated cathode active material slurry 120, wherein the rolling force is the pressure between the upper and lower rolls 171 and 172, that is, the force that plastically deforms the cathode active material slurry 120.
The bipolar plate 11 is coated with electrode active materials with different polarities on two side surfaces thereof, so that the amount of inactive materials can be reduced to improve the energy density of the finished battery. The material of the bipolar plate 11 is usually metal foil such as Al, cu, ni, ti, etc., or stainless steel SUS, etc., and the thickness is usually 5 μm to 30 μm, for example, the thickness of the bipolar plate 11 may be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, and is selected according to actual needs. In this embodiment, stainless steel SUS is used for the bipolar plate 11.
In another embodiment, the positive electrode composite unit may be formed by directly bonding and pulverizing the positive electrode active material powder, the conductive agent, the binder, and the solid electrolyte particles without using a solvent, extruding the resultant mixture by an extruder to form a sheet-like positive electrode active material in the form of a thin film, covering the sheet-like positive electrode active material layer on the bipolar plate, and sufficiently bonding the sheet-like positive electrode active material to the bipolar plate by roll pressing.
In the anode composite unit forming step S200, the anode active material layer 22 is formed by combining the anode active material 220 on one surface of the solid electrolyte layer 21, and the anode composite unit 20 composed of the anode active material layer 22 and the solid electrolyte layer 21 is obtained.
The active material of the anode active material layer 22 includes, but is not limited to, a metal such as lithium, sodium, potassium, or an alloy composed of a plurality of metals.
The preparation method of the negative electrode composite unit comprises the following steps: first, the solid electrolyte layer 21 is heated by heating to a temperature exceeding and maintained at the melting point of the anode active material layer 22 or higher. For example, if metallic lithium is used as the negative active material, since the melting point of metallic lithium is 180 ℃, the hot stage temperature may be 200 ℃. Further, the negative electrode active material 220 in a molten state may be coated on one side of the solid electrolyte layer 21 to form the negative electrode composite unit 20 (refer to the following examples). The thickness of the anode active material layer 22 is usually 1 μm to 50 μm, and may be, for example, 1 μm,2 μm,3 μm, 823048 μm,49 μm, or 50 μm, although the thickness of the anode active material layer 22 may be selected according to the actual circumstances.
Another way to prepare the anode composite unit 20 is: the anode active material layer 22 having a size equivalent to that of the solid electrolyte layer 21 is separately prepared, and the separately prepared anode active material layer 22 is usually a metal foil such as a lithium foil, a sodium foil, or the like. The anode active material layer 22 is then placed over the solid electrolyte layer 21. Before the anode active material layer 22 is placed over the solid electrolyte layer 21, the solid electrolyte layer 21 is heated by heating and kept at the melting point of the anode active material layer 22 or more, and the anode active material layer 22 becomes molten.
A prefabricated module forming step S300 of putting the anode active material layer 22 in a molten state, stacking the cathode composite unit 10 over the anode composite unit 20, and facing the other surface of the bipolar plate 11 toward the molten anode active material layer 22, so that the other surface of the bipolar plate 11 is bonded to the molten anode active material layer 22, and solidifying the molten anode active material layer 22 to obtain a prefabricated module 100.
Specifically, the anode composite unit 20 is formed, the anode composite unit 20 is heated to make the anode active material layer 22 in a molten state, and the cathode composite unit 10 is placed over the anode composite unit 20 with one surface of the bipolar plate 11 bonded and fixed to the molten anode active material layer 22. Alternatively, the solid electrolyte layer 21 is heated to a temperature higher than or equal to the melting point of the anode active material layer 22, the anode active material 220 is combined with one surface of the solid electrolyte layer 21 to form the molten anode active material layer 22, and the cathode composite unit 10 is placed on the anode composite unit 20, and one surface of the bipolar plate 11 is bonded and fixed to the molten anode active material layer 22.
The material of the solid electrolyte layer 21 is of perovskite type (e.g., li) 0.33 La 0.56 TiO 3 LLTO), NASICON type (e.g. Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 LATP), LISICON type (e.g. Li) 10 GeP 2 S 12 LGPS) and garnet type (e.g. Li) 7 La 3 Zr 2 O 12 LLZO) solid electrolyte.
As shown in fig. 3, fig. 3 illustrates a preparation apparatus for preparing the anode composite unit 20 according to an embodiment, the preparation apparatus including: a storage bin 23, a second extrusion die head 24, and a heating assembly 25, wherein the storage bin 23 has a heating function and is used for storing the molten negative active material 220, and the storage bin 23 is communicated with the second extrusion die head 24 and can convey the molten negative active material 220 to the second extrusion die head 24. The heating unit 25 is configured to heat the solid electrolyte layer 21 to a temperature higher than a melting point of the negative electrode active material 220, and coat the molten negative electrode active material 220 on one surface of the solid electrolyte layer 21 through the second extrusion die 24, wherein the thickness of the negative electrode active material 220 coated on one surface of the solid electrolyte layer 21 is generally 1 μm to 50 μm, and may be, for example, 1 μm,2 μm,3 μm \823048μ m,49 μm, or 50 μm. The specific coating thickness can be adjusted by adjusting the width of the die opening of the second extrusion die 24. After the anode active material 220 is coated on one side of the solid electrolyte layer 21, the anode active material 220 and the solid electrolyte layer 21 can be tightly combined, and the anode active material layer 22 is kept in a molten state for a certain time.
In the above embodiment, the negative electrode active material layer 22 is formed by closely bonding the molten negative electrode active material 220 to the solid electrolyte layer 21, so that the loss of lithium and contamination of impurities in the negative electrode active material layer 22 can be effectively avoided and the capacity of the finished solid-state battery can be further improved, as compared with the conventional method of rolling.
In this embodiment, the positive electrode composite unit 10 is placed above the molten negative electrode active material layer 22, and the other surface of the bipolar plate 11 faces the molten negative electrode active material layer 22, and after the molten negative electrode active material layer 22 is solidified, the prefabricated module 100 composed of the positive electrode active material layer, the bipolar plate, the negative electrode active material layer, and the solid electrolyte layer is finally formed.
Specifically, the solid electrolyte layer 21 is heated by the heating assembly 25 to a temperature higher than the melting point of the negative electrode active material layer 22, the molten negative electrode active material 220 is coated on one surface of the solid electrolyte layer 21 by the second extrusion die 24, the negative electrode active material 220 is kept in a molten state by the action of the heating assembly 25, the heating assembly 25 is kept to heat the solid electrolyte layer 21 all the time, the positive electrode composite unit 10 is placed above the molten negative electrode active material 220, the other surface of the bipolar plate 11 faces the molten negative electrode active material 220, and after the molten negative electrode active material layer 22 is solidified, the prefabricated module 100 composed of the positive electrode active material layer, the bipolar plate, the negative electrode active material layer and the solid electrolyte layer is finally formed.
In the above embodiment, the heating member 25 is kept heating the solid electrolyte layer 21 until the cathode composite unit 10 is placed above the negative electrode active material 220 in a molten state.
In this embodiment, the heating temperature of the heating element 25 to the solid electrolyte layer 21 is 200 ℃ or more, that is, the melting point of the anode active material layer 22 is lower than 200 ℃.
In other embodiments, instead of extrusion coating the molten anode active material 220, the anode active material layer 22 may be separately prepared, and the anode active material layer 22 may be prepared separately, wherein the anode active material layer 22 is typically a metal foil, such as lithium foil, sodium foil, etc., having a size comparable to that of the solid electrolyte sheet. Then, the anode active material layer 22 is placed on the solid electrolyte layer 21, and since the solid electrolyte layer 21 is positioned on the heating member 25 and the temperature of the heating member 25 is higher than the melting point of the anode active material, the anode active material layer 22 becomes molten, and the anode composite unit 20 is obtained.
In one embodiment, the anode composite unit 20 is formed after the molten anode active material layer 22 is solidified. As shown in fig. 4, fig. 4 shows a manner of preparing a prefabricated module in an embodiment, the anode composite unit 20 is heated by the heating assembly 25 to a temperature above the melting point of the anode active material layer 22 so that the anode active material layer 22 solidified on one side of the solid electrolyte layer 21 reaches a molten state, the cathode composite unit 10 is placed over the molten anode active material layer 22 with the other side of the bipolar plate 11 facing the molten anode active material layer 22, and the prefabricated module 100 is formed after the molten anode active material layer 22 is solidified.
The process for preparing the anode composite unit 20 is performed in a nitrogen or inert gas (e.g., argon, helium, neon, etc.) environment or at least in a dry room.
A solid-state battery forming step S400 of stacking at least two prefabricated modules 100, disposing an ion conductor adhesive layer 200 between two adjacent prefabricated modules 100, so that the other surface of the solid electrolyte layer 21 of the last prefabricated module 100 of the two adjacent prefabricated modules 100 is adhered to the positive electrode active material layer 12 of the next prefabricated module 100, and obtaining a solid-state battery 300 after the ion conductor adhesive layer 200 is cooled and solidified.
In this embodiment, the ion conductor adhesive slurry may be combined on the surface of the positive electrode active material layer 12 to form the ion conductor adhesive layer 200.
It is understood that solid-state battery 300 may be formed from a plurality of prefabricated modules 100 stacked one on top of the other, and ion conductor adhesive layer 200 may not be provided on the uppermost prefabricated module.
The ion conductor adhesive layer 200 material is an organic polymer or organic-inorganic composite material with ion conduction, wherein the organic ion conductor polymer comprises: one or more of perfluorosulfonic acids, polyionic liquids, PEO (Polyethylene oxide), PEG (Polyethylene glycol), PAA (Polyacrylic acid), sulfonated polyurethane, or sulfonated polyetheretherketone.
The organic-inorganic composite material is a composite material of an organic material and an inorganic material, wherein the organic material comprises: one or more of perfluorosulfonic acids, polyionic liquids, PEO (Polyethylene oxide), PEG (Polyethylene glycol), PAA (Polyacrylic acid), sulfonated polyurethane, sulfonated polyetheretherketone, PVDF (Polyvinylidene difluoride), PTFE (polytetrafluoroethylene), CMC (Carboxymethyl Cellulose) or SBR (Polymerized Styrene Butadiene Rubber) and perovskite type (e.g. Li, styrene Butadiene Rubber) 0.33 La 0.56 TiO 3 LLTO), NASICON type (e.g. Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 LATP), LISICON type (e.g. Li) 10 GeP 2 S 12 LGPS) and garnet type (e.g. Li) 7 La 3 Zr 2 O 12 LLZO) solid electrolyte.
In this embodiment, the ion conductor adhesive layer 200 is a self-polymerizable 1-vinyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide (VBimTFSI ionic liquid) -LLZO material, VBimTFSI, 10% LLZO and 0.5wt% AIBN are uniformly mixed, coated on the surface of the positive electrode active material layer 12, and cured by in-situ polymerization under heating so that the thickness of the positive electrode active material layer 12 is 1 μm to 10 μm, for example, 1 μm,2 μm,3 μm \8230, 8 μm, 9 μm, and 10 μm, which are selected according to actual needs.
In the present embodiment, in the anode composite unit forming step S200, the process of forming the anode composite unit 20 composed of the anode active material layer 22 and the solid electrolyte layer 21 by compositing the anode active material 220 on one side of the solid electrolyte layer 21 is performed in an atmosphere of nitrogen or an inert gas (e.g., argon, helium, neon, etc.), or at least in a drying room.
In this embodiment, regarding the molten negative electrode active material layer, in one embodiment, the solid electrolyte layer 21 is heated to a temperature equal to or higher than the melting point of the negative electrode active material layer 22, and the negative electrode active material 220 is combined with one surface of the solid electrolyte layer to form the negative electrode active material layer 22, so that the molten negative electrode active material layer 22 is obtained. In another embodiment, the anode composite unit 20 is heated, and the heating temperature is brought to the melting point of the anode active material layer 22 or more to obtain the anode active material layer 22 in a molten state.
The specific process of the method for manufacturing a solid-state battery provided in this embodiment is as follows:
regarding the preparation of the positive electrode composite unit 10, the positive electrode active material slurry 120 was composed of a 60% solid content consisting of 95% by mass of the positive electrode active material NMC622, 1% of polyvinylidene fluoride (PVDF), 2% of carbon black conductive agent (SP), and 2% of solid electrolyte particles, and 40% by mass of nmp solvent combination, wherein NMC622 was a nickel manganese cobalt ternary material, liNi 1-x-y Co x Mn y O 2 (wherein, x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.5), when x =0.2 y =0.2 is NMC622, the material of the solid electrolyte particles is lithium lanthanum zirconium oxygen LLZO (Li) 7 La 3 Zr 2 O 12 ) The bipolar plate 11 is made of stainless steel having a thickness of 10 μm. The positive active material slurry 120 was fed to the first extrusion die 14 to be coated on one side of the bipolar plate 11 to a coating thickness of 200 d. The anode active material slurry 120 coating is dried by a drying component 16, the dried anode active material slurry and the bipolar plate exert a linear load of 1000N/mm or more by a rolling component 17 to realize 3.2g/cm 3 And the coating layer is compacted to reach the positive active material layer 12 with the thickness of 50 mu m, and the positive composite unit 10 is obtained.
In another embodiment, in the preparation of the positive electrode composite member 10, 95% by mass of the positive electrode active material NMC622, 1% by mass of polyvinylidene fluoride (PVDF), 2% by mass of carbon black conductive agent (SP), and 2% by mass of solid electrolyte particles are mixed to obtain a mixture, large particles in the mixture are crushed by mechanical pressing to form a powdery mixture, 73kN/cm is applied to the powdery mixture 2 And compression-molded at 80 ℃. Specifically, it was compressed to 50 μm by rolling at 80 ℃ to obtain a sheet-like positive electrodeAnd the active material, namely, the flaky positive active material is covered on a stainless steel bipolar plate with the thickness of 10 mu m, and linear load of 1000N/mm or more is applied to the bipolar plate through a rolling assembly 17, so that the flaky positive active material is fully contacted with the bipolar plate, and the positive composite unit 10 consisting of the positive active material layer 12 and the bipolar plate 11 is obtained.
Regarding the preparation of the negative electrode composite unit 20, an oxide solid electrolyte powder is selected, and the material of the solid electrolyte powder is also lithium lanthanum zirconium oxygen LLZO (Li) 7 La 3 Zr 2 O 12 ) Pressurizing garnet type oxide solid electrolyte to obtain a solid electrolyte sheet with the thickness of 30 mu m, placing solid electrolyte powder between two carbon sheets, quickly heating to more than 1500 ℃ by high-power electrification, sintering and cooling to obtain a sheet-shaped and compact solid electrolyte layer 21. The solid electrolyte layer 21 is heated to 200 ℃ by the heating element 25. The negative electrode active material 220 is prepared and heated to a molten state, and the negative electrode active material 220 (for example, lithium composite metal) in the molten state is fed to the second extrusion die 24 in a nitrogen atmosphere, and is rapidly coated on one side of the solid electrolyte layer 21 through the second extrusion die 24 to a coating thickness of 20 μm, to obtain the negative electrode composite unit 20.
Regarding the preparation of the prefabricated module 100, the anode composite unit is heated by the heating assembly 25, the other side of the solid electrolyte layer is kept in contact with the heating assembly 25, the heating temperature is up to 200 ℃, when the anode active material layer 22 reaches a molten state, the anode composite unit 10 is placed above the anode composite unit 20, the other side of the bipolar plate 11 is kept in contact with the molten anode active material layer 22, the anode active material 220 is rapidly bonded with the solid electrolyte layer 21 by using high temperature, and the prefabricated module 100 is obtained after cooling and solidification.
Regarding the preparation of the solid-state battery 300, a plurality of prefabricated modules 100 are taken, an ion conductor adhesive layer 200 is coated on the surface of the positive electrode active material layer of each prefabricated module 100, the ion conductor adhesive layer 200 is used for bonding the other surface of the solid-state electrolyte layer 21 of the previous prefabricated module 100 in two adjacent prefabricated modules 100 and the surface of the positive electrode active material layer 12 of the next prefabricated module 100 in series, and then the prefabricated modules are packaged and integrated into the solid-state battery 300.
In another embodiment, regarding the preparation of the prefabricated module 100, after the anode composite unit 20 is prepared, the heating of the anode composite unit 20 by the heating assembly 25 is kept to be continued so that the anode active material layer 22 is kept in a molten state, then the prepared cathode composite unit 10 is placed over the molten anode active material layer with the other side of the bipolar plate 11 facing the molten anode active material layer 22, and after the molten anode active material layer 22 is cooled and solidified, the prefabricated module 100 is obtained.
In summary, in the prefabricated module of the solid-state battery, the solid-state battery and the manufacturing method thereof provided by the present application, the positive electrode composite unit and the negative electrode composite unit are separately manufactured, and the positive electrode active material layer can have the predetermined compacted density under the rolling with a large rolling force, so as to increase the capacity of the finished solid-state battery and avoid the problem that the solid-state electrolyte layer cannot realize a large compacted density due to consideration of the mechanical strength. In the preparation process of the solid-state battery, the prefabricated modules are bonded through the ion conductor bonding layer, so that the solid-state electrolyte layer can be prevented from being subjected to brittle fracture due to compaction splicing, and the contradiction between the compaction density of the positive electrode active material layer in the solid-state battery and the brittle fracture of the solid-state electrolyte layer is avoided. The molten negative electrode active material layer is formed by heating, so that the capacity loss caused by rolling of the negative electrode composite unit is avoided, and meanwhile, the plurality of prefabricated modules are bonded by the ion conductor bonding layers to prepare the solid-state battery, so that the preparation efficiency can be effectively improved.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. Numerous simple deductions, modifications or substitutions may also be made by those skilled in the art in light of the present teachings.

Claims (9)

1. A prefabricated module for a solid-state battery, comprising: the positive electrode composite unit and the negative electrode composite unit are arranged in a stacked mode; the positive electrode composite unit includes: the bipolar plate comprises a bipolar plate and a positive electrode active material layer, wherein the positive electrode active material layer is compounded on one surface of the bipolar plate and has a preset compaction density; the anode composite unit includes: a solid electrolyte layer and an anode active material layer, the anode active material layer being combined on one surface of the solid electrolyte layer; the negative electrode active material layer is bonded to the other surface of the bipolar plate in a molten state; the preparation method of the prefabricated module comprises the following steps: the anode composite unit is formed first, then the anode composite unit is heated to make the anode active material layer in a molten state, then the anode composite unit is placed above the anode composite unit, and one surface of the bipolar plate is bonded with the molten anode active material layer.
2. The prefabricated module for a solid-state battery of claim 1, wherein the predetermined compacted density is 2.8 g/cm or greater 3 。
3. A solid-state battery, comprising: at least two prefabricated modules according to claim 1 or 2 arranged in a stacked manner, and an ion conductor adhesive layer arranged between two adjacent prefabricated modules, wherein the ion conductor adhesive layer is used for bonding the other surface of the solid electrolyte layer of the prefabricated module in the upper part of the two adjacent prefabricated modules with the surface of the positive electrode active material layer of the next prefabricated module and conducting ions.
4. The solid-state battery according to claim 3, wherein a material of the ion conductor adhesive layer is an organic polymer or an organic-inorganic composite material having ion conduction.
5. The solid-state battery according to claim 4, wherein the organic polymer comprises: one or more of perfluorosulfonic acids, polyionic liquids, PEO, PEG, PAA, sulfonated polyurethane, or sulfonated polyether ether ketone.
6. The solid-state battery according to claim 4, wherein the organic-inorganic composite material is a composite material of an organic material and an inorganic material, the organic material including: one or more combinations of perfluorosulfonic acids, polyionic liquids, PEO, PEG, PAA, sulfonated polyurethane, sulfonated polyetheretherketone, PVDF, PTFE, CMC, or SBR, and the inorganic material comprises one or more combinations of perovskite, NASICON, LISICON, and garnet solid electrolytes.
7. A method for manufacturing a solid-state battery based on any one of claims 3 to 6, comprising the steps of:
compounding the positive active material slurry on one surface of the bipolar plate to form a positive active material layer to obtain a positive composite unit consisting of the positive active material layer with preset compaction density and the bipolar plate;
compounding a negative electrode active material on one surface of the solid electrolyte layer to form a negative electrode active material layer, thereby obtaining a negative electrode composite unit composed of the negative electrode active material layer and the solid electrolyte layer;
the negative electrode active material layer is in a molten state, the positive electrode composite unit is stacked above the negative electrode composite unit, the other surface of the bipolar plate faces the molten negative electrode active material layer, the other surface of the bipolar plate is bonded with the molten negative electrode active material layer, and the prefabricated module is obtained after the molten negative electrode active material layer is solidified;
and stacking at least two prefabricated modules, arranging an ion conductor bonding layer between every two adjacent prefabricated modules, bonding the other surface of the solid electrolyte layer of the upper prefabricated module in the two adjacent prefabricated modules with the surface of the positive electrode active material layer of the lower prefabricated module, and curing the ion conductor bonding layer to obtain the solid-state battery.
8. The method of manufacturing a solid-state battery according to claim 7, wherein in the step of forming the positive electrode active material layer by laminating the positive electrode active material slurry on one surface of the bipolar plate to obtain the positive electrode composite unit composed of the positive electrode active material layer and the bipolar plate, after the positive electrode active material slurry is laminated on one surface of the bipolar plate, the positive electrode active material layer having a predetermined compacted density is formed after the positive electrode active material slurry is cured and rolled.
9. The method for producing a solid-state battery according to claim 7, wherein the solid-state electrolyte layer is heated to a temperature higher than a melting point of the negative electrode active material layer, and the negative electrode active material is compounded on one surface of the solid-state electrolyte layer to form the negative electrode active material layer in a molten state.
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