CN116632248B - Preparation method of solid-state battery and solid-state battery - Google Patents
Preparation method of solid-state battery and solid-state battery Download PDFInfo
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- CN116632248B CN116632248B CN202310899010.2A CN202310899010A CN116632248B CN 116632248 B CN116632248 B CN 116632248B CN 202310899010 A CN202310899010 A CN 202310899010A CN 116632248 B CN116632248 B CN 116632248B
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The application discloses a preparation method of a solid-state battery and the solid-state battery, which belong to the technical field of solid-state batteries, wherein the preparation method comprises the steps of obtaining an anode high-molecular polymer solution and a cathode high-molecular polymer solution; mixing the positive high molecular polymer solution with a positive active substance, a conductive agent and a binder to obtain positive active slurry, and coating the positive active slurry on the surface of a current collector to obtain a positive plate; mixing the negative high polymer solution with a negative active substance, a conductive agent and a binder to obtain negative active slurry, and coating the negative active slurry on the surface of a current collector to obtain a negative electrode plate; mixing a plasticizer, a solid electrolyte material and a binder to obtain electrolyte slurry, and preparing a solid electrolyte sheet; and assembling the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process to obtain the composite electrode. The application improves the interface contact between the electrode and the solid electrolyte from the aspect of molecular movement and improves the stability of the interface between the electrode and the solid electrolyte.
Description
Technical Field
The application relates to the technical field of solid-state batteries, in particular to a preparation method of a solid-state battery and the solid-state battery.
Background
In order to relieve energy crisis and protect environment, various batteries have become necessities of life, and play an important role in the fields of consumer electronics, electric automobiles, aerospace and the like. However, lithium ion batteries containing liquid electrolytes are extremely susceptible to ignition and even explosion due to the use of flammable organic solvents; conventional sodium ion batteries using liquid organic electrolytes still suffer from safety problems caused by the inherent flammability and leakage characteristics of the electrolyte. Therefore, the non-flammable solid electrolyte is used as a carrier for lithium ion and sodium ion transmission instead of flammable liquid electrolyte, so that the safety of the battery can be greatly improved. In addition, due to the high mechanical strength of the solid electrolyte, the solid-state battery is expected to suppress overgrowth of lithium dendrites and sodium dendrites to some extent, thereby enabling the application of metallic lithium or metallic sodium as a negative electrode, which greatly increases the energy density of the battery. Therefore, solid-state batteries are considered as one of the key battery technologies in the future, and have attracted great attention in recent years.
The interface problem of the solid-state battery is the most important difficulty problem which is accepted in the current academic world and affects the performance of the solid-state battery, and both solid-state lithium ion batteries and sodium ion batteries face the challenge of improving the compatibility of electrodes and solid electrolyte layers. The interface in the solid-state battery is changed from a solid-liquid contact interface in the traditional liquid-state battery to a solid-solid contact interface contact mode, the contact area is small in most cases, and the interface can be initially in surface contact under a small part of battery systems, but with the circulation of the battery, the electrode material inevitably expands in volume, so that originally good contact is deteriorated, the ion transmission path is reduced, the interface impedance is increased, and the battery performance is continuously deteriorated.
In patent No. CN115472917a, a method for manufacturing a solid-state battery, and a prior art of a solid-state battery, a solid electrolyte membrane and a negative electrode sheet are compounded together by a primary compounding process to form a negative electrode composite material tape, then the negative electrode composite material tape and a positive electrode sheet are secondarily compounded to form a pole piece composite material tape, and the pole piece composite material tape is stacked to form a battery cell. According to the technology, the interface modification layers are arranged between the solid electrolyte membrane and the positive plate and between the solid electrolyte membrane and the negative plate, so that on one hand, the volume energy density of the battery is reduced due to the existence of the modification layers, and the thickness consistency of the pole pieces and mass production are also not facilitated; on the other hand, the technology only increases the physical contact of the solid-solid interface, and does not promote the compatibility of the electrode and the solid electrolyte layer in terms of interface chemistry.
As other solutions to the solid-solid interface problem in the solid-state battery, a rolling method is often adopted to compact the electrode and the solid electrolyte layer, so that the contact between the electrode and the solid electrolyte layer is promoted to be tighter to a certain extent, but only the physical contact layer is improved, and the problem of poor compatibility of the interface between the electrode and the solid electrolyte layer is not solved.
Meanwhile, the interface problem of the solid electrolyte layer may cause serious problems due to the existence of an unstable interface, such as short cycle life, rapid performance degradation, etc., and physical mismatch at the solid-solid interface may cause irreversible emerging grain boundary damage, poor physical contact, increased internal resistance and migration of foreign ions, thereby forming cracks in the positive electrode particles. In addition, the volume change of the active material during repeated lithiation-delithiation and intercalation-deintercalation of sodium ions further increases the interfacial stress and weakens the bond-contact interface, indicating that good interfacial mechanical stability is also critical to obtain high performance solid state batteries.
Therefore, how to improve the compatibility of the interface of the solid electrolyte layer in the solid-state battery, thereby improving the cycle and stability thereof, is an urgent need.
Disclosure of Invention
The application aims to provide a preparation method of a solid-state battery, which aims at the problem of solid-solid interface in the solid-state battery, improves interface contact between an electrode and a solid electrolyte from the aspect of molecular movement, enables the electrode and the solid electrolyte to be better contacted, reduces interface impedance, improves the stability of the interface between the electrode and the solid electrolyte, and further prepares the solid-state battery with high interface compatibility. Meanwhile, the application also provides a solid-state battery based on the preparation method of the solid-state battery.
The aim of the application is mainly realized by the following technical scheme: a method of manufacturing a solid state battery comprising the steps of:
respectively preparing a positive high polymer solution and a negative high polymer solution from high polymer;
mixing the positive high molecular polymer solution with a positive active substance, a conductive agent and a binder to obtain positive active slurry, coating the surface of a current collector with the positive active slurry, drying, cold pressing and cutting to obtain a positive plate;
mixing the negative high polymer solution with a negative active substance, a conductive agent and a binder to obtain negative active slurry, coating the negative active slurry on the surface of a current collector, drying, cold pressing and cutting to obtain a negative pole piece;
dissolving a plasticizer in a solvent to form a solution, mixing the solution with a solid electrolyte material and a binder, stirring to a uniform state to obtain electrolyte slurry, pouring, drying and cutting the electrolyte slurry to obtain a solid electrolyte sheet;
and assembling the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process to obtain the solid battery.
Based on the preparation method, the high molecular polymer and the plasticizer of the positive high molecular polymer solution and the negative high molecular polymer solution satisfy the following conditions:
the blend of the high molecular polymer and the plasticizer has only one glass transition temperature;
or alternatively, the first and second heat exchangers may be,
in a DSC curve with temperature as the abscissa, a blend of a high polymer and a plasticizer generates two glass transition temperatures, tg1 and Tg2, respectively, and Tg1, tg2, tg3 and Tg4 satisfy:。
based on the preparation method, the high molecular polymer in the positive pole high molecular polymer solution and/or the negative pole high molecular polymer solution is one or the combination of more than two of polyvinyl chloride, polystyrene-butadiene-styrene, polystyrene and polymethyl methacrylate;
the solvent of the positive high polymer solution and/or the negative high polymer solution is one or the combination of two substances of toluene and acetone.
Based on the preparation method, in the positive electrode active slurry, the mass ratio of the high molecular polymer to the positive electrode active material, the conductive agent and the binder is 0.05-2.5: 80-99:1-5:1-5.
Based on the preparation method, in the negative electrode active slurry, the mass ratio of the high molecular polymer to the negative electrode active material, the conductive agent and the binder is 0.05-2.5: 80-99: 1-5: 1-5.
Based on the preparation method, the mass ratio of the plasticizer to the solid electrolyte material to the binder is 5-30: 10-40: 40-85.
Based on the preparation method, the plasticizer is one or the combination of more than two of dioctyl phthalate, dibutyl phthalate, diethyl phthalate, acetyl tri-n-butyl citrate, chlorinated polyethylene, ethylene carbonate, propylene carbonate and dimethyl carbonate.
Based on the preparation method, the negative electrode plate, the solid electrolyte plate and the positive electrode plate are assembled through a lamination process to obtain the solid battery, and the preparation method comprises the following specific steps:
forming a single-layer cell unit or a multi-layer cell unit by the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process;
and (3) carrying out hot pressing and heat preservation operation on a single-layer cell unit or a multi-layer cell unit, and then placing the single-layer cell unit or the multi-layer cell unit in an outer package for packaging and molding to obtain the solid-state battery.
Based on the preparation method, the temperature of the hot pressing operation is 45-85 ℃, the pressure is 5-300 MPa, and the heat preservation time of the heat preservation operation is 0.5-20 h.
Based on the preparation method, the positive electrode active material is lithium metal oxide or modified lithium metal oxide, and the lithium metal oxide is one structure or the combination of any two or more structures in an olivine structure, a layered structure or a spinel structure.
Based on this preparation method, the positive electrode active material may also be a transition metal layered oxide, a polyanion compound, or a prussian blue analog.
Based on the preparation method, the negative electrode active material is one or the combination of more than two of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxygen compound, silicon carbon compound, lithium titanate and sulfur.
Based on the preparation method, the binder is one or the combination of more than two of polyvinylidene fluoride, polytetrafluoroethylene, lithium polyacrylate, styrene-butadiene rubber, nitrile rubber, butene rubber, styrene rubber and polyurethane.
Based on the preparation method, the conductive agent is one or the combination of more than two of conductive carbon black, acetylene black, vapor grown carbon fiber, carbon nano tube and graphene.
Compared with the prior art, the application has the following beneficial effects: in the preparation process, high molecular polymers are added into the positive electrode plate and the negative electrode plate, and a plasticizer is added into the solid electrolyte layer. Under the action of a certain temperature and pressure, the molecular diffusion movement of the plasticizer and the high molecular polymer is accelerated, and the plasticizer and the high molecular polymer migrate to the surface of the solid electrolyte layer and the surface of the positive electrode and the negative electrode respectively in a short time, and the high molecular polymer and the plasticizer are compatible, so that the positive electrode and the solid electrolyte layer are adhered, and the negative electrode and the solid electrolyte layer are adhered, and the interface compatibility of the solid battery is improved under the linking action among the polymers. The blend of the selected high molecular polymer and the plasticizer has only one glass transition temperature or has two glass transition temperatures (glass transition temperature, tg), and the two glass transition temperature peaks are closer to each other than the glass transition temperature peak of each polymer, so that the positive electrode and the solid electrolyte surface and the negative electrode and the solid electrolyte surface have high compatibility. In addition, the hot-pressing operation of the battery cell unit can accelerate the migration of the plasticizer and promote the diffusion of the high-molecular polymer, and can realize the close physical contact and chemical contact of the positive electrode plate and the negative electrode plate with the solid electrolyte layer in a short time, thereby improving the compatibility of interfaces and being easier to realize industrial production. In addition, the addition of the plasticizer in the solid electrolyte layer can increase the elastic deformation capability of the solid electrolyte layer, so that the contact area between the solid electrolyte layer and the electrode material is large, the formation of a continuous ion channel network in the electrode is facilitated, the problem caused by the volume change of the electrode active material in the charge and discharge process can be relieved, and particularly, the addition of the plasticizer in the polymer solid electrolyte can increase the movement speed of a polymer chain segment, so that the polymer swells to provide liquid conductive characteristics and reduce the glass transition temperature.
Meanwhile, the application also provides a solid-state battery prepared based on the preparation method.
The solid-state battery is based on the preparation method of the solid-state battery, the prepared battery improves the interface problem between the electrode and the solid electrolyte from the aspect of molecular movement, better physical and chemical contact is achieved, interface impedance of the electrode and the solid electrolyte is reduced, and stability of the interface between the electrode and the solid-state electrolyte is improved, so that the battery has high interface compatibility, and the cycle life of the battery can be more than 500 circles.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
fig. 1 is a flowchart of a method of manufacturing a solid-state battery;
FIG. 2 is a schematic diagram of a single-layer cell structure;
FIG. 3 is a schematic diagram of molecular motion of a single-layer cell unit during incubation;
fig. 4 is a schematic structural view of a solid-state battery multi-layer cell unit in an embodiment;
FIG. 5 is a graph of electrochemical impedance measured by a solid state battery prior to cycling in an exemplary embodiment;
fig. 6 is a graph of cycle performance of a solid-state battery in a specific embodiment;
reference numerals in the drawings are respectively expressed as:
1. a negative electrode plate; 2. a positive electrode sheet; 3. a solid electrolyte sheet; 4. a high molecular polymer in the negative plate; 5. a high molecular polymer in the positive plate; 6. and (3) a plasticizer.
Detailed Description
The present application will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present application more apparent, and the description thereof is merely illustrative of the present application and not intended to be limiting.
As shown in fig. 1, an embodiment of the present application provides a method for manufacturing a solid-state battery, including the steps of:
s1, obtaining a high molecular polymer solution
Respectively preparing a positive high polymer solution and a negative high polymer solution from high polymer
In this step, the positive electrode high molecular polymer solution and/or the negative electrode high molecular polymer solution can be prepared by:
the preparation method comprises the steps of selecting the same or different types of high molecular polymers as solutes, selecting any one or combination of two groups of substances of toluene and acetone as solvents, and respectively preparing the high molecular polymers by completely dissolving the high molecular polymers in the solvents according to the quality of the required high molecular polymers.
As a specific choice, the high molecular polymer may be one or a combination of any two or more of polyvinyl chloride (PVC), polystyrene-butadiene-styrene (SBS), polystyrene (PS), polymethyl methacrylate (PMMA).
When preparing the positive high polymer solution or the negative high polymer solution, the solvent is used for dissolving the high polymer, so that the high polymer is better mixed with the active substance, the conductive agent and the binder, when different high polymer are selected, the solubility of the high polymer in the solvent is different, the amount of the solvent is also different, the specific high polymer is determined according to the mass ratio of the high polymer to the active substance, the conductive agent and the binder, and the use amount of the solvent can be selected according to the solubility of the high polymer.
S2, preparing a positive pole piece
In the step, the specific preparation method of the positive pole piece comprises the following steps:
and mixing the positive high polymer solution with a positive active substance, a conductive agent and a binder to obtain positive active slurry, coating the surface of a current collector with the positive active slurry, drying, cold pressing and cutting to obtain the positive electrode plate.
As a specific option, in the positive electrode active slurry, the mass ratio of the high molecular polymer to the positive electrode active material, the conductive agent and the binder is 0.05-2.5: 80-99:1-5:1-5.
As a specific option, the positive electrode active material is a lithium metal oxide or a modified lithium metal oxide, and the lithium metal oxide is one structure or a combination of any two or more structures of an olivine structure, a layered structure or a spinel structure.
As a specific option, the positive electrode active material may also be a transition metal layered oxide, a polyanion compound, or a prussian blue analog.
S3, preparing a negative pole piece
In the step, the specific preparation method of the negative electrode plate comprises the following steps: and mixing the negative high polymer solution with a negative active substance, a conductive agent and a binder to obtain negative active slurry, coating the negative active slurry on the surface of a current collector, drying, cold pressing and cutting to obtain a negative pole piece.
As a specific option, in the negative electrode active slurry, the mass ratio of the high molecular polymer to the negative electrode active material, the conductive agent and the binder is 0.05-2.5: 80-99: 1-5: 1-5.
As a specific option, the negative electrode active material is one or a combination of any two or more of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxygen compound, silicon carbon compound, lithium titanate and sulfur.
S4 preparation of solid electrolyte sheet
In the step, the specific preparation method of the solid electrolyte sheet comprises the following steps:
dissolving a plasticizer in a solvent to form a solution, mixing the solution with a solid electrolyte material and a binder, stirring to a uniform state to obtain electrolyte slurry, pouring, drying and cutting the electrolyte slurry to obtain a solid electrolyte sheet;
as a specific option, the mass ratio of the plasticizer, the solid electrolyte material and the binder is 5-30: 10-40: 40-85.
In specific implementation, the plasticizer is one or a combination of any two or more of dioctyl phthalate (DOP), dibutyl phthalate (DBP), diethyl phthalate (DEP), phthalate (PAEs), acetyl tri-n-butyl citrate (ATBC), chlorinated Polyethylene (CPE), ethylene Carbonate (EC), propylene Carbonate (PC) and dimethyl carbonate (DMC).
In particular embodiments, the solid electrolyte material is an oxide-based solid electrolyte (e.g., perovskite type, nasicon type, lisicon type, liPON type, garnet type, sodium super ion conductor, etc.), a sulfide-based solid electrolyte (e.g., li) 10 GeP 2 S 12 LGPS and Na 3 PS 4 Etc.) and a polymer solid electrolyte, and combinations of any two or more thereof.
In specific implementation, the solvent is any one or a combination of two groups of substances of toluene and acetone.
In the concrete implementation, a polytetrafluoroethylene mold can be used for pouring electrolyte slurry.
S5 assembling
In the step, the negative electrode plate, the solid electrolyte plate and the positive electrode plate are assembled through a lamination process, so that the solid battery is obtained.
In a specific implementation, the specific lamination process comprises the following assembly steps:
s51, forming a single-layer cell unit or a multi-layer cell unit by the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process;
s52, carrying out hot pressing and heat preservation operation on a single-layer cell unit or a multi-layer cell unit, and then placing the single-layer cell unit or the multi-layer cell unit in an outer package for packaging and molding to obtain the solid-state battery. As a specific choice, in the step S51-S52, the temperature of the hot pressing operation is 45-85 ℃, the pressure is 5-300 MPa, and the heat preservation time of the heat preservation operation is 0.5-20 h.
In a further implementation process, in the steps S2, S3 and S4, the criteria for selecting the high molecular polymer and the plasticizer are as follows:
1) The blend formed by the high polymer and the plasticizer has only one glass transition temperature, the high polymer and the plasticizer can be completely dissolved at the interface between the electrode and the solid electrolyte layer, so that the physical contact and the chemical contact of the interface are increased, the solid-solid interface between the electrode and the solid electrolyte layer is eliminated to a certain extent, and the interface compatibility is improved;
or alternatively, the first and second heat exchangers may be,
2) The blend formed by the high polymer and the plasticizer in the positive electrode plate and the negative electrode plate has two Tg (glass transition temperature), and the two Tg peaks are closer to each other than the Tg peak of each polymer, so that the high polymer and the plasticizer can be partially compatible at the interface between the electrode and the solid electrolyte layer, the physical contact and the chemical contact of the interface are increased, and the interface compatibility is improved to a certain extent
It should be noted that, when the blend formed by the high polymer and the plasticizer in the positive electrode sheet and the negative electrode sheet has two Tg peaks, the two Tg peaks are closer than the Tg peak of each polymer, specifically:
in a DSC curve with temperature as the abscissa, a blend of a high molecular polymer and a plasticizer generates two glass transition temperatures, tg1 and Tg2 respectively, and the glass transition temperatures of the high molecular polymer and the plasticizer themselves are Tg respectively3 and Tg4, tg1, tg2, tg3, tg4 satisfies:。
in a further implementation, in the steps S2 and S3, the current collector may be any of various materials suitable for use in the art as a current collector of an electrochemical energy storage device, for example, the current collector may be a metal foil, and more specifically may be a nickel foil, an aluminum foil, or the like.
In a further implementation, in the steps S2 and S3, the positive electrode active paste and the negative electrode active paste may be disposed on one surface of the current collector or may be disposed on both surfaces of the current collector.
In a further implementation process, in the steps S2, S3 and S4, the drying mode may be one or two or more selected from heat drying, freeze drying and natural air drying. Specifically, the drying mode is heating drying, the heating drying temperature is 30-85 ℃, and the drying time is not changed any more until the object quality of the corresponding step is changed, for example, in the steps S2 and S3, the drying temperature is 45-85 ℃, and in the step S4, the drying temperature is 30-80 ℃.
In a further implementation process, in the steps S2, S3 and S4, the mixing manner may include one or two or more of ball milling, mechanical stirring, and grinding mixing.
In a further implementation process, in the steps S2 and S3, the binder is one or a combination of any two or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), lithium Polyacrylate (PAALi), styrene-butadiene rubber, nitrile rubber, butene rubber, styrene rubber, and polyurethane.
In a further implementation process, in the steps S2 and S3, the conductive agent is one or a combination of any two or more of conductive carbon black (super-P), acetylene black, vapor grown carbon fiber (Vapor grown carbon fiber, VGCF for short), carbon nanotubes and graphene.
In the implementation, the selected high polymer, binder and conductive agent can be the same single substance or combination of multiple substances, or can be different single substances or combination of multiple substances, and can be selected according to specific situations. For example, the positive electrode sheet and the negative electrode sheet can be prepared by using the same type or different types of high molecular polymers as solutes and then using the same type or different types of high molecular polymer negative electrode solutions or high molecular polymer positive electrode solutions to prepare batteries, so that a blend formed by the high molecular polymers and the plasticizer has only one Tg (glass transition temperature) or two Tg peaks, and the two Tg peaks are closer to each other than the Tg peak of each polymer.
Based on this, the preparation method of the solid-state battery of the present embodiment has the following advantageous effects:
(1) In view of the solid-solid interface problem in solid-state batteries, the conventional solid-state battery preparation method is only improved from the physical contact level, and the problem of compatibility between the electrode and the solid electrolyte layer interface is not solved. The present embodiment provides a method for improving the stability and compatibility of the interface between the electrode and the solid electrolyte in the solid-state battery from the chemical contact level for the first time, and by improving the interface contact between the electrode and the solid electrolyte from the aspect of molecular motion, the better contact will reduce the interface impedance, improve the stability of the interface between the electrode and the solid electrolyte, and obtain the solid-state battery with high interface compatibility.
(2) In this example, a high molecular polymer was added to the electrode of the solid-state battery, and a plasticizer was added to the solid-state electrolyte layer; under the condition of heating and pressurizing, the plasticizer migrates from the inside of the solid electrolyte to the surface due to the diffusion movement of molecules; under the action of the plasticizer, the high molecular polymer in the positive and negative plates is easier to cross the interface between the positive and negative plates and the solid electrolyte to generate a molecular diffusion phenomenon, so that the surfaces of the positive electrode and the solid electrolyte and the surfaces of the negative electrode and the solid electrolyte are bonded due to the similar compatibility of the high molecular polymer and the plasticizer in the solid electrolyte, the compatibility of the electrode and the solid electrolyte interface is improved, and the solid battery with high interface compatibility is obtained.
(3) According to the embodiment, after the negative electrode plate, the solid electrolyte membrane and the positive electrode plate are sequentially laminated, hot-pressing operation is performed on the battery cell unit, so that migration of a plasticizer can be accelerated, diffusion of a high-molecular polymer is promoted, high compatibility between the positive electrode plate and the solid electrolyte can be realized in a short time, and industrial production is easier to realize.
(4) The addition of the plasticizer in the solid electrolyte layer can increase the elastic deformation capability of the solid electrolyte layer, so that the contact area between the solid electrolyte layer and the electrode material is large, the formation of a continuous ion channel network in the electrode is facilitated, the problem caused by the volume change of the electrode active material in the charge and discharge process can be relieved, and the electrolyte has excellent thermal stability and thermal oxidation stability in inert and oxidation gas environments.
A second embodiment of the present application also provides a solid-state battery produced by the above production method, on the basis of the above production method.
Based on the above, the solid-state battery improves the interface contact property between the electrode and the solid electrolyte from the aspect of molecular movement, the better contact reduces the interface impedance of the electrode and the solid electrolyte, and the stability of the interface between the electrode and the solid-state electrolyte is improved, so that the battery has high interface compatibility, and the cycle life of the battery can be more than 500 circles.
The foregoing is a complete description of the method for manufacturing a solid-state battery and the solid-state battery according to the present application, and for better understanding and implementation, the method for manufacturing a solid-state battery according to the present application will be further described with reference to specific examples.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
A preparation method of a solid-state battery comprises the following steps of S1-S5:
s1, taking a high polymer to prepare a positive high polymer solution and a negative high polymer solution respectively
Adding the high molecular polymer-polyvinyl chloride of 2.5 and g into toluene for dissolution to form an anode high molecular polymer solution;
2.5 of g of high molecular polymer-polymethyl methacrylate is added into toluene for dissolution, and a negative high molecular polymer solution is formed.
S2, preparing a positive pole piece
Mixing the positive high polymer solution with lithium iron phosphate, conductive carbon black and polyvinylidene fluoride, wherein the mass ratio of polyvinyl chloride to the lithium iron phosphate, the conductive carbon black and the polyvinylidene fluoride is 2.5:93.5:2:2, mixing to obtain lithium iron phosphate active slurry; coating the active slurry on the surface of an aluminum foil, drying the coated pole piece at 85 ℃ until the quality is not changed, rolling, and die-cutting to obtain the product with the compaction density of 2.3 g/cm 3 Is a positive electrode sheet of the battery.
S3, preparing a negative pole piece
Fully stirring and uniformly mixing the high polymer negative electrode solution, graphite, conductive carbon black and polyvinylidene fluoride in deionized water, wherein the mass ratio of polymethyl methacrylate to graphite to conductive carbon black to polyvinylidene fluoride is 2.5:94.5:1:2, mixing to form anode active slurry with 80% of solid content, coating the anode active slurry on the surface of copper foil, drying the coated pole piece at 85 ℃ until the quality is not changed, rolling, and die cutting to obtain the anode active slurry with 0.9 g/cm of compacted density 3 Is a negative electrode plate.
S4 preparation of solid electrolyte sheet
Adding 17 g phthalate into acetone to be completely dissolved to form phthalate solution, wherein the mass ratio of the phthalate to the lithium bistrifluoromethyl sulfonate to the hydrogenated nitrile rubber is 17:21:62, mixing, and stirring under the action of a vacuum stirrer until the system is uniform to obtain electrolyte slurry; pouring the electrolyte slurry into a polytetrafluoroethylene mold, drying for 24 hours in a nitrogen atmosphere at 50 ℃, and demolding and cutting to obtain the polymer solid electrolyte sheet.
S5 assembling
And (3) laminating the negative electrode plate, the polymer solid electrolyte plate and the positive electrode plate through a lamination process to prepare a multi-layer battery unit, namely a multi-layer battery core unit, and placing the battery core unit in an outer package for packaging and forming after heat preservation of 8 h under the conditions of 60 ℃ and 50 MPa to obtain the solid battery.
When a single-layer cell unit structure is prepared, the negative electrode plate 1, the solid electrolyte plate 3 and the positive electrode plate 2 sequentially form a laminated structure with a detailed interface, as shown in fig. 2; when the multi-layer cell unit structure is prepared, the negative electrode plate 1, the solid electrolyte plate 3 and the positive electrode plate 2 sequentially form a laminated structure with detailed interfaces, namely the multi-layer cell unit structure as shown in fig. 4.
Taking the single-layer cell unit shown in fig. 2 as an example, the molecular diffusion motion generated in the heat preservation and pressurization process is shown in fig. 3. Specifically, after a certain heat preservation time, due to the diffusion movement of molecules, the high polymer 4 in the negative electrode plate and the high polymer 5 in the positive electrode plate migrate to the surfaces of the negative electrode plate 1 and the positive electrode plate 2 respectively, the plasticizer 6 migrates from the inside of the solid electrolyte plate 3 to the surface, the surfaces of the positive electrode plate 2 and the solid electrolyte plate 3 and the surfaces of the negative electrode plate 1 and the solid electrolyte plate 3 are bonded due to the similar compatibility of the high polymer and the plasticizer 6 of the solid electrolyte plate 3, the high polymer 4 in the negative electrode plate and the high polymer 5 in the positive electrode plate partially enter the solid electrolyte plate 3, and the plasticizer 6 in the solid electrolyte plate 3 partially enters the negative electrode plate 1 and the positive electrode plate 2, so that the compatibility of an electrode and a solid electrolyte interface is improved.
Fig. 5 shows the electrochemical impedance profile of a solid-state battery prepared in accordance with an embodiment measured prior to cycling; as can be seen from fig. 5, the optimized design of the present application can obtain a solid-state battery with a low interface impedance.
Fig. 6 is a graph showing the cycle performance of the solid-state battery prepared in the embodiment, and as can be seen from fig. 6, the battery has good cycle performance, and after 500 cycles, the capacity retention rate is 84%.
Table 1 is a table of glass transition temperature data for selected high molecular polymers and blends thereof for solid state batteries prepared in the specific examples.
Table 1: glass transition temperature data sheet
As shown in Table 1, the PVC/PAEs and PMMA/PAEs blend has only one glass transition temperature, and the high-molecular polymer and the plasticizer are completely similar to each other, so that the prepared solid-state battery has lower interface resistance and higher stability, and the capacity of the prepared solid-state battery can be better exerted after 500 circles of cyclic test, therefore, the application improves the interface contact between the electrode and the solid electrolyte through the angle of molecular movement, and improves the stability of the interface between the electrode and the solid electrolyte, so that the battery has high interface compatibility, is feasible and effective, and can effectively solve the solid-solid interface problem of the solid-state battery.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (6)
1. A method of manufacturing a solid-state battery, comprising the steps of:
respectively preparing a positive high polymer solution and a negative high polymer solution from high polymer;
mixing the positive high molecular polymer solution with a positive active substance, a conductive agent and a binder to obtain positive active slurry, coating the surface of a current collector with the positive active slurry, drying, cold pressing and cutting to obtain a positive plate;
mixing the negative high polymer solution with a negative active substance, a conductive agent and a binder to obtain negative active slurry, coating the negative active slurry on the surface of a current collector, drying, cold pressing and cutting to obtain a negative pole piece;
dissolving a plasticizer in a solvent to form a solution, mixing the solution with a solid electrolyte material and a binder, stirring to a uniform state to obtain electrolyte slurry, pouring, drying and cutting the electrolyte slurry to obtain a solid electrolyte sheet;
assembling the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process to obtain the solid battery;
wherein,,
the high molecular polymer and the plasticizer of the positive high molecular polymer solution and the negative high molecular polymer solution satisfy the following conditions:
the blend of the high molecular polymer and the plasticizer has only one glass transition temperature;
or alternatively, the first and second heat exchangers may be,
in a DSC curve with temperature as the abscissa, a blend of a high polymer and a plasticizer generates two glass transition temperatures, tg1 and Tg2, respectively, and Tg1, tg2, tg3 and Tg4 satisfy:；
the high molecular polymer in the positive pole high molecular polymer solution and/or the negative pole high molecular polymer solution is one or the combination of more than two of polyvinyl chloride, polystyrene-butadiene-styrene, polystyrene and polymethyl methacrylate; the solvent of the positive high polymer solution and/or the negative high polymer solution is one or the combination of two substances of toluene and acetone;
the plasticizer is one or the combination of more than two of dioctyl phthalate, dibutyl phthalate, diethyl phthalate, acetyl tri-n-butyl citrate, chlorinated polyethylene, ethylene carbonate, propylene carbonate and dimethyl carbonate;
the binder is one or the combination of more than two of polyvinylidene fluoride, polytetrafluoroethylene, lithium polyacrylate, styrene-butadiene rubber, nitrile rubber, butene rubber, styrene rubber and polyurethane;
assembling the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process to obtain the solid battery, wherein the method comprises the following specific steps of: forming a single-layer cell unit or a multi-layer cell unit by the negative electrode plate, the solid electrolyte plate and the positive electrode plate through a lamination process; and (3) carrying out hot pressing and heat preservation operation on a single-layer cell unit or a multi-layer cell unit, and then placing the single-layer cell unit or the multi-layer cell unit in an outer package for packaging and molding to obtain the solid-state battery.
2. The preparation method of claim 1, wherein in the positive electrode active slurry, the mass ratio of the high molecular polymer to the positive electrode active material, the conductive agent and the binder is 0.05-2.5: 80-99:1-5:1-5.
3. The preparation method of claim 1, wherein in the negative electrode active slurry, the mass ratio of the high molecular polymer to the negative electrode active material, the conductive agent and the binder is 0.05-2.5: 80-99: 1-5: 1-5.
4. The preparation method of claim 1, wherein the mass ratio of the plasticizer, the solid electrolyte material and the binder is (5-30): 10-40: 40-85.
5. The preparation method according to claim 1, wherein the hot pressing operation is performed at a temperature of 45-85 ℃, a pressure of 5-300 mpa, and a heat preservation time of the heat preservation operation is 0.5-20 h.
6. A solid-state battery produced by the production method according to any one of claims 1 to 5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012018932A (en) * | 2011-09-12 | 2012-01-26 | Nissan Motor Co Ltd | Solid electrolyte cell |
| WO2013146896A1 (en) * | 2012-03-28 | 2013-10-03 | 日本ゼオン株式会社 | All-solid-state secondary battery |
| CN111063930A (en) * | 2018-10-16 | 2020-04-24 | 多氟多化工股份有限公司 | Solid polymer electrolyte for lithium ion battery and application thereof |
| CN114759269A (en) * | 2022-05-18 | 2022-07-15 | 电子科技大学 | Integrated all-solid-state battery based on ceramic-based electrolyte sheet and preparation method |
| CN116396323A (en) * | 2023-04-13 | 2023-07-07 | 四川启睿克科技有限公司 | Azobenzene electrolyte, synthesis method, application and solid-state battery and preparation method |
-
2023
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012018932A (en) * | 2011-09-12 | 2012-01-26 | Nissan Motor Co Ltd | Solid electrolyte cell |
| WO2013146896A1 (en) * | 2012-03-28 | 2013-10-03 | 日本ゼオン株式会社 | All-solid-state secondary battery |
| CN111063930A (en) * | 2018-10-16 | 2020-04-24 | 多氟多化工股份有限公司 | Solid polymer electrolyte for lithium ion battery and application thereof |
| CN114759269A (en) * | 2022-05-18 | 2022-07-15 | 电子科技大学 | Integrated all-solid-state battery based on ceramic-based electrolyte sheet and preparation method |
| CN116396323A (en) * | 2023-04-13 | 2023-07-07 | 四川启睿克科技有限公司 | Azobenzene electrolyte, synthesis method, application and solid-state battery and preparation method |
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