CN114122317A - Positive pole piece for solid-state battery and preparation method and application thereof - Google Patents

Positive pole piece for solid-state battery and preparation method and application thereof Download PDF

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Publication number
CN114122317A
CN114122317A CN202111396351.5A CN202111396351A CN114122317A CN 114122317 A CN114122317 A CN 114122317A CN 202111396351 A CN202111396351 A CN 202111396351A CN 114122317 A CN114122317 A CN 114122317A
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solid electrolyte
solid
active material
positive
conductive agent
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CN114122317B (en
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李瑞杰
周宇楠
张琪
陈少杰
杨红新
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Svolt Energy Technology Wuxi Co Ltd
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Svolt Energy Technology Wuxi Co Ltd
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention provides a positive pole piece for a solid-state battery and a preparation method and application thereof. The positive pole piece comprises a current collector and an electrode layer positioned on the surface of the current collector, wherein the electrode layer comprises a positive active substance, a solid electrolyte, a conductive agent and a binder; the solid electrolyte is coated on the surface of the positive active material, and the conductive agent is inserted between the positive active material and the solid electrolyte. The positive pole piece provided by the invention is coated by the solid electrolyte hydrate, so that the solid electrolyte is in closer contact with the positive active material, complete ion and electron transfer channels are formed among particles, the capacity, the rate capability and the cycle performance of the positive pole piece can be better exerted, and meanwhile, the preparation method provided by the invention can be suitable for positive pole pieces with various shapes and sizes, and the flexibility and the applicability of the positive pole piece are improved.

Description

Positive pole piece for solid-state battery and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid-state batteries, relates to a positive pole piece for a solid-state battery and a preparation method and application thereof, and particularly relates to a positive pole piece for an all-solid-state battery and a preparation method and application thereof.
Background
Solid state batteries are a battery technology. The solid-state battery adopts non-flammable solid-state battery electrolyte to replace flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved, the high-energy anode and cathode can be better adapted, the weight of the system is reduced, and the synchronous improvement of energy density is realized. Among various new battery systems, solid-state batteries are the next-generation technology closest to the industry, which has become a consensus of the industry and the scientific community.
The anode plate in the existing solid-state battery is usually manufactured by adopting the processes of homogenizing and coating. For example, CN111799514A discloses a method for preparing a positive plate or a negative plate for a solid-state battery, and a plate and a solid-state battery, wherein the method for preparing comprises: putting inorganic solid electrolyte powder with lithium ion conductivity and an organic polymer electrolyte material into an organic solvent, and uniformly mixing; pre-dispersing the obtained composite electrolyte coating slurry; uniformly spraying the pre-dispersed composite electrolyte coating slurry on the positive plate or the negative plate by adopting an ultrasonic atomization spraying machine; and drying the pole piece sprayed with the composite electrolyte coating slurry to obtain the positive pole piece or the negative pole piece coated with the composite electrolyte layer.
However, in this process, in order to ensure continuity of the positive electrode sheet, it is necessary to add a binder to the powder mixture. However, the adhesive of this type generally has no ionic conductivity, and after the polymer adhesive is dissolved in a solvent and dried, the adhesive is coated on the surface of the powder particles, which results in unsmooth transmission of ions and electrons between the particles, thereby significantly reducing the ionic conductivity and the electronic conductivity in the solid electrolyte positive electrode plate, and finally causing a serious loss of the rate capability and the capacity performance of the battery. And the binder is coated on the surfaces of the particles in the common wet homogenate coating, so that the using amount of the binder is increased. And because the solid electrolyte (particularly sulfide electrolyte) and most of the solvent are unstable, even if the stable solvent reacts, the ion conductivity of the solid electrolyte is reduced to some extent by the reaction of the solvent and the solid electrolyte, so that the impedance of a pole piece and a battery is increased, the multiplying power performance of the battery is reduced, and the cycle performance of the battery is influenced. In addition, the processes of drying, solvent recovery and treatment are added, such as (CN109256525A, CN108269966A), etc., which increases the cost and may cause environmental pollution.
Therefore, there is a method for preparing a positive electrode plate of a solid-state battery by a solvent-free method, such as CN109950633A, in which a positive active material, solid electrolyte particles, and conductive carbon are uniformly spread in a prefabricated mold sleeve, and are extruded by applying pressure. The disadvantages of this approach are: the process needs to evenly spread the powder in a mould, so that the size of the prepared anode depends on the size of the mould, and due to the problem of the uniformity of the spread powder, the size of an electrolyte layer pressed by the method is smaller, usually 0.5cm2～1cm2This makes the process impractical for large-scale industrial application.
Therefore, how to obtain a positive electrode plate with excellent electrochemical performance and a wide application range and a small limitation is an urgent technical problem to be solved.
Disclosure of Invention
The invention aims to provide a positive pole piece for a solid-state battery and a preparation method and application thereof. According to the invention, the solid electrolyte is coated on the surface of the positive active material in a layered coating manner by coating the positive active material with the solid electrolyte hydrate, and the conductive agent is inserted between the positive active material and the solid electrolyte, so that the solid electrolyte and the positive active material are in closer contact, complete ion and electron transfer channels are formed among particles, the capacity, the rate capability and the cycle performance of the positive pole piece are better exerted, and meanwhile, the preparation method provided by the invention can be suitable for the positive pole pieces in various shapes and sizes, and the flexibility and the applicability of the positive pole piece are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode plate for a solid-state battery, including a current collector and an electrode layer located on a surface of the current collector, where the electrode layer includes a positive active material, a solid electrolyte, a conductive agent, and a binder; the solid electrolyte is coated on the surface of the positive active material, and the conductive agent is inserted between the positive active material and the solid electrolyte.
In the invention, the solid electrolyte is coated on the surface of the positive active material, and the conductive agent is inserted between the positive active material and the solid electrolyte, so that the solid electrolyte is in closer contact with the positive active material, and complete ion and electron transfer channels are formed among particles, and the positive pole piece can exert better capacity and rate performance; and if the solid electrolyte is coated on the surface of the positive pole piece in a particle-coated form, the solid electrolyte is in point-point contact, the contact area is small, and the transmission impedance of lithium ions among particles is further increased.
In the invention, the conductive agent is inserted between the positive active material and the solid electrolyte, the electrolyte plays a role of conducting ions, the conductive agent plays a role of conducting electrons, and the conductive carbon inserted between the electrolytes plays a role of preventing the solid electrolyte from obstructing the electron conduction, thereby forming a complete ion and electron transfer channel between particles.
Preferably, the raw material of the solid electrolyte is solid electrolyte hydrate, preferably halide solid electrolyte hydrate; the chemical formula of the halide solid electrolyte hydrate is LiaMXb·xH2O, X is more than 0, wherein M comprises any one or the combination of at least two of Al, Ga, In, Sc, Y, La, Ho and Sc, and X comprises any one or the combination of at least two of F, Cl and Br0. ltoreq. a.ltoreq.10, 1. ltoreq. b.ltoreq.13, for example a can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 etc., b can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13 etc., x can be 0.5, 1, 2, 3, 4 or 5 etc.
In the invention, the halogen solid electrolyte is selected as the matrix of the hydrate, because the halogen solid electrolyte has the characteristic of forming the hydrate after contacting with water, and the hydration reaction is a reversible process, namely crystal water in the halogen solid electrolyte can be removed at high temperature to achieve the aim of recovering the structure and the conductivity of the halogen electrolyte, and the hydrates of other types of electrolytes have the problems of irreversible hydration reaction, harsh dehydration conditions and the like.
According to the invention, the solid electrolyte hydrate is used for coating the anode active material, the hydrate is firstly distributed in a point shape on the surface of the anode active material, and has a self-assembly tendency after further dehydration, so that the surface of the anode active material is coated in a layered manner after dehydration, and the conductive agent can be coated in the solid electrolyte.
Preferably, the solid electrolyte is coated on the surface of the positive electrode active material in a layered coating form.
In the present invention, the solid electrolyte is coated on the surface of the positive electrode active material in a layered coating manner, so that the solid electrolyte and the positive electrode active material are in closer contact. Preferably, the conductive agent includes any one of or a combination of at least two of carbon nanotubes, carbon nanowires, or graphene.
In the invention, the conductive agent is selected from substances with certain length, such as carbon nano tubes, carbon nano wires or graphene, and the conductive agent with certain length can well realize that the conductive agent can not only be contacted with the internal positive active substance and provide an electronic path, but also be positioned between solid electrolytes simultaneously, so that a complete ion and electron transfer channel is formed together, and the capacity, the rate capability and the cycle performance of the positive pole piece can be better exerted.
Preferably, the binder is subjected to an external shear force to obtain a filamentous structure.
According to the invention, the adhesive is processed by external shearing force to obtain a filiform structure, so that the preparation of the positive pole piece without a solvent can be realized, the filiform adhesive has viscosity, point-point contact is realized between positive mixed powder, and the adhesive is different from surface-surface contact between the adhesive and particles in the traditional wet coating process, so that the ion and electron transmission impedance between the particles is reduced, and the using amount of the adhesive can be reduced.
Preferably, the maximum length of the conductive agent is greater than the thickness of the coating layer of the solid electrolyte.
The positive electrode active material is preferably contained in the electrode layer in a mass ratio of 80 to 90%, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%, preferably 85 to 90%.
Compared with the conventional positive pole piece for the solid-state battery, the positive pole piece provided by the invention has the advantages that the mass of the positive active material can be further increased, so that the use amount of the solid-state electrolyte in the positive pole piece is favorably reduced, and the integral energy density of the battery is favorably improved.
Preferably, the mass ratio of the conductive agent in the electrode layer is 0.1 to 1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or the like.
Preferably, the binder is present in the electrode layer in a mass ratio of 0.2 to 1%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
Preferably, the solid electrolyte accounts for 8 to 15% of the electrode layer, such as 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%, and preferably 8 to 13%.
In the invention, the solid electrolyte is coated on the surface of the positive active material in a layered coating mode, so that the using amount of the solid electrolyte is reduced, but the problem of incomplete coating and poor contact between the electrolyte and the positive active material is easily caused when the content of the electrolyte is too small, namely the coating layer is too thin; if the electrolyte content is high, namely the coating layer is thick, although the specific capacity of the positive active material is favorably exerted, the energy density of the whole battery is reduced due to the fact that the proportion of the positive active material in the positive pole piece is reduced, therefore, in the invention, the electrolyte can be uniformly and compactly coated on the surface of the positive active material by the mass ratio of 8-13%, meanwhile, the mass ratio of the positive active material can be further improved, and the energy density of the battery is improved.
In a second aspect, the present invention provides a method for preparing a positive electrode plate for a solid-state battery according to the first aspect, wherein the method for preparing the positive electrode plate comprises the following steps:
(1) dissolving a solid electrolyte in water, adding a conductive agent, and drying to obtain a mixture of a solid electrolyte hydrate and the conductive agent;
(2) and (2) coating the surface of the positive active material with the mixture of the solid electrolyte hydrate and the conductive agent in the step (1), then adding the binder for mixing, and then compounding with a current collector to prepare the positive pole piece.
According to the invention, the solid electrolyte is subjected to hydration reaction, so that the solid electrolyte realizes a crystalline hydrate form after the step (1), and the crystalline hydrate form has the characteristic of affinity with the positive active material, and is further easier to coat on the surface of the positive active material, so that the positive pole piece with improved rate capability, cycle performance and capacity is obtained.
In the step (1) of the present invention, the amount of water used is not particularly limited, and the solid electrolyte may be completely dissolved.
In the invention, the binder is added later, if the binder is directly mixed with the mixture of the solid electrolyte hydrate and the conductive agent to the positive active material, the binder is wrapped in the solid electrolyte phase and can not play a role in binding the surfaces of active material particles, so that the surface of the active material is firstly coated with the solid electrolyte and the conductive carbon, and then the binder is introduced to the surface of the solid electrolyte to achieve the role of binding the particles.
In the present invention, the drying in step (1) is used to remove free water, resulting in a solid electrolyte hydrate.
Preferably, the solid electrolyte in step (1) is a halide solid electrolyte, and the solid electrolyte hydrate is a halide solid electrolyte hydrate.
Preferably, the drying temperature in step (1) is 50 to 100 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Preferably, the adhesive of step (2) is subjected to a filamentation structure treatment by the action of shear force.
According to the invention, the adhesive is processed by external shearing force to obtain a filiform structure, so that the preparation of the positive pole piece without a solvent can be realized, the filiform adhesive has viscosity, point-point contact is realized between positive mixed powder, and the adhesive is different from surface-surface contact between the adhesive and particles in the traditional wet coating process, so that the ion and electron transmission impedance between the particles is reduced, and the using amount of the adhesive can be reduced.
Preferably, the means for applying shear forces comprises a paddle mixer.
Preferably, the rotation speed of the mixer is 500-3000 rpm, such as 500rpm, 1000rpm, 1500rpm, 2000rpm, 2500rpm or 3000rpm, etc., and the treatment time is 10-60 min, such as 10min, 20min, 30min, 40min, 50min or 60min, etc.
Preferably, after the mixing in the step (2), the positive electrode plate is obtained by hot rolling or by heating and then rolling, and preferably, the positive electrode plate is hot rolled.
In the present invention, Li may be mixed and then heated or hot rolledaMXb·xH2Dehydration of O to form LiaMXbTo restore its conductivity, and LiaMXb·xH2O has the characteristic of self-assembly in the process of desolventizing, and can wrap conductive carbon in the dried solid electrolyte LiaMXbIn the positive electrode active material, the surface of the positive electrode active material is uniformly coated, and a hot rolling mode is selected, so that the step of independent heating can be omitted,the working procedure is saved.
Preferably, the temperature of the hot rolling is 150 to 250 ℃, for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃.
Preferably, the method of mixing in step (2) comprises dry mixing or wet mixing, preferably dry mixing.
According to the invention, dry mixing is selected, so that the solvent-free preparation of the positive pole piece can be realized, and the damage to the solid electrolyte caused by the contact of the electrolyte and an organic solvent is avoided, while wet mixing is selected, and except for the influence of the solvent, after the binder is added for wet mixing, the solid electrolyte and the conductive agent coated on the surface of the positive active material can fall off to a certain extent, so that the coating effect of the solid electrolyte on the positive active material is influenced, and the solid electrolyte and the positive active material cannot be fully contacted, so that the effect of the invention is reduced.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) dissolving a halide solid electrolyte in water, adding a conductive agent, and drying at 50-100 ℃ to obtain a mixture of a halide solid electrolyte hydrate and the conductive agent;
(2) coating the surface of the positive active material with the mixture of the halide solid electrolyte hydrate and the conductive agent in the step (1), then adding a binder for dry mixing, then compounding with a current collector, and carrying out hot rolling at 150-150 ℃ to prepare the positive pole piece;
and stirring the binder for 10-60 min at a rotating speed of 500-3000 rpm by a mixer with blades to obtain a filamentous structure.
In a third aspect, the present invention also provides a solid-state battery, including the positive electrode plate for a solid-state battery according to the first aspect.
Preferably, the solid-state battery is an all-solid-state battery.
If the positive pole piece provided by the invention is applied to a semi-solid battery, the problem that the solid electrolyte is incompatible with the electrolyte exists, namely the existence of the electrolyte can cause the conductivity of the inorganic solid electrolyte to be reduced and the structure to be damaged.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the solid electrolyte is coated on the surface of the positive active material in a layered coating manner by coating the positive active material with the solid electrolyte hydrate, and the conductive agent is inserted between the positive active material and the solid electrolyte, so that the solid electrolyte and the positive active material are in closer contact, complete ion and electron transfer channels are formed among particles, the capacity, the rate capability and the cycle performance of the positive pole piece are better exerted, and meanwhile, the preparation method provided by the invention can be suitable for the positive pole pieces in various shapes and sizes, and the flexibility and the applicability of the positive pole piece are improved. According to the all-solid-state battery provided by the invention, the discharge specific capacity ratio of 0.33C/0.1C can reach more than 87.2%, the capacity retention ratio after 50-week circulation at 0.33C can reach more than 86.7%, after a conductive agent with a certain length is further selected, the discharge specific capacity ratio of 0.33C/0.1C can reach more than 90.2%, the capacity retention ratio after 50-week circulation at 0.33C can reach more than 89.6%, meanwhile, dry mixing is further selected, the discharge specific capacity ratio of 0.33C/0.1C can reach more than 92.5%, and the capacity retention ratio after 50-week circulation at 0.33C can reach more than 95.4%.
Drawings
Fig. 1 is an SEM image of the solid electrolyte and the carbon nanotube-coated positive active material in the positive electrode sheet in example 1.
Fig. 2 is an SEM image of the solid electrolyte hydrate and the carbon nanotube-coated positive active material (i.e., before hot rolling) in example 1.
Fig. 3 is an SEM image of the positive electrode sheet provided in example 1.
Fig. 4 is a schematic view of the coating preparation process provided in example 1.
Fig. 5 is an SEM image of the active material coated with the solid electrolyte provided in comparative example 4.
Fig. 6 is an SEM image of the positive electrode active material provided in comparative example 1 after being mixed with a solid electrolyte.
Fig. 7 is an SEM image of the positive electrode sheet in comparative example 2.
Fig. 8 is an SEM image of NCM811 provided in examples and comparative examples.
Fig. 9 is an SEM image of the solid electrolyte provided in comparative example 1 in which the contact of the dots is formed on the surface of the active material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a positive electrode plate for a solid-state battery, which comprises an aluminum foil and an electrode layer located on the surface of the aluminum foil, wherein the electrode layer comprises NCM811 and a solid electrolyte Li3ScCl6Carbon nanotubes and polytetrafluoroethylene; the solid electrolyte is coated on the surface of the positive active material in a layered coating mode, and the conductive agent is inserted between the positive active material and the solid electrolyte;
wherein, in the electrode layer, the mass ratio of NCM811 is 85%, and Li3ScCl6The mass ratio of (2) is 13%, the mass ratio of the carbon nano tube is 1%, the mass ratio of the polytetrafluoroethylene is 1%, and the maximum length of the carbon nano tube is larger than the thickness of the solid electrolyte coating layer.
The preparation method of the positive pole piece comprises the following steps:
(1) mixing Li3ScCl6Dissolving in pure water, adding carbon nanotube after dissolving completely, stirring with stirring paddle, drying at 80 deg.C for 6 hr, removing free water to form Li3ScCl6·xH2O(0<x<5) A powder mixture with carbon nanotubes;
(2) mixing Li3ScCl6·xH2Mixing and coating the powder mixture of O and the carbon nano tube and NCM811 in a high-energy ball mill at the rotating speed of 500rpm for 2h, and then adding polytetrafluoroethylene which forms a filiform structure and is stirred for 60min at 2000rpm by a high-speed mixer into the mixtureAnd mixing, namely performing hot rolling on the mixed solid with viscoelasticity at 230 ℃, rolling to a thickness of 60 mu m, and then attaching the solid with the aluminum foil together to obtain the positive pole piece.
Fig. 1 shows an SEM image of the solid electrolyte and the carbon nanotube-coated positive electrode active material in the positive electrode sheet in example 1.
Fig. 2 shows an SEM image of the solid electrolyte hydrate and the carbon nanotube-coated positive active material (i.e., before hot rolling) in example 1.
Fig. 3 shows an SEM image of the positive electrode sheet provided in example 1.
Fig. 4 is a schematic diagram illustrating a process for preparing the solid electrolyte and conductive agent coated positive active material provided in example 1, and it can be seen from fig. 4 that the solid electrolyte hydrate is dehydrated and self-assembled after being subjected to hot rolling, a layered coating is formed on the surface of the positive active material, and the conductive agent is inserted between the solid electrolyte and the positive active material.
Example 2
The present embodiment provides a positive electrode plate for a solid-state battery, where the positive electrode plate includes an aluminum foil and an electrode layer located on the surface of the aluminum foil, and the electrode layer includes NCM622 and a solid electrolyte Li3YCl6Carbon nanowires and polytetrafluoroethylene; the solid electrolyte is coated on the surface of the positive active material in a layered coating mode, and the conductive agent is inserted between the positive active material and the solid electrolyte;
wherein, in the electrode layer, the mass ratio of NCM622 is 90%, Li3YCl6The mass ratio of the carbon nano wire is 8 percent, the mass ratio of the carbon nano wire is 1 percent, the mass ratio of the polytetrafluoroethylene is 1 percent, and the maximum length of the carbon nano wire is larger than the thickness of the solid electrolyte coating layer.
The preparation method of the positive pole piece is consistent with that of the embodiment 1, the hot rolling temperature is 150 ℃, and the rolling is carried out until the rolling reaches 80 mu m.
Example 3
The embodiment provides a positive electrode plate for a solid-state battery, the positive electrode plate comprises an aluminum foil and an electrode layer located on the surface of the aluminum foil, the electrode layer comprises NCM523 and solid-state electrolysisProton Li2ScBr5Graphene and polytetrafluoroethylene; the solid electrolyte is coated on the surface of the positive active material in a layered coating mode, and the conductive agent is inserted between the positive active material and the solid electrolyte;
wherein, in the electrode layer, the mass ratio of NCM523 is 88%, Li2ScBr5The mass ratio of (2) is 10%, the mass ratio of graphene is 1%, the mass ratio of polytetrafluoroethylene is 1%, and the maximum length of graphene is greater than the thickness of the solid electrolyte coating layer.
The preparation method of the positive pole piece is consistent with that of the embodiment 1, the hot rolling temperature is 200 ℃, and the rolling is carried out until the rolling reaches 60 mu m.
Example 4
The present example is different from example 1 in that the mass ratio of NCM811 in the present example is 75%, and Li is3ScCl6The mass ratio of (2) is 23%.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between this embodiment and embodiment 1 is that the conductive agent in this embodiment is Super P.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this example and example 1 is that, in this example, a positive electrode plate is prepared by wet coating;
the preparation method of the positive pole piece comprises the following steps:
(1) mixing Li3ScCl6Dissolving in pure water, adding carbon nanotube after dissolving completely, stirring with stirring paddle, drying at 80 deg.C for 6 hr, removing free water to form Li3ScCl6·xH2A powder mixture of O and carbon nanotubes;
(2) mixing Li3ScCl6·xH2Mixing and coating powder mixture of O and carbon nano tube and NCM811 in a high-energy ball mill at the rotating speed of 500rpm for 2h, adding polyvinylidene fluoride and NMP for continuous mixing to obtain mixed slurry, and mixingAnd drying the combined slurry, performing hot rolling at 230 ℃, rolling to a thickness of 60 mu m, and then attaching the slurry and an aluminum foil together to obtain the positive pole piece.
Comparative example 1
This comparative example provides a positive electrode sheet whose raw material was consistent with that of example 1, and in this comparative example, the solid electrolyte was coated on the surface of the positive active material in a particle-coated form.
The comparative example differs from example 1 in that the step (1) is not performed, and the surface of the positive electrode active material is coated with the solid electrolyte and the conductive carbon.
The remaining preparation methods and parameters were in accordance with example 1.
Fig. 9 shows an SEM image of the solid electrolyte provided in comparative example 1 in which the active material surface is dot-coated.
Fig. 6 shows an SEM image of the positive electrode sheet provided in comparative example 1.
Comparative example 2
This comparative example provides a positive electrode sheet whose raw material was consistent with that of example 1.
The preparation method adopts the traditional wet coating process to prepare:
dissolving polyvinylidene fluoride powder in a solvent toluene to prepare sol; putting the positive active material, the solid electrolyte particles, the conductive carbon and the sol into a stirrer together, and uniformly mixing to form slurry with uniform texture; and coating the slurry on an aluminum foil of a positive current collector, adjusting the coating thickness to be 60 mu m, and drying at 90 ℃ to obtain the positive pole piece.
Fig. 7 shows an SEM image of the positive electrode sheet in comparative example 2.
Fig. 8 shows SEM images of NCM811 provided in examples and comparative examples.
Comparative example 3
The present comparative example is different from example 1 in that Li is directly added in step (2) of the present comparative example3ScCl6·xH2O and a powder mixture of carbon nanotubes, NCM811 and polytetrafluoroethylene.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
The difference between the comparative example and the example 1 is that in the step (1) of the comparative example, the solid electrolyte hydrate is directly obtained without adding the carbon nano tube, and then the solid electrolyte hydrate is directly coated in the step (2), and then the binder and the conductive agent are added.
The remaining preparation methods and parameters were in accordance with example 1.
Fig. 9 shows an SEM image of the solid electrolyte-coated positive electrode active material in the positive electrode sheet in comparative example 4.
As can be seen from fig. 1 and 5, using the method of example 1, the conductive carbon and the solid electrolyte can be coated on the positive electrode active material at the same time, i.e., a structure in which the conductive carbon is inserted into the solid electrolyte (one end of the conductive carbon is in contact with the positive electrode active material, and the other end thereof protrudes out of the solid electrolyte layer) to form a mixed conductor of ions and electrons can be obtained, while the method of comparative example 4 can only coat the solid electrolyte on the positive electrode active material, and cannot insert the conductive carbon therein, resulting in that only an ion conductor is formed and an electron conductor is constructed at the same time, causing the electron conduction to be hindered. .
As can be seen from fig. 1, 2 and 9, when the hydrate of the solid electrolyte is mixed with the positive electrode active material, the hydrate of the solid electrolyte is in point contact with the surface of the positive electrode (fig. 2); the solid electrolyte can be layered (i.e. in surface-to-surface contact) on the surface of the positive electrode after the temperature is raised and the solid electrolyte is dehydrated (figure 1); when the solid electrolyte and the positive electrode active material were directly mixed, the two materials were in point contact with each other (fig. 9).
As can be seen from fig. 1, 8 and 9, after the positive active material is coated, the solid electrolyte can be coated on the surface of the positive active material in a layered coating manner, and the flocculent substance in fig. 1 is a carbon nanotube which is inserted between the solid electrolyte and the positive active material instead of the dot-shaped coating of the active material by the solid electrolyte obtained in a general coating manner (fig. 9), which makes the contact area between the solid electrolyte and the positive material more sufficient, and as can be seen from fig. 1 and 9, the solid electrolyte can be coated on the positive active material only in the conventional coating manner, and the solid electrolyte and the conductive agent can be coated simultaneously by the method in the present invention, so that a more perfect ion and electron mixing channel is constructed.
As can be seen from the comparison between fig. 2 and fig. 6, after the hydrate of the solid electrolyte is coated, the hydrate of the solid electrolyte is distributed in a dotted manner on the surface of the positive active material, and the hydrate of the solid electrolyte has a self-assembly tendency in the dehydration process, so that the surface of the positive powder is coated in a layered manner after dehydration, and the conductive agent can be coated in the solid electrolyte; as can be seen from fig. 6, the larger spherical particles are positive electrode active materials, and the smaller amorphous particles are solid electrolyte particles. The mixed powder is prepared by the method in the comparative example 1, that is, the surface of the positive active material is not coated by the solid electrolyte and the conductive carbon, but the solid electrolyte, the conductive carbon and the positive active material are mechanically mixed together, and then, with reference to fig. 9, the positive active material and the solid electrolyte exist in a granular shape, and the contact between the positive active material and the solid electrolyte is point-point contact, so that the contact area is small, and the transmission impedance of lithium ions among the granules is increased.
As can be seen from fig. 3, the binder exists in a filament shape by the method of the present invention, and the contact between the binder and the positive electrode active material particles is point-to-point contact, which has little effect of inhibiting the transmission of ions and electrons.
As can be seen from fig. 7, when the wet coating process is used, i.e., after the binder is dissolved in the solvent and dried, the binder is present in a coating form on the particle surface, i.e., the binder is in surface-to-surface contact with the active material particles and the electrolyte particles, and the binder is an insulator for ions and electrons, and thus the contact form has a large blocking effect on the transmission of ions and electrons, resulting in poor rate performance.
The positive electrode plates provided in examples 1 to 6 and comparative examples 1 to 4 were used as positive electrodes, Li6PS5And Cl is used as an electrolyte layer and metal In is used as a negative electrode, and the all-solid-state battery is obtained by assembling. The battery is set at 0.1C and 0.33CThe data results of the charge and discharge tests at the magnification of (1) are shown in table.
TABLE 1
Figure BDA0003370474730000151
Figure BDA0003370474730000161
The positive electrode active materials in the embodiments 2 and 3 are different from the positive electrode active material in the embodiment 1, so the specific discharge capacities of the positive electrode active materials at different multiplying powers are different, but the positive electrode active materials are still beneficial to exerting the gram capacity of the positive electrode active material compared with the positive electrode active materials of the same type, and the multiplying power performance and the cycle performance of the positive electrode active material are improved.
From the data results of example 1 and example 4, it is understood that the mass fraction of the positive electrode active material is too small, which is advantageous for the positive electrode active material to exhibit gram capacity, but significantly lowers the mass energy density of the battery.
As is clear from the data results of examples 1 and 5, selecting a length or not a length of the conductive agent causes difficulty in electron transport between particles, and further causes a decrease in gram capacity of the positive electrode active material and deterioration in rate capability.
From the data results of example 1 and example 6, it can be seen that, compared to the dry mixing method in example 1, when the positive electrode plate is prepared by the wet method in example 6, the solvent may damage the solid electrolyte, thereby reducing the conductivity of the solid electrolyte, reducing the gram volume of the active material, and the solvent may reduce the stability of the solid electrolyte, thereby reducing the cycle retention rate.
As can be seen from the data results of example 1 and comparative example 1, the solid electrolyte is directly coated on the surface of the positive electrode active material in the form of particles, and the contact area is small due to point-to-point contact, so that the transmission resistance of lithium ions between particles is increased, and the electrochemical performance is poor.
As can be seen from the data results of example 1 and comparative example 2, the contact between the solid electrolyte and the positive active material is tighter, and complete ion and electron transfer channels are formed between the particles, so that damage to the solid electrolyte caused by the contact between the electrolyte and the organic solvent is avoided during the preparation of the electrode plate, and the used binder is in point-like contact with the particles, so that the obstruction to the ion and electron transfer is avoided, so that the electrode plate prepared in example 1 has better capacity performance and rate capability. And no solvent damages the solid electrolyte in the preparation process, so the positive pole piece in the embodiment 1 has higher cycle retention rate.
As can be seen from the data results of example 6 and comparative example 3, compared with the common wet coating process, the positive active material is not coated, and the positive electrode sheet provided by the invention can still realize higher capacity exertion and rate exertion;
from the data results of example 1 and comparative example 4, it is known that the simultaneous coating of the solid electrolyte and the conductive carbon on the positive electrode active material cannot be achieved only by coating the positive electrode active material with the solid electrolyte hydrate without adding the conductive agent during the coating, that is, a mixed conductive network of ions and electrons cannot be formed on the surface of the positive electrode active material, which results in poor electron transfer and a decrease in rate capability.
In summary, the solid electrolyte is coated on the surface of the positive active material in a layered coating manner by coating the positive active material with the solid electrolyte hydrate, and the conductive agent is inserted between the positive active material and the solid electrolyte, so that the solid electrolyte and the positive active material are in closer contact, and complete ion and electron transfer channels are formed between particles, and the capacity, rate capability and cycle performance of the positive pole piece are better exerted. According to the all-solid-state battery provided by the invention, the discharge specific capacity ratio of 0.33C/0.1C can reach more than 87.2%, the capacity retention ratio after 50-week circulation at 0.33C can reach more than 86.7%, after a conductive agent with a certain length is further selected, the discharge specific capacity ratio of 0.33C/0.1C can reach more than 90.2%, the capacity retention ratio after 50-week circulation at 0.33C can reach more than 89.6%, meanwhile, dry mixing is further selected, the discharge specific capacity ratio of 0.33C/0.1C can reach more than 92.5%, and the capacity retention ratio after 50-week circulation at 0.33C can reach more than 95.4%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The positive pole piece for the solid-state battery is characterized by comprising a current collector and an electrode layer positioned on the surface of the current collector, wherein the electrode layer comprises a positive active substance, a solid electrolyte, a conductive agent and an adhesive; the solid electrolyte is coated on the surface of the positive active material, and the conductive agent is inserted between the positive active material and the solid electrolyte.
2. The positive electrode sheet for the solid-state battery according to claim 1, wherein a raw material of the solid electrolyte is a solid electrolyte hydrate, preferably a halide solid electrolyte hydrate;
preferably, the solid electrolyte is coated on the surface of the positive electrode active material in a layered coating form;
preferably, the conductive agent comprises any one of carbon nanotubes, carbon nanowires or graphene or a combination of at least two of the same;
preferably, the binder is subjected to an external shear force to obtain a filamentous structure.
3. The positive electrode sheet for solid-state batteries according to claim 1 or 2, wherein the maximum length of the conductive agent is greater than the thickness of the coating layer of the solid-state electrolyte.
4. The positive electrode plate for the solid-state battery according to any one of claims 1 to 3, wherein the mass proportion of the positive active material in the electrode layer is 80 to 90%, preferably 85 to 90%;
preferably, the mass ratio of the conductive agent in the electrode layer is 0.1-1%;
preferably, the mass ratio of the binder in the electrode layer is 0.2-1%;
preferably, the mass ratio of the solid electrolyte in the electrode layer is 8-15%, and preferably 8-13%.
5. A preparation method of the positive electrode plate for the solid-state battery according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) dissolving a solid electrolyte in water, adding a conductive agent, and drying to obtain a mixture of a solid electrolyte hydrate and the conductive agent;
(2) and (2) coating the surface of the positive active material with the mixture of the solid electrolyte hydrate and the conductive agent in the step (1), then adding the binder for mixing, and then compounding with a current collector to prepare the positive pole piece.
6. The method for preparing the positive electrode plate for the solid-state battery according to claim 5, wherein the solid electrolyte in the step (1) is a halide solid electrolyte, and the solid electrolyte hydrate is a halide solid electrolyte hydrate;
preferably, the drying temperature in the step (1) is 50-100 ℃;
preferably, the adhesive in the step (2) is subjected to filamentation structure treatment by the action of shearing force;
preferably, the device on which the shear forces act comprises a paddle mixer;
preferably, the rotating speed of the mixer is 500-3000 rpm, and the processing time is 10-60 min.
7. The preparation method of the positive electrode plate for the solid-state battery according to claim 5 or 6, wherein the positive electrode plate is obtained by hot rolling or heating and then rolling after the mixing in the step (2), preferably hot rolling;
preferably, the temperature of the hot rolling is 150-250 ℃.
8. The method for preparing the positive electrode sheet for the solid-state battery according to any one of claims 5 to 7, wherein the mixing method in the step (2) comprises dry mixing or wet mixing, preferably dry mixing.
9. The method for manufacturing a positive electrode plate for a solid-state battery according to any one of claims 5 to 8, comprising the steps of:
(1) dissolving a halide solid electrolyte in water, adding a conductive agent, and drying at 50-100 ℃ to obtain a mixture of a halide solid electrolyte hydrate and the conductive agent;
(2) coating the surface of the positive active material with the mixture of the halide solid electrolyte hydrate and the conductive agent in the step (1), then adding a binder for dry mixing, then compounding with a current collector, and carrying out hot rolling at 150-150 ℃ to prepare the positive pole piece;
and stirring the binder for 10-60 min at a rotating speed of 500-3000 rpm by a mixer with blades to obtain a filamentous structure.
10. A solid-state battery comprising the positive electrode sheet for a solid-state battery according to any one of claims 1 to 4;
preferably, the solid-state battery is an all-solid-state battery.
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