CN111312991A - Chargeable and dischargeable solid battery and preparation method and application thereof - Google Patents
Chargeable and dischargeable solid battery and preparation method and application thereof Download PDFInfo
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- CN111312991A CN111312991A CN202010132217.3A CN202010132217A CN111312991A CN 111312991 A CN111312991 A CN 111312991A CN 202010132217 A CN202010132217 A CN 202010132217A CN 111312991 A CN111312991 A CN 111312991A
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- active material
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- negative electrode
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Images
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a chargeable and dischargeable solid battery and a preparation method and application thereof, wherein the solid battery comprises a multifunctional composite positive plate and a multifunctional composite negative plate which are mutually attached, the solid battery is composed of the multifunctional composite positive plate, the multifunctional composite positive plate and an encapsulating material, and is free of a diaphragm component and a liquid electrolyte component, so that the safety of the chargeable and dischargeable solid battery is improved, and the energy density, the rate characteristic, the high-low temperature characteristic, the service life, the cycle life and the like are taken into consideration. The rechargeable solid battery provided by the invention can realize the function of series connection in the battery, thereby simplifying the series-parallel connection structural design of a battery module and a battery pack in an actual large battery. The preparation method of the chargeable and dischargeable solid battery is simple and easy to operate. The rechargeable solid-state battery of the present invention is suitable for, but not limited to, solid-state secondary batteries such as lithium ion, sodium ion, potassium ion, magnesium ion, and aluminum ion.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage devices and new energy materials, and particularly relates to a chargeable and dischargeable solid battery and a preparation method and application thereof.
Background
The traditional secondary battery mainly comprises a positive plate, a diaphragm, a negative plate, liquid electrolyte and packaging materials, wherein each component is in a uniform structural design and has a unique function of independent running, and a short plate exists on the aspect of realizing the comprehensive performance of the lithium ion battery, so that the energy density, the safety, the rate characteristic, the high-low temperature characteristic, the service life, the cycle life and the like cannot be considered at the same time. In addition, the conventional secondary battery employs a liquid electrolyte, which has flammability, and thus, the conventional secondary battery has poor safety.
In recent years, with the rapid development of the fields of new energy automobiles, large-scale energy storage, national defense safety, aerospace and the like worldwide, the requirements of various fields on the performance of batteries are higher and higher, and taking the new energy automobiles as an example, the government subsidizes the new energy automobiles by taking the energy density of the batteries and the endurance mileage as reference bases. The higher the energy density is, the farther the endurance mileage is, the higher the obtained subsidy amount is, in order to improve the endurance of the vehicle, the energy density of the battery is gradually improved by a battery supplier, wherein the most direct and effective way is to adopt positive and negative electrode materials with high energy density, such as a high nickel positive electrode material and a silicon negative electrode material, although the use of the electrode materials can obviously improve the energy density of the battery, the safety is poor because the thermal decomposition temperature of the positive electrode material with high energy density is lower, and the volume change is large in the circulation process of the silicon negative electrode material with high capacity and the cyclicity is poor; the energy density of the battery is improved, and meanwhile, the safety and the service life of the battery cannot be effectively guaranteed. In addition, in some special fields, such as military industry national defense, unmanned aerial vehicle, under operating mode conditions such as extreme low temperature, traditional lithium ion battery also exists not enoughly in the aspect of the comprehensive properties guarantee.
In order to solve the safety problem and simultaneously take the comprehensive performance of the battery into consideration, a great deal of work is done by battery factories and vehicle enterprises on the aspects of battery structure rigidity, battery management systems and battery pack cooling system design so as to ensure that the safety problem of a driver is not caused under the condition that the battery breaks down, but the effect is limited.
Disclosure of Invention
In order to overcome the above problems, the present inventors have made intensive studies to develop a rechargeable and dischargeable solid-state battery including a multifunctional composite positive electrode sheet and a multifunctional composite negative electrode sheet attached to each other, having no separator component and no liquid electrolyte component, which improves the safety of the rechargeable and dischargeable solid-state battery and is compatible with energy density, safety, rate characteristics, high and low temperature characteristics, service life, cycle life, and the like. The rechargeable solid battery provided by the invention can realize the function of series connection in the battery, and can simplify the series-parallel connection structural design of a battery module and a battery pack in an actual large battery. The preparation method of the chargeable and dischargeable solid battery is simple and easy to operate. The rechargeable solid-state battery of the present invention is applicable to, but not limited to, solid-state secondary batteries such as lithium ion, sodium ion, potassium ion, magnesium ion, and aluminum ion, and the present invention has been completed.
The invention aims to provide a chargeable and dischargeable solid battery which comprises a multifunctional composite positive plate and a multifunctional composite negative plate which are mutually attached.
The invention also provides a preparation method of the chargeable and dischargeable solid battery, which comprises the following steps: and (3) jointing the multifunctional composite positive plate and the multifunctional composite negative plate after physical treatment and/or chemical treatment to obtain the solid battery.
The invention also provides application of the chargeable and dischargeable solid battery, and the chargeable and dischargeable solid battery is preferably suitable for secondary batteries such as lithium ion, sodium ion, potassium ion, magnesium ion and aluminum ion.
The invention has the following beneficial effects:
(1) the multifunctional composite positive plate or the multifunctional negative plate adopted by the invention comprises a plurality of positive electrode or negative electrode active material components, so that the structure of the positive electrode or negative electrode active material layer is optimized, and the performance of the multifunctional positive plate or the multifunctional negative plate is improved;
(2) according to the invention, by designing the structure of the positive electrode active substance assembly or the negative electrode active substance assembly, such as a two-dimensional or three-dimensional stacking structure, the functional defect of a single structure is overcome, and the contact areas between the active substance layers and the ion conduction electron insulating layer are increased, so that the transmission efficiency of ions or electrons is increased, and the rate capability, the cycle performance and the like of the battery are improved;
(3) the rechargeable solid battery provided by the invention is composed of a multifunctional positive plate, a multifunctional negative plate and a packaging material, is free of a diaphragm component and a liquid electrolyte component, and is provided with an ion conduction electronic insulating layer, so that the transport of ions in the battery is realized;
(4) the rechargeable solid battery provided by the invention can realize the function of series connection in the battery, so that in an actual large battery, a battery module is simplified, and the series-parallel connection structure design of a battery pack is realized;
(5) the rechargeable solid battery provided by the invention has excellent comprehensive performance, gives consideration to energy density, safety, rate characteristic, high and low temperature characteristic, service life, cycle life and the like, and is suitable for but not limited to solid secondary batteries of lithium ions, sodium ions, potassium ions, magnesium ions, aluminum ions and the like.
Drawings
Fig. 1 shows a schematic view of the operating principle of a secondary battery;
fig. 2 is a schematic view showing a structure of a conventional secondary battery;
fig. 3 is a schematic view showing the structure of a positive electrode sheet of a conventional secondary battery according to comparative example 1;
fig. 4 is a schematic view showing the structure of a negative electrode sheet for a conventional secondary battery of comparative example 2;
fig. 5 is a schematic view showing the structure of a multifunctional composite positive electrode sheet according to embodiment 1 of the present invention;
fig. 6 shows a schematic structural view of a multifunctional composite negative electrode sheet according to example 2 of the present invention;
fig. 7 is a schematic structural view showing a multifunctional composite positive electrode sheet according to embodiment 3 of the present invention;
fig. 8 shows a schematic structural view of a multifunctional composite negative electrode sheet according to example 4 of the present invention;
fig. 9 shows a schematic structural view of a multifunctional composite negative electrode sheet according to example 5 of the present invention;
fig. 10 is a schematic view showing the structure of a multifunctional composite negative electrode sheet according to example 6 of the present invention;
fig. 11 is a schematic structural view showing a chargeable and dischargeable solid-state battery according to embodiment 7 of the present invention;
fig. 12 is a schematic structural view showing a chargeable and dischargeable solid-state battery according to embodiment 8 of the present invention;
fig. 13 is a schematic view showing the structure of a chargeable and dischargeable solid-state battery according to embodiment 9 of the present invention;
fig. 14 shows an SEM image of the multifunctional composite positive electrode sheet according to example 10 of the present invention;
FIG. 15 is a graph showing a comparison of full electrical DSC test results for example 1 of the present invention and comparative example 1;
fig. 16 shows cycle characteristics at a high temperature of 80 ℃ of the secondary battery according to example 7 of the invention;
fig. 17 shows cycle characteristics at a high temperature of 80 c of the secondary battery of comparative example 3 of the present invention.
The reference numbers illustrate:
100-positive plate;
101-positive current collector layer;
102-positive electrode active material layer;
102' -rectangular teeth;
103' -inverted rectangular teeth;
103-positive ion conduction electron insulation layer;
200-a membrane;
300-negative pole piece;
301-negative current collector layer;
302-negative electrode active material layer;
3021-first negative active material assembly;
3022-a second negative active material assembly;
303-negative ion conducting electron insulating layer.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
As shown in fig. 1, which is a basic operation diagram of a lithium ion secondary battery, during charging, lithium ions reach the particle surface from the inside of positive electrode material particles in a positive electrode active material layer in a diffusion manner, and then reach the surface of negative electrode material particles in a negative electrode active material layer after passing through a porous diaphragm through surface migration and liquid electrolyte transportation, and at the same time, electrons are transported to the surface of the negative electrode material particles from the positive electrode material particles through a positive electrode current collector aluminum foil and an external circuit, and are diffused into the inside of the negative electrode material particles after being compounded with the lithium ions migrated from the positive electrode, thereby completing a charging process; the discharge process is reversed.
In the working principle of the battery, the positive current collector and the negative current collector respectively play roles in supporting an electrode active substance layer and conducting electrons, when the battery is charged, the positive active substance layer provides lithium ions, the liquid electrolyte plays a role in transporting ions in the battery, the diaphragm plays a role in isolating a positive plate from a negative plate, and the negative active substance layer is mainly used for storing electrons and ions from the positive electrode.
Fig. 2 shows a schematic diagram of a basic structure of a secondary battery, which mainly includes four major parts, a positive electrode sheet 100, a separator 200, a negative electrode sheet 300, and a liquid electrolyte soaked therein. In which the positive electrode sheet 100 is composed of a positive electrode current collector layer 101 and a positive electrode active material layer 102, as shown in fig. 3, the separator 200 is composed of an organic polymer material, and the negative electrode sheet 300 is composed of a negative electrode current collector layer 301 and a negative electrode active material layer 302, as shown in fig. 4, and a liquid electrolyte is injected into the secondary battery in a dry inert atmosphere by negative pressure.
In the invention, the positive plate, the diaphragm and the negative plate in the traditional secondary battery and the liquid electrolyte are all components which independently perform a single function and cannot be fused or replaced with each other, and in addition, the organic liquid electrolyte participating in the working medium of the battery has flammability, and the liquid injection link has harsh requirements on the environment and affects the health of personnel.
According to the present invention, there is provided a rechargeable solid-state battery comprising a multifunctional positive electrode tab and a multifunctional negative electrode tab attached to each other, and preferably further comprising a sealing material, the multifunctional positive electrode tab and the multifunctional negative electrode tab being enclosed in the sealing material to constitute the rechargeable solid-state battery, and preferably, the multifunctional positive electrode tab and the multifunctional negative electrode tab being attached together by physical or chemical treatment and enclosed in the sealing material to constitute the rechargeable solid-state battery.
According to the invention, the chargeable and dischargeable solid battery has no diaphragm component and no liquid electrolyte component, so that the structure of the chargeable and dischargeable solid battery is simplified, and the safety of the battery is improved.
In the invention, the chargeable and dischargeable solid battery can realize the function of series connection in the battery, thereby simplifying the series-parallel connection structural design of a battery module and a battery pack in the actual large battery and widening the application of the chargeable and dischargeable solid battery.
The rechargeable solid-state battery of the present invention is suitable for, but not limited to, applications in solid secondary batteries such as lithium ion, sodium ion, potassium ion, magnesium ion, and aluminum ion.
According to the present invention, the multifunctional composite positive electrode sheet 100 includes a positive electrode current collector layer 101 and a positive electrode ion conducting electron insulating layer 103, and a positive electrode active material layer 102 located between the positive electrode current collector layer 101 and the positive electrode ion conducting electron insulating layer 103.
In the invention, the positive current collector layer mainly realizes the functions of structural support and electron drainage, the positive active material layer (an electron-ion mixed conducting layer) mainly realizes energy storage and transfer, the ion conduction electron insulating layer is used for conducting ions, the transport of the ions in the battery is realized, meanwhile, the electronic insulation can ensure that the battery is not short-circuited, the positive plate is used in a solid battery, the function of ion and electron transmission can be simultaneously realized in a dry electrode state, liquid electrolyte does not need to be injected, and the safety of the battery can be obviously improved.
According to the present invention, the base material of the positive electrode current collector layer 101 is an oxidation-resistant metal foil or alloy, preferably at least one of aluminum foil, nickel foil, titanium foil, iron foil, and alloys thereof, for example, aluminum foil.
According to the present invention, the positive ion conducting electron insulating layer 103 includes an ion conductive material that can form an ion conductive network, preferably the ion conductive material is at least one of materials applicable to lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion solid electrolytes, more preferably the ion conductive material is composed of at least one of polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum zirconium oxide, lithium germanium phosphorus sulfur, lithium phosphorus oxynitride, lithium lanthanum titanium oxide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, polypropylene carbonate, polyethylene carbonate, and the like by physical or chemical bonding.
According to the present invention, the thickness of the base material of the positive electrode current collector layer 101 is 8 to 25 μm, preferably 10 to 20 μm, and more preferably 16 μm.
According to the present invention, the sum of the thicknesses of the positive electrode active material layer and the ion conducting electron insulating layer is 2 to 500 μm, preferably 50 to 200 μm, and more preferably 80 to 150 μm.
The inventor finds that the active material layer of the existing positive plate has single component and can not meet various requirements in the practical use of the battery, such as the requirements of comprehensive indexes of power density, energy density, low-temperature discharge rate, high-temperature cycle life, safety and the like. For example, the lithium iron phosphate has a long cycle life, but has poor rate performance, and the lithium manganate has good rate characteristics.
According to the present invention, the positive electrode active material layer 102 includes a plurality of (two or more) positive electrode active material components, and the plurality of positive electrode active material components are different in physical properties or chemical compositions.
According to the present invention, the positive electrode active material assembly is made of a positive electrode material, a binder, an electron conductive additive and an ion conductive additive, and preferably, a plurality of positive electrode active materials are connected together by means of physical contact or chemical bonding.
According to the invention, in the positive electrode active material assembly, the mass fraction (concentration) of the positive electrode material is 50-99.6%, the mass fraction (concentration) of the binder is 0.5-20%, the mass fraction (concentration) of the electron conductive additive is 0.5-15%, the mass fraction (concentration) of the ion conductive additive is 0.05-40%, and the sum of the mass fractions of the positive electrode material, the binder, the electron conductive additive and the ion conductive additive is 100%.
According to a preferred embodiment of the present invention, the positive electrode material is at least one of positive electrode materials that can be used for lithium ion, sodium ion, potassium ion, magnesium ion, and aluminum ion secondary batteries, preferably, the positive electrode material is at least one selected from lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel manganese oxide, sodium iron copper manganese oxide, sodium manganese oxide, prussian blue, sodium vanadium phosphate, and sodium titanium phosphate, and preferably selected from one or more selected from lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, and lithium manganate.
According to a preferred embodiment of the present invention, the positive electrode active material assembly in the plurality of positive electrode active material layers 102 is distributed in a two-dimensional stacked structure between the positive electrode current collector layer 101 and the positive electrode ion-conducting electron insulating layer 103.
According to another preferred embodiment of the present invention, the positive electrode active material assembly in the plurality of positive electrode active material layers 102 is distributed in a three-dimensional stack structure between the positive electrode current collector layer 101 and the positive electrode ion-conducting electron insulating layer 103.
According to a preferred embodiment of the present invention, when the plurality of positive electrode active material assemblies are distributed in a two-dimensional stacked structure or a three-dimensional stacked structure, the positive electrode materials in the plurality of positive electrode active material assemblies are the same in kind, and the mass fractions (concentrations) of the positive electrode materials are different.
According to another preferred embodiment of the present invention, when the plurality of positive electrode active material assemblies are distributed in a two-dimensional stacked structure or a three-dimensional stacked structure, the types of positive electrode materials in the plurality of positive electrode active material assemblies are different, and the concentrations of the positive electrode materials are preferably the same.
According to a preferred embodiment of the present invention, when the plurality of positive electrode active material assemblies are distributed in a two-dimensional stacked structure, the positive electrode materials in the plurality of positive electrode active material assemblies are the same, and the plurality of positive electrode active material assemblies are distributed in a gradient structure, preferably, the concentration of the positive electrode material in the plurality of positive electrode active material assemblies is changed in a gradient manner, and more preferably, the plurality of positive electrode active material assemblies are gradually decreased or gradually decreased from high to low in accordance with the mass fraction (concentration) of the positive electrode material contained therein in the direction from the positive electrode current collector layer to the separator.
According to a preferred embodiment of the present invention, in the positive electrode active material layer, different positive electrode active material assemblies may be combined in a two-dimensional layered distribution, and preferably, the positive electrode active material assemblies are combined in a stacked manner, and the thickness of each positive electrode active material assembly is uniform, for example, two-dimensional double-layer lamination combination, two-dimensional multilayer lamination combination.
According to a preferred embodiment of the present invention, the positive electrode active material layer may have different types of positive electrode materials in different positive electrode active material assemblies, and the different positive electrode active material assemblies in the positive electrode active material layer may be distributed in a two-dimensional stacked structure or a three-dimensional stacked structure.
According to a preferred embodiment of the present invention, in the positive electrode active material layer, different positive electrode active material assemblies containing different types of positive electrode materials are two-dimensionally layered, that is, different active material assemblies are two-dimensionally layered and stacked on the positive electrode current collector layer, such as two-dimensionally layered and stacked distribution, and preferably, the thickness of each positive electrode active material assembly is uniform, and more preferably, the thickness of each positive electrode active material assembly is the same or different, and the thickness of each positive electrode active material assembly is designed according to actual needs.
According to another preferred embodiment of the present invention, in the positive electrode active material layer, a plurality of positive electrode active material members containing different kinds of positive electrode materials are combined in a three-dimensional stacking manner, which is a three-dimensional regular structure or a three-dimensional irregular structure.
According to a preferred embodiment of the present invention, the plurality (e.g., two) of positive active material assemblies are distributed in a three-dimensional prong structure or in an equally spaced structure, and the three-dimensional prong structure is preferably distributed in a castellated array structure.
According to a preferred embodiment of the present invention, the plurality of positive electrode active material assemblies are alternately distributed or distributed in an equally spaced structure on the positive electrode current collector layer, that is, the plurality of positive electrode active material assemblies are respectively in alternate contact with the positive electrode current collector layer, and are equally spaced, such as equally spaced rectangular distribution, equally spaced trapezoidal distribution, or equally spaced triangular distribution. Wherein, rectangle, trapezoid, triangle are the cross section shape of positive electrode active material subassembly.
According to a preferred embodiment of the invention, different positive electrode active material assemblies are distributed in a tooth-shaped array structure, so that the contact area of active material layers between the two positive electrode active material assemblies is increased, the binding force between the different positive electrode active material assemblies is enhanced, meanwhile, the contact area of a positive electrode active material and an ion conductive material can be enlarged, the electrochemical performance of a positive electrode material is improved, and the rate characteristic of a battery is further improved.
According to a preferred embodiment of the present invention, the three-dimensional tine structural distribution (tooth array structural distribution) is preferably one or more of a rectangular tooth array type, a triangular tooth array type, a trapezoidal tooth array type, and the like.
According to a preferred embodiment of the present invention, the binder is an organic polymer material that can be used as a binder for a positive electrode material of a secondary battery, and preferably, the binder is one or more selected from polyvinylidene fluoride, polytetrafluoroethylene, polymethyl acrylate, and the like.
According to a preferred embodiment of the present invention, in the multifunctional composite positive electrode sheet, the electron conductive additive is a carbon material, preferably at least one selected from carbon black, carbon nanotubes, graphene, acetylene black, and the like.
According to the invention, in the multifunctional composite positive plate, the ion conductive additive is selected from one or more of bis (trifluoromethyl) sulfonyl imide lithium, nano lithium aluminum titanium phosphate and polyethylene oxide.
According to the present invention, the process of preparing the positive electrode active material layer: preparing a slurry from a positive electrode material, an electronic conductive additive, a binder and an ionic conductive additive, coating the slurry on the positive electrode current collector layer and drying.
According to a preferred embodiment of the present invention, the positive electrode collector layer 101, the positive electrode active material layer 102, and the positive electrode ionically conductive insulating layer 103 are sequentially stacked in a two-dimensional stacked structure distribution.
According to a preferred embodiment of the present invention, the positive electrode active material layer 102 and the ion conducting electronic insulating layer 103 may be distributed by a two-dimensional or three-dimensional stacking structure, and preferably, the positive electrode active material layer 102 and the ion conducting electronic insulating layer 103 are distributed by a three-dimensional tine structure, preferably, a tooth array structure, more preferably, at least one of a rectangular tooth array distribution, a triangular tooth array distribution or a trapezoidal tooth array distribution, such as a rectangular tooth array distribution, a triangular tooth array distribution or a trapezoidal tooth array distribution.
According to the invention, when the positive electrode active material layer and the negative electrode active material layer are distributed in a tooth array structure, the positive tooth contact surface and the inverted tooth contact surface are combined, so that the contact area of the positive electrode active material layer and the ion conduction electron insulation layer is increased, the transmission efficiency of ions or electrons is increased, and the rate capability, the cycle performance and the like of the battery are improved.
According to a preferred embodiment of the present invention, the multifunctional composite positive electrode sheet is formed by preparing the positive electrode active material layer 102 and the positive electrode ion conduction electron insulation layer 103 on the positive electrode current collector layer 101 by spraying, extrusion coating at equal intervals, sputtering with a mask structure, rolling, casting, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, 3D printing, and the like.
The multifunctional composite positive plate can realize an ion transmission network in a dry electrode state, and can ensure that the prepared solid secondary battery can normally work without introducing liquid electrolyte, thereby improving the safety of the solid secondary battery.
According to the invention, the multifunctional composite positive plate is prepared by the following method: sequentially forming a positive electrode active material layer and a positive electrode ion conduction electron insulation layer on the positive electrode current collector layer,
preferably, the positive electrode active material layer and the positive electrode ion conduction electron insulation layer are formed by spraying, equal-interval extrusion coating, sputtering with a mask structure, rolling, casting, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, 3D printing, and the like,
more preferably, the positive electrode active material layer is firstly prepared on the positive electrode current collector layer, and then the positive electrode ion conduction electron insulation layer is prepared on the positive electrode active material layer in at least one of spraying, extrusion coating (equal-interval extrusion coating), sputtering with a mask structure, rolling, casting, pulsed laser deposition, chemical vapor deposition, atomic layer deposition and 3D printing.
According to a preferred embodiment of the present invention, the positive electrode active material layer is formed by one or more of spraying, extrusion coating (e.g., extrusion coating at equal intervals), sputtering with a mask structure (reticle sputtering), rolling, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, 3D printing, and the like, of the positive electrode active material assembly.
According to a preferred embodiment of the invention, the preparation process of the multifunctional composite positive plate comprises the following steps: mixing a positive electrode material, an electronic conductive additive, an ionic conductive additive and a binder to prepare slurry, coating the slurry on a positive electrode current collector layer, and drying to obtain a pole piece formed by a first active material component and the positive electrode current collector layer, preferably forming other active material components on the pole piece according to the structural design of the positive electrode active material component to obtain a positive electrode active material layer; then forming an ion conduction electronic insulating layer on the positive active material layer to obtain a multifunctional composite positive plate;
preferably, the positive electrode material, the electronic conductive additive, the ionic conductive additive and the binder are weighed according to the mass ratio, are gradually added into a solvent (such as NMP), the solid content is controlled to be 40% -60%, and are uniformly stirred to obtain a mixed slurry, the mixed slurry is coated on the positive electrode current collector layer, other active material components are formed according to the structural design of the positive electrode active material layer, and then the ionic conduction electronic insulating layer is prepared on the positive electrode active material layer to obtain the multifunctional composite positive electrode sheet, for example, the positive electrode active material layer and the ionic conduction electronic insulating layer with a two-dimensional laminated structure or an equal-interval (rectangular) distribution structure can be obtained through spraying, equal-interval extrusion coating, rolling and the like.
According to another preferred embodiment of the invention, the preparation process of the multifunctional composite positive plate comprises the following steps: the positive electrode material, the electron conductive additive, the ion conductive additive and the binder are mixed according to the mass ratio to form a dry powder mixture, the dry powder mixture is deposited on a positive electrode current collector layer (or other positive electrode active material components), a first positive electrode active material component is formed, according to the structural design of the positive electrode active material layer, similarly, other positive electrode active material components are formed on the first positive electrode active material component, and then a pole piece formed by the positive electrode active material layer and the positive electrode current collector layer is obtained, according to the structural design of the positive electrode active material layer and the ion conduction electron insulation layer, the ion conduction electron insulation layer is formed on the pole piece, and the multifunctional composite positive electrode piece is obtained. For example, the tooth array structure can be obtained by space coating, sputtering with a mask structure, rolling, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, 3D printing, and the like.
According to the present invention, the multifunctional composite negative electrode sheet 300 includes a negative electrode current collector layer 301 and a negative electrode ion-conducting electron insulating layer 303, and a negative electrode active material layer 302 between the negative electrode current collector layer 301 and the negative electrode ion-conducting electron insulating layer 303.
According to the present invention, the thickness of the substrate of the negative current collector layer 301 is 4 to 10 μm, more preferably 6 to 8 μm, such as 6 μm or 8 μm.
According to the present invention, the sum of the thicknesses of the negative electrode active material layer 302 and the negative electrode ion conducting electron insulating layer 303 is 2 to 200 μm, preferably 70 to 160 μm.
According to the invention, the negative current collector layer mainly realizes the functions of structural support and electron drainage, the negative active material layer (an electron-ion mixed conducting layer) mainly realizes energy storage and transfer, the ion conduction electron insulation layer is used for conducting ions, the transport of the ions in the battery is realized, meanwhile, the electronic insulation can ensure that the battery is not short-circuited, the negative plate is used in a solid battery, the function of ion and electron transmission can be realized simultaneously in a dry electrode state, liquid electrolyte does not need to be injected, and the safety of the battery can be obviously improved.
According to the present invention, the base material of the negative current collector layer 301 is a metal foil or an alloy, preferably at least one of a copper foil, a copper alloy containing 90% or more copper, stainless steel, titanium, a titanium alloy, nickel, a nickel alloy, iron, an iron alloy, and the like, and more preferably a copper foil and a copper alloy containing 90% or more copper, for example, a copper foil.
According to the present invention, the negative ion conducting electron insulating layer 303 includes an ion conductive material which can form an ion conductive network, preferably the ion conductive material is at least one of materials applicable to lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion solid electrolyte, more preferably the ion conductive material is composed of at least one of polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium lanthanum zirconium oxide, lithium germanium phosphorus sulfur compound, lithium phosphorus nitrogen oxide, lithium lanthanum titanium oxide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, polypropylene carbonate, polyethylene carbonate, and the like by physical or chemical bonding.
The inventor finds that the active material layer of the conventional negative plate has a single component and can not meet various requirements in the practical use of the battery, such as the requirements of comprehensive indexes of power density, energy density, low-temperature discharge rate, high-temperature cycle life, safety and the like. The graphite negative plate with a conventional single structural design is used in a lithium ion secondary battery, and during low-temperature high-rate charging, a lithium separation phenomenon easily occurs, so that the safety and the cycle life of the battery are rapidly deteriorated; the inventor finds that the composite negative plate designed by combining graphite and hard carbon can effectively solve the problems of potential safety hazard and cycle life deterioration caused by low-temperature high-rate charging on the premise of not sacrificing other original performance advantages such as energy density and the like.
According to the present invention, the anode active material layer 302 includes a plurality of (two or more) anode active material assemblies, which are different in physical properties or chemical composition.
According to the present invention, the negative electrode active material assembly is made of a negative electrode material, a binder, a conductive additive, and an ion conductive additive, and preferably, a plurality of negative electrode active materials are connected together by physical contact or chemical bonding.
According to the invention, in the negative active material component, the mass fraction (concentration) of the negative material is 60-99.9%, the binder is 0.05-20%, the conductive additive is 0.05-15%, and the ionic conductive additive is 0.05-40%.
According to a preferred embodiment of the present invention, the negative electrode material is at least one of negative electrode materials that can be used in lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion secondary batteries, and the negative electrode material is selected from at least one of metals and their alloys, carbon negative electrode materials, lithium titanate, silicon-containing negative electrodes, tin-containing negative electrodes, and transition metal compound negative electrodes.
According to the invention, the metal and its alloy is selected from at least one of metal lithium, lithium alloy, metal sodium, sodium alloy, metal potassium and potassium alloy; the carbon negative material is selected from at least one of natural graphite, artificial mesocarbon microbeads, hard carbon and soft carbon, the silicon-containing negative electrode is selected from at least one of silicon monoxide, silicon and silicon-carbon composite negative electrodes, the silicon-carbon composite negative electrode is selected from nano silicon/hard carbon, nano silicon/amorphous carbon, nano silicon/soft carbon, nano silicon/graphite and nano silicon/artificial mesocarbon microbeads, and the tin-containing negative electrode is selected from one or more of tin dioxide, tin monoxide and tin-antimony alloy.
According to the invention, the transition metal compound is represented by AxByA is a variable valence transition metal element, including but not limited to at least one of Ti, V, Cr, Fe, Co, Ni, Mn, Cu, Zn, Ru, Mo, Sn, Sb, Co; b is at least one of non-metal elements including but not limited to C, F, O, S, N, and preferably, the transition metal compound is at least one of titanium dioxide, tin monoxide, tin dioxide and manganese dioxide.
According to a preferred embodiment of the present invention, a plurality of anode active material assemblies in the anode active material layer 302 are distributed in a two-dimensional stacked structure between the anode current collector layer 301 and the anode ion-conducting electron insulating layer 303.
According to another preferred embodiment of the present invention, the anode active material assembly in the plurality of anode active material layers 302 is distributed between the anode current collector layer 301 and the anode ion-conducting electron insulating layer 303 in a three-dimensional stacked structure.
According to a preferred embodiment of the present invention, when the plurality of negative electrode active material assemblies are distributed in a two-dimensional stacked structure or a three-dimensional stacked structure, the types of the negative electrode materials in the plurality of negative electrode active material assemblies are the same, and the mass fractions (concentrations) of the negative electrode materials are different.
According to another preferred embodiment of the present invention, when the plurality of negative electrode active material assemblies are distributed in a two-dimensional stacked structure or a three-dimensional stacked structure, the types of the negative electrode materials in the plurality of negative electrode active material assemblies are different, and the concentrations of the negative electrode materials are preferably the same.
According to a preferred embodiment of the present invention, when the plurality of negative electrode active material assemblies are distributed in a two-dimensional stacked structure, the negative electrode materials in the plurality of negative electrode active material assemblies are the same, and the plurality of negative electrode active material assemblies are distributed in a gradient structure, preferably, the concentration of the negative electrode material in the plurality of negative electrode active material assemblies is continuously changed in a gradient manner, and more preferably, the plurality of negative electrode active material assemblies are gradually decreased or gradually decreased from high to low in accordance with the mass fraction (concentration) of the negative electrode material contained therein in the direction from the negative electrode current collector layer to the separator.
According to a preferred embodiment of the present invention, in the anode active material layer, different anode active material assemblies may be combined in a two-dimensional layered distribution, and preferably, the anode active material assemblies are combined in a stacked manner, and the thickness of each layer of the anode active material assembly is uniform, for example, two-dimensional double-layer lamination combination, two-dimensional multilayer lamination combination.
According to a preferred embodiment of the present invention, the anode active material layer may have different kinds of anode materials in different anode active material assemblies, and the different anode active material assemblies in the anode active material layer may be distributed by a two-dimensional stacked structure or a three-dimensional stacked structure.
According to a preferred embodiment of the present invention, in the negative electrode active material layer, different negative electrode active material assemblies containing different types of negative electrode materials are two-dimensionally layered, that is, the different negative electrode active material assemblies are two-dimensionally layered and stacked on the negative electrode current collector layer, such as two-dimensionally layered and stacked distribution, and preferably, the thickness of each negative electrode active material assembly is uniform, and more preferably, the thickness of each negative electrode active material assembly is the same.
According to another preferred embodiment of the present invention, in the anode active material layer, a plurality of anode active material members containing different kinds of anode materials are combined in a three-dimensional stacking manner, and the three-dimensional stacking manner is a three-dimensional regular structure or a three-dimensional irregular structure.
According to a preferred embodiment of the present invention, the plurality (e.g., two) of negative active material assemblies are distributed in a three-dimensional prong structure or in an equally spaced structure, and the three-dimensional prong structure is preferably distributed in a castellated array structure.
According to a preferred embodiment of the present invention, the plurality of negative electrode active material assemblies are alternately distributed or distributed in an equally spaced structure on the negative electrode current collector layer, that is, the plurality of negative electrode active material assemblies are respectively in alternate contact with the negative electrode current collector layer, and are equally spaced, such as equally spaced rectangular distribution, equally spaced trapezoidal distribution, or equally spaced triangular distribution.
According to a preferred embodiment of the invention, different negative electrode active material assemblies are distributed in a tooth-shaped array structure, so that the contact area of active material layers between two negative electrode active material assemblies is increased, the binding force between different negative electrode active material assemblies is enhanced, meanwhile, the contact area between the negative electrode active material layer and an ion conductive material can be enlarged, the electrochemical performance of the negative electrode material is improved, and the rate characteristic of the battery is further improved.
According to a preferred embodiment of the present invention, the three-dimensional tine structural distribution (tooth array structural distribution) is preferably one or more of a rectangular tooth array type, a triangular tooth array type, a trapezoidal tooth array type, and the like.
According to a preferred embodiment of the present invention, the binder is an organic polymer material that can be used as a binder for a negative electrode material of a secondary battery, and preferably, the binder is one or more selected from polyvinylidene fluoride, polytetrafluoroethylene, polymethyl acrylate, polyacrylonitrile, sodium carboxymethylcellulose, styrene butadiene rubber emulsion, and the like.
According to a preferred embodiment of the present invention, the electron conductive additive is a carbon material, preferably at least one selected from carbon black, carbon nanotube, graphene, acetylene black, ketjen carbon, and the like.
According to the invention, in the multifunctional composite negative plate, the ion conductive additive is selected from one or more of bis (trifluoromethyl) sulfonyl imide lithium, nano lithium aluminum titanium phosphate and polyethylene oxide.
According to the present invention, the process of preparing the anode active material layer: preparing a slurry from a negative electrode material, an electronic conductive additive, a binder and an ionic conductive additive, coating the slurry on the negative current collector layer, and drying.
According to a preferred embodiment of the present invention, the anode current collector layer 301, the anode active material layer 302, and the anode ion conducting insulating layer 303 are sequentially stacked in a two-dimensional stacked structure distribution manner.
According to a preferred embodiment of the present invention, the negative electrode active material layer 302 and the negative electrode ion-conducting electronic insulating layer 303 may be distributed by a two-dimensional or three-dimensional stacking structure, and preferably, the negative electrode active material layer 302 and the ion-conducting electronic insulating layer 303 are distributed in a three-dimensional fork tooth structure, preferably, in a tooth array structure, and more preferably, in at least one of a rectangular tooth array distribution, a triangular tooth array distribution, or a trapezoidal tooth array distribution.
According to the invention, when the positive electrode active material layer and the negative electrode active material layer are distributed in a tooth array structure, the positive tooth contact surface and the inverted tooth contact surface are combined, so that the contact area of the negative electrode active material layer and the ion conduction electron insulation layer is increased, the ion transmission efficiency is increased, and the rate capability, the cycle performance and the like of the battery are improved.
According to a preferred embodiment of the present invention, the multifunctional composite negative electrode sheet is formed by preparing a negative electrode active material layer 302 and a negative electrode ion conduction electron insulation layer 303 on the negative electrode current collector layer 301 through spraying, equal-interval extrusion coating, sputtering with a mask structure, rolling, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, 3D printing, and the like.
The multifunctional composite negative plate for the chargeable and dischargeable solid battery can realize the simultaneous conduction of ions and electrons in a dry electrode state, and can ensure that the prepared solid secondary battery can normally work without introducing liquid electrolyte, thereby improving the safety of the solid secondary battery.
The invention provides a preparation method of a multifunctional composite negative plate, which comprises the following steps: a negative electrode active material layer and a negative electrode ion conduction electron insulation layer are sequentially formed on the negative electrode current collector layer,
preferably, the negative electrode active material layer and the negative electrode ion conduction electron insulation layer are prepared on the negative electrode current collector layer by spraying, equal-interval extrusion coating, sputtering with a mask structure, rolling chemical vapor deposition, atomic layer deposition, electrochemical deposition, 3D printing and the like,
more preferably, the negative electrode active material layer is first prepared on the negative electrode current collector layer, and then the ion conducting electron insulating layer is prepared on the negative electrode active material layer by at least one of spraying, extrusion coating, sputtering with a mask structure, rolling, casting, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, and 3D printing.
According to a preferred embodiment of the present invention, the negative electrode active material layer is formed by one or more of spraying, extrusion coating (e.g., extrusion coating at equal intervals), sputtering with a mask structure (reticle sputtering), rolling, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, 3D printing, and the like, of the negative electrode active material member.
According to a preferred embodiment of the present invention, the preparation process of the multifunctional composite negative electrode sheet comprises: mixing a negative electrode material, an electronic conductive additive, an ionic conductive additive and a binder to prepare slurry, coating the slurry on a negative electrode current collector layer substrate, and drying to obtain a pole piece formed by a first negative electrode active material component and a negative electrode current collector layer, preferably forming other active material components on the pole piece according to the structural design of the negative electrode active material component to obtain a negative electrode active material layer; then forming a negative ion conduction electron insulation layer on the negative active material layer to obtain a multifunctional composite negative plate;
preferably, the negative electrode material, the electronic conductive additive, the ionic conductive additive and the binder are weighed according to the mass ratio, are gradually added into a solvent (such as NMP), the solid content is controlled to be 40% -60%, the mixture is uniformly stirred to obtain a mixed slurry, the mixed slurry is coated on the negative electrode current collector layer, other active material components are formed according to the structural design of the negative electrode active material layer, and then the negative electrode ion conduction electronic insulating layer is prepared on the negative electrode active material layer to obtain the multifunctional composite negative electrode sheet.
According to another preferred embodiment of the present invention, the preparation process of the multifunctional composite negative electrode sheet comprises: the negative electrode material, the electronic conductive additive, the ionic conductive additive and the binder are mixed according to the mass ratio to form a dry powder mixture, the dry powder mixture is deposited on a negative electrode current collector layer (or other negative electrode active material components), a first negative electrode active material component is formed, according to the structural design of the negative electrode active material layer, similarly, other negative electrode active material components are formed on the first negative electrode active material component, and then a pole piece formed by the negative electrode active material layer and the negative electrode current collector layer is obtained, according to the structural design of the negative electrode active material layer and the negative electrode ionic conduction electronic insulation layer, the negative electrode ionic conduction electronic insulation layer is formed on the pole piece, and the multifunctional composite negative electrode piece is obtained. For example, the tooth array structure can be obtained by space coating, sputtering with a mask structure, rolling, pulsed laser deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, 3D printing, and the like.
According to the invention, the rechargeable solid battery is only composed of the multifunctional composite positive plate, the multifunctional composite negative plate and the packaging material, has no diaphragm component and liquid electrolyte component, has excellent comprehensive performance and high battery safety, has an internal series function, can realize the internal series-parallel structure design of a single battery, for example, a multifunctional composite positive plate and a multifunctional composite negative plate are used as a group, and a plurality of groups of series-parallel structures form a battery module and a battery pack, thereby simplifying the structure design of an actual large battery.
According to the invention, the packaging material is an aluminum plastic film, a square stainless steel shell, a square aluminum shell, insulating resin, insulating glass and the like.
According to the present invention, the chargeable and dischargeable solid-state battery is prepared by the following method: and (3) jointing the multifunctional composite positive plate and the multifunctional composite negative plate through physical and/or chemical treatment to obtain the solid battery.
The invention provides a preparation method of a chargeable and dischargeable solid battery, which comprises the following steps: and (3) the multifunctional composite positive plate and the multifunctional composite negative plate are subjected to physical and/or chemical treatment and then are attached together to obtain the rechargeable solid battery.
According to a preferred embodiment of the present invention, the physical treatment comprises one or more of high-temperature hot pressing, high-temperature annealing, cold isostatic pressing, vacuum pumping and electron beam irradiation, wherein the high-temperature hot pressing is performed at a temperature of 45-220 ℃ for 10-60 min, preferably at a temperature of 80-150 ℃ for 20-40 min, for example, at a temperature of 85 ℃ for 30 min; the chemical treatment comprises the following steps: one or more of ultraviolet exposure ultraviolet irradiation, high-temperature in-situ electrochemical coupling, high-temperature curing, high-temperature in-situ electrochemical curing and the like.
In the invention, after physical treatment or chemical treatment, the multifunctional positive plate and the multifunctional composite negative plate are attached together, preferably through chemical bonds.
According to a preferred embodiment of the invention, the multifunctional composite positive plate and the multifunctional composite negative plate are respectively subjected to deburring, trimming and tab welding treatment, and then are assembled/combined together in a physical mode to form a laminated or coiled structure, and then are filled into an aluminum plastic film, and are subjected to high-temperature in-situ electrochemical coupling action (an electrochemical charging and discharging instrument) to form dense lamination, so that the rechargeable and dischargeable solid battery is obtained.
The invention provides an application of a chargeable and dischargeable solid battery, which is suitable for but not limited to solid secondary batteries of lithium ions, sodium ions, potassium ions, magnesium ions, aluminum ions and the like.
The rechargeable solid battery provided by the invention is only composed of the multifunctional positive plate, the multifunctional negative plate and the packaging material, does not need the participation of a diaphragm and a liquid electrolyte, has excellent comprehensive performance and high safety. For example, the capacity retention rate of the solid secondary battery of the invention is more than 90% and reaches 92% after the battery is cycled for 100 weeks at 80 ℃, while the capacity retention rate of the conventional secondary battery is only 89% after the battery is cycled for 35 weeks, and the solid secondary battery of the invention has more excellent high-temperature cycle characteristics and safety.
Examples
Example 1
As shown in FIG. 5, a multifunctional positive electrode sheet for a rechargeable solid-state battery, which comprises a positive electrode current collector layer 101, a positive electrode active material layer 102 and a positive electrode ion-conducting electronic insulating layer 103, wherein the base material of the anode current collector layer is aluminum foil, the anode material of the anode active material layer is nickel cobalt lithium manganate with the mass fraction of 82%, the binder is polyvinylidene fluoride with the mass fraction of 7%, the conductive additive is carbon black with the mass fraction of 3%, the ionic conductive additive is bis-trifluoromethyl sulfimide lithium and nano titanium aluminum lithium phosphate with the mass fraction of 4%, the anode ion conduction electronic insulation layer is a nano titanium aluminum lithium phosphate and polyvinylidene fluoride compound, wherein the mass fraction of the lithium titanium aluminum phosphate is 95%, the mass fraction of the polyvinylidene fluoride is 5%, and the positive current collector layer 101, the positive active material layer 102 and the positive ion conduction electronic insulation layer 103 are distributed in a two-dimensional laminated manner.
The preparation process of the multifunctional composite positive plate for the chargeable and dischargeable solid battery comprises the following steps:
(1) mixing nickel cobalt lithium manganate, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate according to a ratio of 80: 9: 3: 4: 4, gradually adding the slurry into an NMP solvent, controlling the solid content to be 50%, uniformly stirring, uniformly and continuously coating the slurry on an aluminum foil by using an automatic coating machine, and drying for later use;
(2) nano lithium aluminum titanium phosphate and polyvinylidene fluoride are mixed according to the weight ratio of 95: and 5, gradually adding the slurry into an NMP solvent, controlling the solid content to be 50%, uniformly stirring, uniformly and continuously coating the slurry on the upper layer of the positive plate in the step (1) by using an automatic coating machine, and drying to obtain the multifunctional composite positive plate.
Example 2
As shown in fig. 6, a multifunctional composite negative electrode sheet for a rechargeable solid battery includes a negative electrode current collector layer 301, a negative electrode active material layer 302, and a negative electrode ion conductive electronic insulation layer 303, which are distributed in a two-dimensional stacked structure, wherein the base material of the negative electrode current collector layer 301 is a copper foil, the active material of the negative electrode active material layer 302 is graphite, the mass fraction of the graphite is 82%, the binder is polyvinylidene fluoride, the mass fraction of the polyvinylidene fluoride is 5%, the electronic conductive additive is carbon black, the mass fraction of the electronic conductive additive is 3%, the ionic conductive additive is bis (trifluoromethyl) sulfimide lithium and nano titanium aluminum lithium phosphate, the mass fractions of the ionic conductive additives are 5%, the negative electrode ion conductive electronic insulation layer 303 is a compound of nano titanium aluminum lithium phosphate and polyvinylidene fluoride, the mass fraction of the titanium aluminum lithium phosphate is 92.
The preparation process of the multifunctional composite negative plate for the chargeable and dischargeable solid battery comprises the following steps:
(1) mixing graphite, polyvinylidene fluoride, carbon black, lithium bis (trifluoromethyl) sulfonyl imide and nano lithium titanium aluminum phosphate according to a weight ratio of 80: 9: 3: 4: 4, gradually adding the slurry into an NMP solvent, controlling the solid content to be 45%, uniformly stirring, uniformly and continuously coating the slurry on a copper foil by using an automatic coating machine, and drying for later use;
(2) mixing nano lithium aluminum titanium phosphate and polyvinylidene fluoride according to a weight ratio of 92: and (3) gradually adding the mass fraction of 8 into an NMP solvent, controlling the solid content to be 35%, uniformly stirring, uniformly and continuously coating the slurry on the upper layer of the negative plate in the step (1) by using an automatic coating machine, and drying to obtain the multifunctional composite negative plate.
Example 3
As shown in fig. 7, a multifunctional composite positive plate for a rechargeable solid battery includes a positive current collector layer 101, a positive active material layer 102, and an ion conducting electronic insulating layer 103, wherein the base material of the positive current collector layer 101 is aluminum foil, the active material of the positive active material layer 102 is lithium iron phosphate, the mass fraction of the active material is 85%, the binder is polyvinylidene fluoride, the mass fraction of the binder is 5%, the electronic conductive additive is carbon black, the mass fraction of the electronic conductive additive is 2%, the ion conductive additive is a composite of lithium bis (trifluoromethyl sulfonyl imide) and polyethylene oxide, the mass fraction of the ion conducting electronic insulating layer 103 is a composite of lithium bis (trifluoromethyl sulfonyl imide) and polyethylene oxide, the mass fraction of the lithium bis (trifluoromethyl sulfonyl imide) is 45%, and the mass fraction of the polyethylene oxide is 55%.
The contact surface between the positive electrode active material layer 102 and the ion conducting electronic insulating layer 103 is a rectangular tooth array structure, wherein the positive electrode active material layer is distributed in a rectangular tooth array structure, the positive electrode active material layer 102 includes a rectangular tooth structure 102 ', the ion conducting electronic insulating layer is distributed in an inverted rectangular tooth array structure, and the ion conducting electronic insulating layer 103 includes an inverted rectangular tooth structure 103'.
The positive electrode current collector layer 101 and the positive electrode active material layer 102 are distributed in a two-dimensional laminated structure, and as shown in the drawing, the positive electrode active material layer 102 and the ion conducting electronic insulating layer 103 are sequentially provided above the positive electrode current collector layer 101.
The preparation method of the multifunctional composite positive plate comprises the following steps:
(1) lithium iron phosphate, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide and polyethylene oxide are mixed according to the weight ratio of 85: 5: 2: 4: 4, weighing and mixing the components in the mass ratio to obtain a mixture, sintering the mixture and the polymer sintering aid by adopting a mask sputtering method to obtain a target material, and sputtering and depositing the mixture in the target material on an aluminum foil for later use according to a rectangular tooth array structure;
(2) lithium bistrifluoromethylsulfonyl imide and polyethylene oxide were mixed according to 45: 55 to obtain a mixture, sintering the mixture and the polymer sintering aid by adopting a mask sputtering method to obtain a target material, and sputtering and depositing the mixture in the target material onto the pole piece in the step (1) according to the rectangular tooth array structure to obtain the multifunctional composite positive pole piece with the rectangular tooth array structure.
Example 4
As shown in fig. 8, a multifunctional composite negative plate for rechargeable solid-state batteries comprises a negative current collector layer 301, a negative active material layer 302 and a negative ion conduction electronic insulation layer 303, wherein the negative current collector layer 301 is a copper foil, the negative active material layer comprises 2 negative active material assemblies, namely a first negative active material assembly 3021 and a second negative active material assembly 3022,
the negative electrode material of the first negative electrode active material assembly 3021 is hard carbon, the mass fraction of the negative electrode material is 92%, the binder is polyvinylidene fluoride, the mass fraction of the binder is 2%, the electronic conductive additive is carbon black, the mass fraction of the electronic conductive additive is 2%, the ionic conductive additive is lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate, the mass fractions are 2% respectively,
the negative electrode material of the second negative electrode active material assembly 3022 is hard carbon, the mass fraction of the negative electrode material is 80%, the binder is polyvinylidene fluoride, the mass fraction of the binder is 9%, the electronic conductive additive is carbon black, the mass fraction of the electronic conductive additive is 3%, the ionic conductive additive is lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate, the mass fractions are 4% respectively, the negative electrode ion conductive electronic insulating layer 303 is a compound of nano lithium titanium aluminum phosphate and polyvinylidene fluoride, wherein the mass fraction of the lithium titanium aluminum phosphate is 85%, and the mass fraction of the polyvinylidene fluoride is 15%.
The first anode active material assembly 3021 and the second anode active material assembly 3022 are distributed in a two-dimensional stacked structure.
The preparation process of the multifunctional composite negative plate for the chargeable and dischargeable solid battery comprises the following steps:
(1) hard carbon, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate are mixed according to the proportion of 90 in 3021: 4: 2: 2: 2, gradually adding the slurry into an NMP solvent, controlling the solid content to be 40%, uniformly stirring, uniformly and continuously coating the slurry on a copper foil by using an automatic coating machine, and drying for later use;
(2) hard carbon, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide, and nano lithium titanium aluminum phosphate were mixed in an assembly 3022 of 80: 9: 3: 4: 4, gradually adding the slurry into an NMP solvent, controlling the solid content to be 40%, uniformly stirring, uniformly and continuously coating the slurry on the upper layer of the pole piece dried in the step (1) by using an automatic coating machine, and drying for later use;
(3) mixing nano lithium aluminum titanium phosphate and polyvinylidene fluoride according to the weight ratio of 85: 15, gradually adding the slurry into an NMP solvent, controlling the solid content to be 35%, uniformly stirring, uniformly and continuously coating the slurry on the upper layer of the negative plate in the step (2) by using an automatic coating machine, and drying to obtain the multifunctional composite negative plate.
Example 5
As shown in figure 9 of the drawings,
a multifunctional composite negative plate for a chargeable and dischargeable solid battery comprises a negative current collector layer 301, a negative active material layer 302 and a negative ion conduction electronic insulation layer 303 which are distributed in a two-dimensional stacking structure, wherein the base material of the negative current collector layer 301 is copper foil, the negative active material layer 302 comprises 2 negative active material assemblies, namely a first negative active material assembly 3021 and a second negative active material assembly 3022 respectively, the active material of the first negative active material assembly 3021 is graphite, the mass fraction of the active material is 80%, the binder is polyvinylidene fluoride, the mass fraction of the active material is 9%, the electronic conductive additive is carbon black, the mass fraction of the electronic conductive additive is 3%, the ionic conductive additive is lithium bis (trifluoromethyl) sulfonyl imide and nano lithium titanium aluminum phosphate, the mass fractions of the ionic conductive additive are 4%, the active material of the second negative active material assembly 3022 is soft carbon, the mass fraction of the active material is 880%, the binder is polyvinylidene, the mass fraction is 4%, the electronic conductive additive is carbon black and the mass fraction is 2%, the ionic conductive additive is bis (trifluoromethyl) sulfonyl imide lithium and nano lithium aluminum titanium phosphate, the mass fractions are respectively 3%, the negative ion conduction electronic insulation layer 303 is a nano lithium lanthanum titanium oxygen and polyvinylidene fluoride compound, wherein the mass fraction of the lithium lanthanum titanium oxygen is 80%, and the mass fraction of the polyvinylidene fluoride is 20%.
The first anode active material assembly 3021 and the second active material assembly 3022 are distributed in a two-dimensional stacked structure.
The preparation process of the multifunctional composite negative plate is as follows:
(1) graphite, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide, and nano lithium titanium aluminum phosphate were mixed in an amount of 80: 9: 3: 4: 4, gradually adding the mixture into an NMP solvent, controlling the solid content to be 40%, uniformly stirring to obtain slurry, uniformly and continuously coating the slurry on a copper foil by using an automatic coating machine, and drying for later use to obtain a pole piece;
(2) soft carbon, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide, and nano lithium titanium aluminum phosphate were mixed in a ratio of 90: 4: 2: 2: 2, gradually adding the mixture into an NMP solvent, controlling the solid content to be 40%, uniformly stirring to obtain slurry, uniformly and continuously coating the slurry on the upper layer of the pole piece dried in the step (1) by using an automatic coating machine, and drying for later use;
(3) mixing nano lithium lanthanum titanium oxide and polyvinylidene fluoride according to the weight ratio of 80: and (3) weighing the mass fraction of 20, gradually adding the weighed mass fraction into an NMP solvent, controlling the solid content to be 50%, uniformly and continuously coating the slurry on the upper layer of the pole piece in the step (2) by using an automatic coating machine after uniformly stirring, and drying to obtain the multifunctional composite negative pole piece.
Example 6
As shown in fig. 10, a multifunctional composite negative plate for rechargeable solid-state batteries comprises a negative current collector layer 301, a negative active material layer 302 and a negative ion conduction electronic insulation layer 303, wherein the negative current collector layer 301 is a copper foil, the negative active material layer comprises 2 negative active material assemblies, namely a first negative active material assembly 3021 and a second negative active material assembly 3022,
the active material of the first negative electrode active material assembly 3021 is lithium titanate with a mass fraction of 86%, the binder is polytetrafluoroethylene with a mass fraction of 3%, the electronic conductive additive is carbon black with a mass fraction of 3%, the ionic conductive additive is lithium bistrifluoromethylsulfonyl imide and polyethylene oxide with a mass fraction of 4% each,
the active material of the second negative electrode active material assembly 3022 is hard carbon with a mass fraction of 90%, the binder is polyvinylidene fluoride with a mass fraction of 3%, the electronic conductive additive is carbon black with a mass fraction of 3%, the ionic conductive additive is lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate with a mass fraction of 2% each,
the ion conduction electronic insulating layer 303 is a nano titanium aluminum lithium phosphate and polyvinylidene fluoride compound, wherein the titanium aluminum lithium phosphate accounts for 85% and the polyvinylidene fluoride accounts for 15% by mass.
The contact surfaces of the first negative electrode active material assembly 3021 and the second negative electrode active material assembly 3022 are arranged in a rectangular tooth array, wherein the first negative electrode active material assembly 3021 is arranged in a rectangular tooth array structure, and the second negative electrode active material assembly 3022 is arranged in an inverted rectangular tooth array structure.
The negative electrode current collector layer and the first negative electrode active material assembly 3021 are two-dimensionally stacked and distributed, and the negative electrode ion-conducting electron insulating layer and the second negative electrode active material assembly 3022 are two-dimensionally stacked and distributed.
The preparation method of the multifunctional composite negative plate comprises the following steps:
(1) according to the first negative electrode active material assembly 3021, lithium titanate, polytetrafluoroethylene, carbon black, lithium bistrifluoromethylsulfonyl imide, polyethylene oxide are mixed in a ratio of 85: 4: 3: 4: 4, mixing to obtain a mixture, sintering the mixture and the polymer sintering aid by adopting a mask sputtering method to obtain a target material, and sputtering and depositing the mixture in the target material on a copper foil according to a rectangular tooth array structure for later use;
(2) according to the second negative electrode active material assembly 3022, hard carbon, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide, and nano lithium titanium aluminum phosphate were mixed in a ratio of 90: 3: 3: 2: 2, weighing and mixing the raw materials to obtain a mixture, sintering the mixture and the high-molecular sintering aid by adopting a mask sputtering method to obtain a target material, and sputtering and depositing the mixture in the target material onto the target material (1) according to a rectangular tooth array structure for later use;
(3) mixing nano lithium aluminum titanium phosphate and polyvinylidene fluoride according to the weight ratio of 85: 15, gradually adding the slurry into NMP, controlling the solid content to be 50%, uniformly stirring, uniformly and continuously coating the slurry on the upper layer of the pole piece in the step (2) by using an automatic coating machine, and drying to obtain the multifunctional composite negative pole piece.
Example 7
As shown in fig. 11, a chargeable and dischargeable solid-state battery includes the multifunctional composite positive electrode sheet of example 1 and the multifunctional composite negative electrode sheet of example 2.
The multifunctional composite positive plate of example 1 and the multifunctional composite negative plate of example 2 were subjected to deburring, edge trimming, and tab welding, respectively, and then subjected to pressure maintaining at 85 ℃ for 30min at high temperature and high temperature to be bonded together, so that the positive ion conductive electronic insulating layer and the negative ion conductive electronic insulating layer were contacted and bonded to form a laminated structure, and then the laminated structure was placed in an aluminum-plastic film, and subjected to high temperature in-situ electrochemical coupling to form a rechargeable solid battery.
Example 8
As shown in fig. 12, a chargeable and dischargeable solid-state battery includes the multifunctional composite negative electrode sheet of example 2 and the multifunctional composite positive electrode sheet of example 3.
The multifunctional composite positive plate and the multifunctional composite negative plate are respectively subjected to deburring, trimming and tab welding treatment, are assembled/combined together in a physical mode to form a laminated structure, are filled into an aluminum-plastic film, and are compactly laminated under the action of high-temperature in-situ electrochemical coupling to obtain the rechargeable solid battery.
Example 9
As shown in fig. 13, a rechargeable solid-state battery, which is a rechargeable internal-string type solid-state battery, was formed by connecting two solid-state batteries obtained in example 7 in series.
Example 10
As shown in FIG. 14, a multifunctional composite positive electrode sheet for a rechargeable solid-state battery, which comprises a positive electrode current collector layer 101, a positive electrode active material layer 102 and a positive electrode ion-conducting electronic insulating layer 103, wherein the base material of the anode current collector layer is aluminum foil, the active material of the anode active material layer is lithium iron phosphate with the mass fraction of 81%, the binder is polyvinylidene fluoride with the mass fraction of 8%, the electronic conductive additive is carbon black with the mass fraction of 3%, the ionic conductive additive is bis-trifluoromethyl sulfimide lithium and nano titanium aluminum lithium phosphate with the mass fraction of 4%, the anode ion conduction electronic insulation layer is a nano titanium aluminum lithium phosphate and polyvinylidene fluoride compound, wherein the mass fraction of the lithium titanium aluminum phosphate is 85%, the mass fraction of the polyvinylidene fluoride is 15%, and the positive electrode current collector layer 101, the positive electrode active material layer 102 and the positive electrode ion conduction electronic insulation layer 103 are distributed in a two-dimensional laminated manner.
The preparation method of the multifunctional composite positive plate comprises the following steps:
(1) lithium iron phosphate, polyvinylidene fluoride, carbon black, lithium bistrifluoromethylsulfonyl imide and polyethylene oxide are mixed according to the weight ratio of 81: 8: 3: 4: 4, gradually adding the slurry into an NMP solvent, controlling the solid content to be 50%, uniformly stirring, uniformly and continuously coating the slurry on an aluminum foil by using an automatic coating machine, and drying for later use;
(2) lithium bistrifluoromethylsulfonyl imide and polyethylene oxide were mixed according to 85: 15, gradually adding the slurry into an NMP solvent, controlling the solid content to be 50%, uniformly stirring, uniformly and continuously coating the slurry on the upper layer of the positive plate in the step (1) by using an automatic coating machine, and drying to obtain the multifunctional composite positive plate.
The obtained multifunctional composite positive plate is subjected to SEM test, and an SEM image of a longitudinal section of the obtained composite positive plate is shown in fig. 14, and it is apparent from fig. 14 that the composite positive plate has a two-dimensional lamination structure, and the composite positive plate includes, in order from bottom to top, an a-positive current collector layer, a B-positive active material layer, and a C-positive ion conducting electronic insulating layer, (B) a distribution diagram of Al elements in the positive current collector layer and the ion conducting electronic insulating layer, (C) a distribution diagram of F elements in the ion conducting electronic insulating layer, and (D) a distribution diagram of Fe elements in the positive active material layer, and it can be seen that each element is uniformly distributed, further, it is evident that characteristics between layers are relatively prominent, which indicates that the composite positive plate can realize industrial quantitative preparation.
Comparative example
Comparative example 1
The traditional secondary battery positive plate comprises a positive current collector layer 101 and a positive active material layer 102, wherein a base body of the positive current collector layer 101 is an aluminum foil, an active material of the positive active material layer 102 is nickel cobalt lithium manganate, the mass fraction of the active material is 82%, a binder is polyvinylidene fluoride, the mass fraction of the binder is 9%, an electronic conductive additive is carbon black, and the mass fraction of the electronic conductive additive is 9%.
The preparation method of the positive plate comprises the following steps:
according to the mass ratio of 82: 9: 9, respectively weighing the nickel cobalt lithium manganate, the polyvinylidene fluoride and the carbon black, gradually adding the nickel cobalt lithium manganate, the polyvinylidene fluoride and the carbon black into an NMP solvent, controlling the solid content to be 50%, uniformly stirring to obtain a slurry, uniformly and continuously coating the slurry on an aluminum foil by using an automatic coating machine, and drying to obtain the positive plate.
Comparative example 2
The traditional secondary battery negative plate comprises a negative current collector layer 301 and a negative active material layer 302, wherein the matrix of the negative current collector layer 301 is copper foil, the active material of the negative active material layer 302 is graphite, the mass fraction of the active material is 82%, the binder is polyvinylidene fluoride, the mass fraction of the active material is 9%, the conductive additive is carbon black, and the mass fraction of the conductive additive is 9%.
The preparation method of the negative plate comprises the following steps:
according to the mass ratio of 82: 9: 9, respectively weighing graphite, polyvinylidene fluoride and carbon black, gradually adding the graphite, the polyvinylidene fluoride and the carbon black into an NMP solvent, controlling the solid content to be 50%, uniformly stirring to obtain slurry, uniformly and continuously coating the slurry on a copper foil by using an automatic coating machine, and drying to obtain the negative plate.
Comparative example 3
A conventional secondary battery comprising the positive electrode sheet of comparative example 1 and the negative electrode sheet of comparative example 2, further comprising a separator and a liquid electrolyte, the separator being a polypropylene porous membrane, the liquid electrolyte being a 1mol/L lithium hexafluorophosphate solution (wherein the solvent used is a solvent in a volume ratio of Ethylene Carbonate (EC): dimethyl carbonate (DMC): methyl ethyl carbonate (DEC): 1: 1: 1).
Examples of the experiments
Experimental example 1
DSC tests were performed on the multifunctional composite positive electrode sheet of example 1 and the positive electrode sheet of comparative example 1, and the test results are shown in fig. 15.
As can be seen from fig. 15, the temperature of the thermal decomposition heat release peak of the multifunctional composite positive electrode sheet of example 1 was about 275 ℃, whereas the temperature of the thermal decomposition heat release peak of the positive electrode sheet of comparative example 1 was about 240 ℃, and it was found that the thermal decomposition temperature of the multifunctional composite positive electrode sheet was about 35 ℃ higher than that of the conventional positive electrode sheet, indicating that the thermal stability of the multifunctional composite positive electrode sheet was good, and the secondary battery obtained from the positive electrode sheet was higher in safety.
Experimental example 2
The chargeable and dischargeable secondary batteries prepared in example 7 and comparative example 3 were subjected to a cycle performance test at a test temperature of 80 ℃ and a cycle charge and discharge rate of 1C/1C, and the test results are shown in fig. 16 to 17.
As can be seen from fig. 16 to 17, the solid secondary battery in example 7 has a capacity retention rate of 92% after being cycled at 80 ℃ for 100 weeks, and the conventional secondary battery in comparative example 3 has a retention rate of only 89% after being cycled at 80 ℃ for 35 weeks.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The solid battery is characterized by comprising a multifunctional composite positive plate and a multifunctional composite negative plate which are attached to each other.
2. The solid battery according to claim 1, wherein the multifunctional composite positive electrode sheet comprises a positive electrode current collector layer, a positive electrode active material layer, and a positive electrode ion conducting electron insulating layer.
3. The solid-state battery according to claim 2,
the positive active material layer comprises one or more positive active material components, the positive active material components are prepared from positive materials, binders, electron conductive additives and ion conductive additives,
preferably, the plurality of positive electrode active material assemblies are distributed in a two-dimensional or three-dimensional stacked structure.
4. The solid battery according to claim 2 or 3, wherein the positive electrode active material layer and the positive electrode ion conducting electron insulating layer are distributed by a two-dimensional or three-dimensional stack structure.
5. The solid-state battery according to claim 1, wherein the multifunctional negative electrode sheet comprises a negative electrode current collector layer, a negative electrode active material layer, and a negative electrode ion conducting electron insulating layer.
6. The solid-state battery according to claim 5,
the negative electrode active material layer includes one or more negative electrode active material assemblies made of a negative electrode material, a binder, an electron conductive additive, and an ion conductive additive,
preferably, the plurality of negative active material assemblies are distributed in a two-dimensional or three-dimensional stacked structure.
7. The solid battery according to claim 5 or 6, wherein the negative electrode active material layer and the negative electrode ion conducting electron insulating layer are distributed by a two-dimensional or three-dimensional stack structure.
8. The solid-state battery according to one of claims 1 to 7, wherein the solid-state battery is free of a separator component, preferably wherein the solid-state battery is free of a liquid electrolyte component, and more preferably wherein the solid-state battery has an internal string function.
9. A method of producing the chargeable/dischargeable solid-state battery according to one of claims 1 to 8, characterized by comprising: and (3) jointing the multifunctional composite positive plate and the multifunctional composite negative plate after physical treatment and/or chemical treatment to obtain the solid battery.
10. The rechargeable solid battery is preferably applicable to secondary batteries of lithium ions, sodium ions, potassium ions, magnesium ions, aluminum ions and the like.
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