CN111293317A - Multifunctional composite negative plate for chargeable and dischargeable solid battery, preparation method and secondary battery - Google Patents
Multifunctional composite negative plate for chargeable and dischargeable solid battery, preparation method and secondary battery Download PDFInfo
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- CN111293317A CN111293317A CN202010132218.8A CN202010132218A CN111293317A CN 111293317 A CN111293317 A CN 111293317A CN 202010132218 A CN202010132218 A CN 202010132218A CN 111293317 A CN111293317 A CN 111293317A
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Images
Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a multifunctional composite negative plate for a chargeable and dischargeable solid battery, which comprises a negative current collector layer, a negative ion conduction electronic insulating layer and a negative active substance layer positioned between the negative current collector layer and the negative ion conduction electronic insulating layer, wherein the negative active substance layer is composed of a plurality of negative active substance components, and a plurality of negative active material components are distributed in a two-dimensional laminated structure or a three-dimensional stacked structure, so that different functions of different negative active material components are fully exerted, the comprehensive performance of the battery is considered, meanwhile, the negative ion conduction electronic insulating layer can realize ion conduction and electronic insulation functions, so that the introduction of liquid electrolyte and internal short-circuit self-discharge are avoided, the safety of the battery is improved, and the multifunctional composite negative plate and the secondary battery which have comprehensive excellent performances such as energy density, safety, rate characteristics, high and low temperature characteristics, service life, cycle life and the like are obtained.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage devices and new energy materials, and relates to a multifunctional composite negative plate for a chargeable and dischargeable solid battery, a preparation method and a secondary battery.
Background
Traditional lithium ion battery negative pole piece, mainly constitute by negative pole mass flow body layer and 2 parts on the negative pole active material layer, wherein the negative pole mass flow body mainly realizes structural support and electron drainage effect, the negative pole active material layer is mainly porous structure, the porous structure pole piece that the negative pole active material layer comprises graininess negative pole active material, graininess/threadiness electron conductive additive and binder, under dry electrode slice attitude or under the condition that does not have electrolyte injection infiltration, can't realize the ion transmission function, can only switch on the electron, the unable normal work of battery, therefore, current lithium ion battery negative pole piece can't directly be applied to in the solid-state battery.
In addition, the traditional secondary battery, such as a lithium ion battery, has a flowable organic liquid electrolyte inside, and a positive plate, a diaphragm, a negative plate and a liquid electrolyte in the lithium ion battery are all components with single independent driving function, which cannot be fused or replaced with each other, and the organic liquid electrolyte has flammability and potential safety hazard, and the link of injecting the organic liquid electrolyte has harsh requirements on the environment, so the safety of the battery is improved; it is necessary to reduce the amount of liquid electrolyte or to use no flammable liquid electrolyte, and if the amount of liquid electrolyte is reduced, the performance of the battery is affected, and the battery basically cannot work normally without adding liquid electrolyte.
Therefore, in order to meet the requirement of normal operation of the battery, solve the safety of the battery, and improve the comprehensive performance of the battery, a safe and reliable negative plate suitable for a solid-state battery needs to be developed.
Disclosure of Invention
In order to overcome the above problems, the present inventors have made intensive studies to design a multifunctional composite negative electrode sheet for a rechargeable solid battery, which comprises a negative electrode current collector layer, an ion conducting electronic insulating layer, and a negative electrode active material layer disposed between the negative electrode current collector layer and the ion conducting electronic insulating layer, wherein the negative electrode active material layer is composed of a plurality of negative electrode active material assemblies, and the plurality of negative electrode active material assemblies are distributed in a two-dimensional lamination structure or a three-dimensional stacking structure, thereby fully playing different functions of the different negative electrode active material assemblies and giving consideration to the comprehensive performance of the battery, and the ion conducting electronic insulating layer can realize the functions of ion conduction and electronic insulation, thereby avoiding the introduction of liquid electrolyte and the internal short circuit self-discharge, improving the safety of the battery, and obtaining the multifunctional composite negative electrode sheet and the secondary battery which give consideration to the comprehensive excellent performances such as safety, rate characteristic, high-low temperature characteristic, service life, cycle life, and the, thus, the present invention has been completed.
The invention aims to provide a multifunctional composite negative plate for a chargeable and dischargeable solid battery, which comprises a negative current collector layer, a negative ion conduction electronic insulating layer and a negative active material layer positioned between the negative current collector layer and the negative ion conduction electronic insulating layer.
Wherein the anode active material layer includes a plurality of anode active material assemblies made of an anode material, a binder, an electron conductive additive, and an ion conductive additive.
The negative electrode active material layer and the ion conduction electron insulation layer can be distributed through a two-dimensional or three-dimensional stacking structure.
The negative electrode material is at least one of negative electrode materials which can be used for lithium ion, sodium ion, potassium ion, magnesium ion and aluminum ion secondary batteries, and is selected from at least one of metals and alloys thereof, carbon negative electrode materials, lithium titanate, silicon-containing negative electrodes, tin-containing negative electrodes and transition metal compound negative electrodes,
the expression of the transition metal compound is AxByA is a variable valence transition metal element including but not limited toAt least one of Ti, V, Cr, Fe, Co, Ni, Mn, Cu, Zn, Ru, Mo, Sn, Sb and 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.
Wherein the ion conducting electronic insulating layer comprises an ion conducting material, the ion conducting material is at least one of materials which can form an ion conducting network and are suitable for lithium ion, sodium ion, potassium ion, magnesium ion and aluminum ion solid electrolytes,
preferably, the ion conductive material is composed of at least one of polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, lithium aluminum titanium phosphate, lithium lanthanum zirconium oxide, lithium germanium phosphorus sulfur compound, lithium phosphorus oxynitride, lithium lanthanum titanium oxide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, polypropylene carbonate, polyethylene carbonate, and the like through physical or chemical bonding.
Wherein the plurality of negative electrode active material assemblies are distributed in a two-dimensional layered structure.
The negative active material assemblies are distributed in a three-dimensional stacking structure, preferably in a three-dimensional regular or irregular distribution, preferably in an equispaced structure distribution or a three-dimensional fork tooth structure distribution, and the three-dimensional fork tooth structure distribution is preferably in a tooth shape array structure distribution, and more preferably in at least one of a rectangular tooth array distribution, a triangular tooth array distribution or a trapezoidal tooth array distribution.
Wherein the anode materials in the plurality of anode active material assemblies are different, and preferably, the concentrations of the anode materials are the same.
Wherein the anode materials in the plurality of anode active material assemblies are the same, and the concentrations of the anode materials are different.
The present invention also provides a method for producing the multifunctional composite negative electrode sheet according to the first aspect, comprising forming a negative electrode active material layer and a negative electrode ion-conducting electron insulating layer in this order on a negative electrode current collector layer,
preferably, the negative electrode active material layer and the ion conducting electron insulating layer are prepared on the negative electrode current collector by at least one of spraying, equal-interval extrusion coating, sputtering with a mask structure, rolling, casting, chemical vapor deposition, atomic layer deposition, 3D printing, and the like.
The invention also provides a chargeable and dischargeable solid battery comprising the multifunctional composite negative plate of the first aspect of the invention.
The invention has the following beneficial effects:
(1) the negative electrode active material layer of the multifunctional composite negative electrode sheet comprises a plurality of negative electrode active material components, and the negative electrode active materials in the negative electrode active material components are different in physical properties or chemical compositions, so that the functions of the negative electrode sheet are enhanced;
(2) according to the invention, by designing a plurality of negative active material components into a two-dimensional layered stacking distribution mode or a three-dimensional stacking structure, the functional defect of a single component is overcome, meanwhile, the contact area between the negative active material components is increased, the binding power is enhanced, and the contact area between different active material components and an ion conductive material is increased, so that the prepared secondary battery has the advantages of excellent rate characteristic, long cycle life, high energy density and the like;
(3) according to the invention, the transport of ions in the battery is realized by designing the ion conduction electronic insulating layer, and meanwhile, the electronic insulating layer can ensure that the battery is not short-circuited, so that a continuous ion transmission network can be formed in the multifunctional composite negative plate in a dry electrode state;
(4) the multifunctional composite negative plate and the secondary battery comprising the same overcome the defects of single component and single function of the active material layer of the negative electrode of the conventional negative plate, avoid the introduction of liquid electrolyte, obtain the multifunctional composite negative plate and the secondary battery with excellent comprehensive performance, have the advantages of high power density, high energy density, good low-temperature discharge rate performance, long high-temperature cycle life, high safety and the like, and are suitable for large-scale popularization.
Drawings
Fig. 1 shows a schematic view of the operating principle of a secondary battery;
fig. 2 shows a schematic view of a secondary battery structure;
fig. 3 shows a schematic view of the structure of the negative electrode sheet of comparative example 1;
fig. 4 shows a schematic structural view of the multifunctional composite negative electrode sheet of example 1;
fig. 5 shows a schematic structural view of a multifunctional composite negative electrode sheet of example 2;
fig. 6 shows a schematic structural view of a multifunctional composite negative electrode sheet of example 3;
fig. 7 shows a schematic structural view of a multifunctional composite negative electrode sheet of example 4;
fig. 8 shows a schematic structural view of the multifunctional composite negative electrode sheet of example 5.
Fig. 9 is a graph comparing the results of the specific discharge capacity tests of the multifunctional composite negative electrode sheet of example 1 and the negative electrode sheet of comparative example 1.
Fig. 10 is a graph comparing the rate and cyclicity test results for the multifunctional composite negative electrode sheet of example 1 and the negative electrode sheet of comparative example 1;
fig. 11 shows an SEM image of the multifunctional composite negative electrode sheet obtained in example 1.
The reference numbers illustrate:
100-positive plate;
101-positive current collector layer;
102-positive electrode active material 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;
302' -rectangular teeth;
303-negative ion conducting electron insulating layer;
303' -inverted rectangular teeth.
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 transferred from the positive electrode, so as to complete 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, the separator 200 is composed of an organic polymer material, as shown in fig. 3, a schematic view of the structure of the negative electrode sheet 300 is shown, the negative electrode sheet 300 is composed of a negative electrode current collector layer 301 and a negative electrode active material layer 302, and the liquid electrolyte is injected into the secondary battery in a dry inert atmosphere by negative pressure.
According to the present invention, there is provided a multifunctional composite negative electrode sheet for a chargeable and dischargeable solid-state battery, comprising 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 located between the negative electrode current collector layer 301 and the negative electrode ion conducting electron insulating layer 303.
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.
The multifunctional composite negative plate is suitable for but not limited to solid secondary batteries based on solid electrolytes, such as lithium ions, sodium ions, potassium ions, magnesium ions, aluminum ions and the like.
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, more preferably copper and a copper alloy containing 90% or more copper, for example, a copper foil.
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 50 to 200 μm, preferably 70 to 160 μm.
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. For example, when the graphite negative electrode sheet with a conventional single structure design is used in a lithium ion secondary battery, a lithium precipitation phenomenon is easy to occur during low-temperature large-current charging, so that the safety and the cycle life of the battery are rapidly deteriorated; the invention discovers that the composite negative plate designed by combining graphite and soft 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, an electron 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 present invention, in the negative electrode active material assembly, the mass fraction (concentration) of the negative electrode material is 60% to 99.9%, the mass fraction of the binder is 0.05% to 20%, the mass fraction of the electron conductive additive is 0.05% to 15%, the mass fraction of the ion conductive additive is 0.05% to 40%, and the sum of the mass fractions of the negative 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 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 a silicon-carbon composite negative electrode, 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 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, and preferably, the concentration of the negative electrode material in the plurality of negative electrode active material assemblies is 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, different 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 or different, and the thickness of each negative electrode active material assembly is designed according to actual needs.
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. Wherein, the rectangle, the trapezoid and the triangle are the cross-sectional shapes of the negative active material component.
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 nanotubes, graphene, acetylene black, ketjen black, and the like, for example, carbon black.
According to the invention, 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 electron insulating layer 303 are sequentially stacked in a two-dimensional stacked structure distribution.
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 an ion transmission network in a dry electrode state, does not need to introduce liquid electrolyte, and can avoid internal short circuit and self-discharge, so that the prepared solid secondary battery can normally work, and the safety of the secondary battery can be improved.
The invention provides a preparation method of a multifunctional composite negative plate, which comprises the following steps: an electron insulating layer for conducting the negative electrode active material layer and the negative electrode ions is 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 means of 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 in 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.
The multifunctional composite negative plate provided by the invention can be used for preparing chargeable and dischargeable solid batteries and secondary batteries.
The invention provides a secondary battery containing a multifunctional composite negative plate for a chargeable and dischargeable solid battery, the secondary battery comprises the multifunctional composite negative plate, the diaphragm and the positive plate, wherein the positive plate, the diaphragm and the multifunctional composite negative plate are combined together in physical modes such as winding, lamination and the like and are filled into a packaging material, injecting electrolyte into the negative plate to obtain the secondary battery or preparing the secondary battery by high-temperature hot-pressing, cold isostatic pressing and other modes, preferably, the diaphragm and the positive plate are conventional positive plates and diaphragms in the field, more preferably, the diaphragm and the positive plate are distributed into an ion conductive film and a multifunctional composite positive plate with a current collector support structure, more preferably, the diaphragm is not needed, the positive plate is a multifunctional composite positive plate with a current collector support structure, the multi-composite positive plate is composed of a current collector layer, ion conduction electron insulation layers and a positive active material layer positioned between the ion conduction electron insulation layers.
According to the present invention, the secondary battery including the multifunctional composite negative electrode sheet has excellent high-temperature cycle performance, rate capability and capacity exertion performance, for example, high-temperature 55 ℃/50 DEG CthThe circulation retention rate is about 97%, and the 1C/0.1C ratio is 91%; the diaphragm-free electrolyte-free secondary battery prepared by the multifunctional composite negative plate has 0.1C and 1C specific discharge capacities of 325mAh/g and 280mAh/g under the test condition of 85 ℃, the 1C/0.1C ratio reaches 86 percent, and the 1C/0.1C ratio is only 38 percent under the condition that the conventional negative plate is not injected with electrolyte.
The multifunctional composite negative plate provided by the invention is designed into a two-dimensional laminated structure or a three-dimensional stacked structure by designing the structure of the negative active material layer, overcomes the defects of single structural component and single function of the conventional negative active material layer, overcomes the design defects in the conventional secondary battery, obtains the multifunctional composite negative plate and the secondary battery with excellent comprehensive performance, and is suitable for large-scale popularization if the multifunctional composite negative plate has the advantages of high power density, high energy density, good low-temperature discharge rate performance, long high-temperature cycle life, high safety and the like.
Examples
Example 1
As shown in fig. 4, 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 conduction electronic insulation layer 303, which are distributed in a two-dimensional stacked structure, wherein a base material of the negative electrode current collector layer 301 is a copper foil, a negative electrode material of the negative electrode active material layer 302 is graphite, a mass fraction of the graphite is 80%, a binder is polyvinylidene fluoride, a mass fraction of the polyvinylidene fluoride is 9%, an electronic conductive additive is carbon black, a mass fraction of the electronic conductive additive is 3%, an ion conductive additive is bis (trifluoromethyl) sulfimide lithium and nano titanium aluminum lithium phosphate, a mass fraction of the ion conductive additive is 4%, the negative electrode ion conduction electronic insulation layer 303 is a compound of nano titanium aluminum lithium phosphate and polyvinylidene fluoride, a mass fraction of the titanium aluminum lithium phosphate is.
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.
The obtained multifunctional composite negative electrode sheet was subjected to SEM test, and the obtained SEM image of the longitudinal section is shown in fig. 11, and as can be seen from fig. 11, the multifunctional composite negative electrode sheet having a two-dimensional laminate structure was obtained in example 1, and the laminate structure of the composite negative electrode sheet can be clearly seen, in which a-a negative electrode current collector layer, b-a negative electrode active material layer, and c-a negative electrode ion conducting electron insulating layer.
Example 2
As shown in fig. 5, 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 with a mass fraction of 90%, the binder is polyvinylidene fluoride with a mass fraction of 4%, the electronic conductive additive is carbon black with a mass fraction of 2%, the ionic conductive additive is lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate with a mass fraction of 2% each,
the negative electrode material of the second negative electrode active material assembly 3022 is hard carbon with a mass fraction of 80%, the binder is polyvinylidene fluoride with a mass fraction of 9%, 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 4% each,
the negative ion conduction electron insulation layer 303 is a nano titanium aluminum lithium phosphate and polyvinylidene fluoride compound, wherein the mass fraction of the titanium aluminum lithium 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 3
As shown in fig. 6, a multifunctional composite negative plate for rechargeable solid-state battery comprises a negative current collector layer 301, a negative active material layer 302 and a negative ion conducting electronic insulation layer 303, which are distributed in a two-dimensional stacked structure, wherein the substrate 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,
the negative electrode material of the first negative electrode active material assembly 3021 is graphite, 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 bis (trifluoromethyl) sulfonyl imide and nano lithium titanium aluminum phosphate, the mass fractions are 4% respectively,
the cathode material of the second cathode active material assembly 3022 is soft carbon with a mass fraction of 90%, the binder is polyvinylidene fluoride with a mass fraction of 4%, the electronic conductive additive is carbon black with a mass fraction of 2%, the ionic conductive additive is lithium bistrifluoromethylsulfonyl imide and nano lithium titanium aluminum phosphate with a mass fraction of 2% each,
the negative ion conduction electron insulation layer 303 is a nano lithium lanthanum titanium oxide and polyvinylidene fluoride compound, wherein the mass fraction of lithium lanthanum titanium oxide is 80%, and the mass fraction of 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 4
As shown in fig. 7, 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 conduction electronic insulation layer 303, wherein the base material of the negative electrode current collector layer 301 is copper foil, the negative electrode material of the negative electrode active material layer 302 is graphite, the mass fraction of the graphite is 80%, the binder is polyvinylidene fluoride, the mass fraction of the polyvinylidene fluoride is 4%, the electronic conductive additive is carbon black, the mass fraction of the electronic conductive additive is 2%, the ionic conductive additive is a composite of lithium bis (trifluoromethyl) sulfonyl imide and polyethylene oxide, the mass fractions of the ionic conductive additives are 7%, the negative electrode ion conduction electronic insulation layer 303 is a composite of lithium bis (trifluoromethyl) sulfonyl imide and polyethylene oxide, the mass fraction of the lithium bis (trifluoromethyl) sulfonyl imide is 40%, and the mass fraction of the.
The contact surface between the negative electrode active material layer 302 and the negative electrode ion conduction electronic insulation layer 303 is a rectangular tooth array structure, wherein the negative electrode active material layer 302 is distributed in a rectangular tooth array structure, the negative electrode active material layer 302 includes a rectangular tooth structure 302 ', the negative electrode ion conduction electronic insulation layer 303 is distributed in an inverted rectangular tooth array structure, and the negative electrode ion conduction electronic insulation layer 303 includes an inverted rectangular tooth structure 303'.
The negative electrode current collector layer 301 and the negative electrode active material layer 302 are distributed in a two-dimensional laminated structure, and as shown in the figure, the negative electrode active material layer 302 and the negative electrode ion conducting electron insulating layer 303 are sequentially provided above the negative electrode current collector layer 301.
The preparation method of the multifunctional composite negative plate comprises the following steps:
(1) mixing graphite, polyvinylidene fluoride, carbon black, lithium bis (trifluoromethyl) sulfonyl imide and polyethylene oxide according to the weight ratio of 80: 4: 2: 7: 7, obtaining 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) lithium bistrifluoromethylsulfonyl imide and polyethylene oxide were mixed according to 40: 60 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 cathode piece with the rectangular tooth array structure.
Example 5
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 lithium titanate with a mass fraction of 85%, the binder is polytetrafluoroethylene with a mass fraction of 4%, 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 negative ion conduction electronic insulation 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.
Comparative example 1
As shown in fig. 3, the conventional secondary battery negative electrode sheet includes a negative electrode current collector layer 301 and a negative electrode active material layer 302, the matrix of the negative electrode current collector layer 301 is copper foil, the negative electrode material of the negative electrode active material layer 302 is graphite, the mass fraction of the negative electrode material is 80%, the binder is polyvinylidene fluoride, the mass fraction of the negative electrode material is 10%, and the conductive additive is carbon black, and the mass fraction of the conductive additive is 10%.
The preparation method of the negative plate comprises the following steps:
according to the mass ratio of 80: 10: 10, 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.
Experimental example 1
The multifunctional composite negative electrode sheet of example 1 and the negative electrode sheet of comparative example 1 were used as working electrodes, secondary batteries were prepared according to the schemes in table 1, and the prepared secondary batteries were subjected to performance tests, wherein the specific battery preparation and test schemes are shown in table 1 below, and the test results are shown in fig. 9 and 10. The preparation and test scheme is that in example 1-a, the multifunctional composite negative plate in example 1 is used as a working electrode, the metal lithium plate is used as a counter electrode, and the diaphragm is prepared by adopting a conventional diaphragm to obtain the secondary battery.
As can be seen from the test data in fig. 9 and 10, the conventional secondary battery prepared using the composite negative electrode sheet in example 1 has close cyclicity, high temperature of 55 ℃/50 ℃ in comparison with the conventional secondary battery prepared using the composite negative electrode sheet in local ratio 1thThe cycle retention rate is about 97 percent; however, the composite negative electrode sheet of example 1 had better rate characteristics, and the 1C/0.1C ratio was 91%, and the 1C/0.1C ratio of the composite negative electrode sheet of comparative example 1 was 89.8%.
In addition, compared with the comparative example 1, the non-diaphragm solid-state secondary battery prepared by using the composite negative electrode sheet in the example 1 has better high-temperature cyclability, rate characteristics and capacity exertion capability under the condition of no electrolyte injection, and the capacity of the 0.1C and 1C specific discharge capacity of the conventional negative electrode sheet is only 42mAh/g and 16mAh/g under the condition of 85 ℃, while the 1C/0.1C ratio of the non-diaphragm non-electrolyte secondary battery prepared by using the composite negative electrode sheet in the example 1 reaches 86 percent and the 1C/0.1C ratio of the conventional negative electrode sheet is only 38 percent under the condition of no electrolyte injection, when the conventional negative electrode sheet is tested under the condition of 85 ℃.
TABLE 1
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 multifunctional composite negative plate for the chargeable and dischargeable solid battery is characterized by comprising a negative current collector layer, a negative ion conduction electronic insulation layer and a negative active material layer positioned between the negative current collector layer and the negative ion conduction electronic insulation layer.
2. The multifunctional composite negative electrode sheet according to claim 1, wherein the negative electrode active material layer comprises a plurality of negative electrode active material assemblies made of a negative electrode material, a binder, an electron conductive additive, and an ion conductive additive,
the negative electrode active material layer and the negative electrode ion conduction electron insulation layer can be distributed through a two-dimensional or three-dimensional stacking structure.
3. The multifunctional composite negative electrode sheet according to claim 1, wherein the negative electrode material is at least one of negative electrode materials usable in lithium ion, sodium ion, potassium ion, magnesium ion, aluminum ion secondary batteries, and is selected from at least one of metals and alloys thereof, carbon negative electrode materials, lithium titanate, silicon-containing negative electrodes, tin-containing negative electrodes, and transition metal compound negative electrodes,
the transition metal compound is represented by AxByWherein A 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.
4. The multifunctional composite negative electrode sheet according to claim 1, wherein the ion conducting electronic insulating layer comprises an ion conducting material, the ion conducting material is at least one of materials suitable for lithium ion, sodium ion, potassium ion, magnesium ion, and aluminum ion solid electrolytes, which can form an ion conducting network,
preferably, the ion conductive material is composed of at least one of polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, lithium aluminum titanium phosphate, lithium lanthanum zirconium oxide, lithium germanium phosphorus sulfur compound, 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.
5. The multifunctional composite negative electrode sheet according to claim 2, wherein the plurality of negative electrode active material assemblies are distributed in a two-dimensional layered structure.
6. The multifunctional composite negative electrode sheet according to claim 3, wherein the plurality of negative active material assemblies are distributed in a three-dimensional stacking structure, preferably in a three-dimensional regular or irregular distribution, preferably in an equi-spaced structure or in a three-dimensional prong structure, preferably in a tooth array structure, more preferably in at least one of a rectangular tooth array distribution, a triangular tooth array distribution or a trapezoidal tooth array distribution.
7. The multifunctional composite negative electrode sheet according to claim 5 or 6, wherein the negative electrode materials in the plurality of negative electrode active material assemblies are different.
8. The multifunctional composite negative electrode sheet according to claim 5 or 6, wherein the negative electrode materials in the plurality of negative electrode active material assemblies are the same, and the concentrations of the negative electrode materials are different.
9. A method for preparing the multifunctional composite negative electrode sheet according to any one of claims 1 to 8, comprising sequentially forming a negative electrode active material layer and a negative electrode ion-conducting electron insulating layer on a negative electrode current collector layer,
preferably, the anode active material layer and the ion conducting electron insulating layer are formed by at least one of spray coating, equal-interval extrusion coating, sputtering or rolling with a mask structure, casting, chemical vapor deposition, atomic layer deposition, 3D printing, pulsed laser deposition, and the like.
10. A secondary battery comprising the multifunctional composite negative electrode sheet according to any one of claims 1 to 8.
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| CN113363419A (en) * | 2021-06-23 | 2021-09-07 | 天津市捷威动力工业有限公司 | Negative pole piece and preparation method and application thereof |
| CN114944489A (en) * | 2022-06-15 | 2022-08-26 | 北京航空航天大学 | Thin film layer with accordion MXene array and preparation method thereof, current collector, electrode and battery |
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