CN113036213A - Composite solid electrolyte material, preparation method thereof and application thereof in lithium ion battery - Google Patents

Composite solid electrolyte material, preparation method thereof and application thereof in lithium ion battery Download PDF

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CN113036213A
CN113036213A CN201911357394.5A CN201911357394A CN113036213A CN 113036213 A CN113036213 A CN 113036213A CN 201911357394 A CN201911357394 A CN 201911357394A CN 113036213 A CN113036213 A CN 113036213A
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layer
electrolyte
slurry
composite
lithium
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付文浩
马朝晖
张莹莹
王英杰
徐晓东
任建国
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BTR New Material Group 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
    • 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
    • H01M10/052—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
    • H01M10/058—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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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Abstract

The invention discloses a composite solid electrolyte material, a preparation method thereof and application in a lithium ion battery, wherein the composite electrolyte material comprises a first layer, a second layer and a third layer which are sequentially stacked, the first layer is a ceramic matrix layer, the second layer and the third layer form a composite film layer, and the second layer is an electrolyte conductor wrapped Al2O3A composite layer formed by particles, and the third layer is an electrolyte conductor layer. The method comprises the following steps: 1) preparing a ceramic matrix biscuit by adopting electrolyte powder; 2) preparation of a composition containing Al2O3Is applied to the surface of the ceramic biscuit by a coating process to form Al2O3A layer; 3) is prepared fromLithium salt slurry is sprayed on Al2O3Forming a lithium salt layer on the surface of the layer; 4) and sintering to obtain the composite solid electrolyte material. The ceramic-based electrolyte prepared by the invention can obtain higher interface ionic conductance, good mechanical property and higher thermal stability.

Description

Composite solid electrolyte material, preparation method thereof and application thereof in lithium ion battery
Technical Field
The invention relates to the field of batteries, and relates to a composite solid electrolyte material, a preparation method thereof and application thereof in a lithium ion battery.
Background
Lithium ion batteries have been widely used in portable electronic products and electric vehicles because of their advantages of high operating voltage, long cycle life, no memory effect, low self-discharge, and environmental friendliness. Currently, several countries, including china, have established strategic goals for further increasing the energy density of power cells to the mid-and long-term range of 300-400 watt-hours/kg.
Since the capacity of lithium metal is 3860mAh/g, which is about 10 times that of graphite, a lithium metal battery using metallic lithium as a negative electrode has been inevitably selected. However, a series of technical problems of the lithium metal negative electrode in the liquid battery still lack an effective solution so far, such as more interface side reactions of the lithium metal and the liquid electrolyte, uneven and unstable SEI film distribution, poor cycle life, uneven deposition and dissolution of the lithium metal, uneven lithium dendrites and holes, and battery safety problems.
For the above reasons, many researchers are looking to solve the application problem of the lithium metal negative electrode to the use of the solid electrolyte. The main idea is to avoid side reactions that continuously occur in the liquid electrolyte, and simultaneously to utilize the mechanical and electrical properties of the solid electrolyte to inhibit the formation of lithium dendrites.
Phosphate of solid electrolyte NASICON structure, the component of which is Li1+xAxB2-x(MO4)3Wherein x is 0.05-0.7, A is one or more of Al, Ga, Sc, Y, Ca, Sr, Zn, Si, In, Lu, La, Fe and Cr,b is Ti or Ge, M is P or Si; titanate electrolyte with Perovskite (Perovskite type) structure and Li as component3xM1/3-2xLa2/3-xNO3Wherein x ranges from 0.01 to 0.16, M is one or more of Ca, Sr, Zn, Mg, Al, Sc, Y, In and Cr, and N is one or two of Ti or Ge; li7+xGexP3-xS11(LGPS) wherein x ranges from 0.05 to 2; has wide electrochemical window, good thermal stability and excellent ionic conductivity.
However, this type of electrolyte also has some problems in using lithium metal as the negative electrode. Such as Ti4+，Ge4+Ti is easy to be reduced in the actual working process3+，Ge3+Thereby destroying the crystal structure of the electrolyte, and the secondary oxidation process is also the process of passing internal electrons, causing internal short circuit of the electrolyte, and the battery can cause serious lithium dendrite problems in the circulating process, which limits the development of the all-solid-state battery.
Therefore, there is a need for an effective method to reduce the above detrimental hazards and improve battery performance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a composite solid electrolyte material, a preparation method thereof, and a use thereof in a lithium ion battery. In the composite solid electrolyte material, the surface of the ceramic substrate layer is provided with the composite film layer with a specific structure, one part of the composite film layer plays a role in transmitting lithium ions, and the other part plays a role in protecting the ceramic-based electrolyte. Compared with the existing ceramic-based solid electrolyte, the ceramic-based solid electrolyte prepared by the invention can obtain higher interface ionic conductance, and meanwhile, the aluminum oxide protective layer can enable the electrolyte to have good mechanical property and higher thermal stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite solid electrolyte material (the structural schematic of which is shown in fig. 1), comprising a composite solid electrolyte material comprising, in orderThe laminated ceramic membrane comprises a first layer, a second layer and a third layer which are stacked, wherein the first layer is a ceramic substrate layer, the second layer and the third layer form a composite membrane layer, and the second layer is an electrolyte conductor wrapped with Al2O3A composite layer formed by particles, and the third layer is an electrolyte conductor layer.
The composite solid electrolyte material of the present invention is an inorganic solid electrolyte material capable of obtaining a lithium ion conductivity range of 10 at room temperature-5～10-2S/cm, and the composite inorganic solid electrolyte has high stability to metal lithium and excellent mechanical performance.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the composite film layer is formed by passing Al2O3The particles are formed by reaction with a lithium salt, for example under high temperature sintering conditions.
Preferably, the thickness of the composite film layer is 0.1 to 50 μm, for example, 0.1 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 15 μm, 17.5 μm, 20 μm, 25 μm, 30 μm, 33 μm, 36 μm, 40 μm, 45 μm, or 50 μm, and the excessively thick composite layer is not suitable for passing lithium ions, and causes a propagation path of lithium ions to be increased and ion conductivity to be low, and thus the above range is preferable, and more preferably 1 to 10 μm, from the aspect of lithium ion dynamics.
Preferably, the electrolyte conductor is LiAlO2。
Preferably, the ceramic matrix layer is a solid fast-ion ceramic matrix layer, and the chemical composition is a lithium ion conductor solid electrolyte, preferably including but not limited to: an electrolyte of NASICON structure and/or an electrolyte of perovskite structure.
Preferably, the electrolyte of NASICON structure has a chemical composition of Li1+xAxB2-x(MO4)3Wherein x is In the range of 0.05-0.7, and A is Al, Ga, Sc, Y, Ca, Sr, Zn, Si, In, Lu, La, Fe or CrAny 1 or a combination of at least 2, B comprises Ti and/or Ge, and M comprises P and/or Si.
Preferably, the chemical composition of the perovskite-structured electrolyte is Li3xM1/3-2xLa2/3-xNO3Wherein x ranges from 0.01 to 0.17, M comprises any 1 or the combination of at least 2 of Ca, Sr, Zn, Mg, Al, Sc, Y, In or Cr, and N comprises any one or two of Ti or Ge.
The invention lists a few Ti and Ge containing variable valence elements in the fast ion conductor, but the invention is not limited to the protection of Ti and Ge elements, and the protection of other ceramic matrixes containing variable valence elements is also in the protection scope of the patent.
Preferably, the lithium ion conductor solid electrolyte D50 is 0.1-10 μm, such as 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. D90 is 0.2 to 20 μm, for example, 0.2, 0.5, 1, 2, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 18 or 20 μm.
Preferably, the lithium ion conductor solid electrolyte is Li with D50 of 2-3 μm and D90 of 1-10 μm1.3Al0.3Ti1.7(PO4)3And Li0.5La0.5TiO3。
Preferably, the Al2O3The chemical composition of the particles comprises alpha-Al2O3、β-Al2O3Or gamma-Al2O3Any 1 or a combination of at least 2 of them. The three different crystal forms of Al2O3Preferably, alpha-Al is used2O3Due to Al2O3The solid phase reaction with lithium carbonate is an interface diffusion process, and in the diffusion process, lithium salts such as lithium carbonate and the like are unidirectionally diffused to aluminum oxide to generate LiAlO2Or a fast ion conductor formed by interdiffusion of lithium ions and aluminum ions through oxygen ion lattice gaps. Therefore, alpha-Al is used2O3Relatively pure alpha-LiAlO can be obtained relatively easily2Fast ion conductors, ions of such electrolytesThe conductivity is higher.
Preferably, the Al2O3The particle diameter D50 is 1 to 50 μm, for example, 1 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, 11 μm, 12 μm, 14 μm, 18 μm, 22 μm, 25 μm, 30 μm, 35 μm, 38 μm, 40 μm, 45 μm or 50 μm.
Preferably, the Al2O3The particles are alpha-Al with D50 of 1-2 mu m2O3。
In a second aspect, the present invention provides a method for producing a composite solid electrolyte material according to the first aspect, characterized in that the method comprises the steps of:
(1) preparing a ceramic matrix biscuit by adopting electrolyte powder through a molding process;
(2) preparation of a composition containing Al2O3By a coating process, the slurry is coated on the surface of the ceramic biscuit in the step (1) to form Al2O3A layer;
(3) preparing lithium salt-containing slurry, and spraying the Al in the step (2)2O3Forming a lithium salt layer on the surface of the layer;
(4) and sintering to obtain the composite solid electrolyte material.
The method combines the coating process and the spraying process to form Al on the surface of the ceramic matrix biscuit in sequence2O3Layer and lithium salt layer, sintering process, Al2O3Al in the layer2O3The surface of the particles reacts with lithium salt to generate an electrolyte conductor composite film layer, the ceramic matrix layer is a first layer, the composite film layer comprises a second layer and a third layer, the second layer is in contact with the ceramic matrix layer, and specifically is Al2O3Particles and coated Al2O3The particulate electrolyte conductor, the third layer, is physically integral with the second layer, is located on the surface of the second layer, and is specifically the electrolyte conductor. In the composite solid electrolyte material prepared by the method, the surface of the ceramic matrix layer is provided with the composite film layer with a specific structure, one part of the composite film layer plays a role in transmitting lithium ions, and the other part plays a role in protecting the ceramic-based electrolyte. FromAnd has higher interface ionic conductivity, excellent mechanical property and higher thermal stability.
In the method of the present invention, Al must be formed on the surface of the ceramic biscuit by a coating process in step (2)2O3Layer, then spraying process is adopted to coat Al in the step (3)2O3A lithium salt layer is formed on the surface of the layer.
If the spraying process is adopted in the step (2), Al formed by spraying can be caused2O3The density of the layer is low, and the second layer (specifically Al) in the formed product2O3Particles and coated Al2O3The electrolyte conductor of the particle) cannot exert an effective protective effect.
If the coating process is adopted in the step (3), the lower alumina layer is easily damaged in the coating process, and if the spraying process is adopted, the operation process becomes very simple and a relatively ideal effect can be achieved.
As a preferable technical scheme of the method, the forming process in the step (1) comprises any 1 of a cold isostatic pressing method, a casting method or a rolling method, and the cold isostatic pressing method is preferable.
Preferably, in the step (1), the ceramic matrix blank is prepared by a cold isostatic pressing method, and the pressure of the pressed sheet is controlled to be 50-150 MPa, such as 50MPa, 60MPa, 75MPa, 85MPa, 100MPa, 110MPa, 120MPa, 130MPa, 140MPa or 150 MPa.
Preferably, the D50 of the electrolyte powder in the step (1) is 0.1-10 μm, such as 0.1 μm, 0.5 μm, 1 μm, 2 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm. D90 is 0.2 to 20 μm, for example, 0.2, 0.5, 1, 2, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 18 or 20 μm.
Preferably, the ceramic matrix blank prepared in step (1) is prepared by a cold isostatic pressing method, and the diameter of the prepared ceramic matrix blank is preferably 2-15 mm, such as 2mm, 5mm, 8mm, 10mm, 12mm or 15 mm. The thickness is preferably 1 to 5mm, for example 1mm, 2mm, 3mm, 3.5mm, 4mm or 5 mm.
Preferably, the ceramic matrix biscuit of step (1) is a solid fast ion ceramic matrix biscuit.
As a preferable embodiment of the method of the present invention, Al in the step (2)2O3Comprises alpha-Al2O3、β-Al2O3Or gamma-Al2O3Any one or a combination of at least 1 and preferably alpha-Al2O3。
Preferably, Al in the step (2)2O3The particle diameter D50 is 1 to 50 μm, for example, 1 μm, 5 μm, 10 μm, 13 μm, 16 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, preferably 1 to 2 μm.
Preferably, Al in the step (2)2O3alpha-Al having a particle size D50 of 2-10 μm2O3. The surface of the alumina with small grain diameter has higher interface energy, which is beneficial to generating LiAlO with small grain diameter2alpha-Al is used2O3Relatively pure alpha-LiAlO can be obtained relatively easily2Fast ion conductor, the electrolyte has high ion conductivity.
Preferably, Al in the step (2)2O3Is smaller than, preferably slightly smaller than, the particle size of the electrolyte powder, so that coating the alumina powder on the sheet pressed with the electrolyte powder will distribute a part of the alumina among the particles of the sheet, and later spraying a lithium salt and sintering the resulting LiAlO2The electrolyte can be more tightly connected with the matrix into a whole to form a compact layer.
Preferably, the solvent used in the slurry preparation in step (2) comprises any 1 or a combination of at least 2 of deionized water, methanol, ethanol, isopropanol, acetone, butanone, or trichloroethylene, preferably deionized water.
Preferably, Al prepared by coating as described in step (2)2O3The thickness of the layer is 1 to 8 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6.5 μm or 7.5 μm, and more preferably 1 to 5 μm.
Preferably, the slurry preparation process in step (2) further comprises a dispersant, wherein the dispersant comprises any 1 or at least 2 of polyethylene glycol, polymethacrylic acid, polyacrylic acid, acrylic acid-acrylate copolymer or polyvinylpyrrolidone.
The invention is realized by optimizing Al with proper size2O3A solvent and a dispersant, Al may be added2O3A single-layer or relatively thin aluminum oxide layer is formed in the coating process, a reaction platform can be provided for the lithium salt sprayed subsequently, and a thin layer of Al is generated2O3And LiAlO2The composite layer of (1).
Preferably, the dispersant is present in an amount of 0.5 to 10 wt.%, such as 0.5 wt.%, 1 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, preferably 2 to 6 wt.%, based on 100 wt.% of the total mass of the slurry of step (2).
Preferably, the solid content of the slurry in the step (2) is 5-30%, such as 5%, 10%, 12%, 15%, 18%, 20%, 25%, 26%, 28%, 30%, etc., preferably 10-15%.
Since step (2) of the present invention is performed by a coating process, Al will be contained2O3Is coated on the surface of the ceramic biscuit in the step (1) to form Al2O3Layer of Al by a subsequent sintering step2O3Al in the layer2O3The surface of the particles reacts with lithium salt to generate an electrolyte conductor composite film layer, one part of the composite film layer plays a role in transmitting lithium ions, the other part of the composite film layer plays a role in protecting the ceramic-based electrolyte, and the solid content of the slurry in the step (2) needs to be controlled within a proper range. If the solid content is less than 10%, the slurry is too dilute, resulting in Al in the second layer formed after a portion of alumina is removed by sintering reaction after coating2O3The particles can not effectively improve the mechanical property, so that Al2O3The layer plays an effective protective role; if the solids content is greater than 30%, the slurry is too concentrated, resulting in Al formation by the coating2O3The layer being too thick, and then sintering only the Al of the surface layer in contact with the lithium salt2O3The particles react with a lithium salt to form an electrolyte conductor layerBut not of contact Al2O3The particles are not reacted, corresponding to a further layer of excess Al between the first and second layers2O3And a layer which is electrically non-conductive, and in which lithium ion transport conductivity of lithium ions between the first layer and the second layer is decreased.
The invention prepares Al-containing alloy in the step (2)2O3The concrete operation of the slurry of (3) is not limited, and for example, Al may be used2O3Adding a dispersing agent into a solvent according to a certain proportion to prepare uniformly dispersed Al2O3And (3) slurry. Or dispersing the dispersant into the solvent, and then adding Al2O3Preparing uniformly dispersed Al2O3And (3) slurry.
As a preferred embodiment of the method of the present invention, the lithium salt in step (3) includes any 1 or a combination of at least 2 of lithium carbonate, lithium nitrate, lithium oxalate, lithium acetate, or lithium citrate. The lithium salt can react with Al at high temperature (such as 600-900 ℃)2O3The electrolyte conductor layer is preferably formed by reaction with Al2O3The reaction produces a lithium salt of an inorganic fast ion conductor, which may be, for example, LiAlO2。
Preferably, the solvent used in the slurry preparation in step (3) comprises any 1 or a combination of at least 2 of deionized water, methanol, ethanol, isopropanol or butanone, preferably acetone.
Preferably, the slurry preparation process in step (3) further comprises a dispersant, wherein the dispersant comprises any 1 or at least 2 of polyethylene glycol, polymethacrylic acid, polyacrylic acid, acrylic acid-acrylate copolymer or polyvinylpyrrolidone.
Preferably, the dispersant is present in an amount of 0.5 to 8 wt.%, such as 0, 0.2 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2.5 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 7 wt.% or 8 wt.%, preferably 3 to 5 wt.%, based on 100 wt.% of the total mass of the slurry of step (3).
Preferably, the solid content of the slurry in the step (3) is 0.1-50%, such as 0.1%, 0.5%, 1%, 3%, 5%, 8%, 12%, 16%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, etc., preferably 5-13%.
Since step (3) of the present invention is performed by a spray coating process, Al is described in step (2)2O3Forming a lithium salt layer on the surface of the layer, and sintering the layer to obtain Al2O3Al in the layer2O3The surfaces of the particles react with lithium salt to generate an electrolyte conductor composite film layer, one part of the composite film layer plays a role in transmitting lithium ions, the other part of the composite film layer plays a role in protecting the ceramic-based electrolyte, and the solid content of the slurry in the step (3) needs to be controlled within a proper range. If the solid content is less than 0.1%, the slurry is too dilute, which may result in insufficient amount of lithium salt reactant to react with Al2O3The electrolyte conductor layer generated by the reaction plays a role in effectively transmitting lithium ions; if the solid content is more than 50%, the slurry is too concentrated, and a part of the lithium salt does not participate in the reaction and remains on the sample surface, such as Li2CO3And LiOH, etc., form an impurity layer, which is not highly conductive to lithium ions in a solid state and greatly reduces the conductivity of lithium ions, so the formation of the impurity layer should be avoided.
In the present invention, the specific operation of preparing the slurry containing the lithium salt in step (3) is not limited, and for example, the lithium salt and the dispersant may be added to the solvent at a certain ratio to prepare a uniformly dispersed lithium salt slurry.
The spraying process in step (3) of the present invention may be specifically performed, for example, by spraying the prepared lithium salt-containing slurry uniformly onto Al with a spray gun2O3On the surface of the layer, a lithium salt layer is formed.
Preferably, the thickness of the lithium salt layer in step (3) is 1-3 μm, such as 1 μm, 1.2 μm, 1.5 μm, 1.7 μm, 2 μm, 2.2 μm, 2.5 μm, or 3 μm, and preferably 1-2 μm.
As a preferred technical scheme of the method of the invention, the device used for sintering in the step (4) comprises any 1 or at least 2 combinations of muffle furnace, tube furnace, box furnace or rotary furnace, but is not limited to the sintering furnace listed above, and other sintering furnaces commonly used in the field can be used for the invention to achieve the same effect.
In the invention, the sintering temperature needs to be controlled within a proper range, so that lithium salt and Al are ensured on the one hand2O3The electrolyte conductor is generated by reaction, and on the other hand, the impurities such as AlPO generated by the decomposition of the ceramic matrix layer and the like caused by overhigh temperature are avoided4Too high a temperature leads to a destruction of the lattice structure of the ceramic substrate layer, which is detrimental to the conduction of lithium ions.
In order to better achieve the effects of generating the electrolyte conductor and avoiding the generation of impurities through the reaction, the sintering temperature in the step (4) is preferably 600 to 900 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like.
Preferably, the sintering time in the step (4) is 3-12 h, such as 3h, 5h, 6h, 8h, 10h, 11h or 12 h.
Preferably, the heating rate for heating to the sintering temperature is 1-10 ℃/min, such as 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 8 ℃/min or 10 ℃/min.
Preferably, the atmosphere for sintering in step (4) is any 1 or a combination of at least 2 of air, oxygen, nitrogen, helium or neon.
Preferably, the method further comprises a step of drying after step (3) and before step (4).
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) preparing a PVA aqueous solution, adding electrolyte powder, grinding, and pressing the ground electrolyte powder into a ceramic matrix biscuit by adopting a cold isostatic pressing method under the pressure of 50-150 MPa;
(2) preparing an aqueous solution by using polyacrylic acid as a dispersing agent, and taking alpha-Al with D50 being 1-2 mu m2O3Preparing slurry with the solid content of 10-30% in the aqueous solution, adjusting the pH value of the solution to 8-9 by using ammonia water, and coating the prepared slurry on the surface of the ceramic biscuit prepared in the step (1) by using a coating method;
(3) lithium salt, a dispersing agent and acetone are adopted to prepare slurry with the solid content of 5-13%, wherein the dispersing agent is polyacrylic acid, the content of the polyacrylic acid accounts for 1 wt% of the slurry, and the prepared slurry is sprayed to the alpha-Al prepared in the step (2) by using a spray gun2O3On the coating layer, on alpha-Al2O3A layer of lithium salt is formed on the surface of the lithium ion battery;
(4) drying the composite electrolyte prepared in the step (3), and then sintering for 3-12 h at 600-900 ℃ to form a layer of alpha-Al on the surface of the ceramic electrolyte2O3And LiAlO2Thereby producing a composite solid electrolyte material.
In the preferred technical scheme, the PVA aqueous solution is limited in the step (1) mainly for increasing the bonding effect of the electrolyte powder in the granulation process, so that microspheres are easier to form among granules, a pressed biscuit is more compact, and brittle fracture is not easy to occur.
In a third aspect, the present invention provides a lithium ion battery comprising the composite solid state electrolyte material of the first aspect.
Preferably, the lithium ion battery is a lithium ion all-solid-state battery.
Preferably, the lithium ion battery uses metal lithium as a negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the composite solid electrolyte material, the surface of the ceramic substrate layer is provided with the composite film layer with a specific structure, one part of the composite film layer plays a role in transmitting lithium ions, and the other part plays a role in protecting the ceramic-based electrolyte. Compared with the existing ceramic-based solid electrolyte, the ceramic-based solid electrolyte prepared by the invention can obtain higher interface ionic conductance, and meanwhile, the aluminum oxide protective layer can enable the electrolyte to have good mechanical property and higher thermal stability.
The composite solid electrolyte can obtain the lithium ion conductivity range of 10 at room temperature-5S/cm～10- 2S/cm, and the composite solid electrolyte has high stability to metal lithium and hasExcellent mechanical performance.
(2) The method combines a coating method and a spraying method, and prepares the composite solid electrolyte (which is a composite inorganic ceramic electrolyte membrane) with excellent performance through a subsequent sintering process.
Drawings
Fig. 1 is a schematic structural view of a composite solid electrolyte material of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The composite solid electrolyte of the present invention will be further described with reference to examples of the present invention, and it will be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
The embodiment provides a composite solid electrolyte material, which comprises a ceramic matrix layer and a composite film layer formed on the surface of the ceramic matrix layer, wherein the ceramic matrix layer is Li1.3Al0.3Ti1.7(PO4)3。
The preparation method of the composite solid electrolyte material comprises the following steps:
(1) preparing 5 wt.% of PVA aqueous solution, adding a certain amount of electrolyte powder with D50 of 0.5 mu m and D90 of 1 mu m into a mortar according to the mass ratio of 95:5 of the electrolyte ceramic powder to the PVA solution, uniformly grinding for 30min, and pressing the ground electrolyte powder under the pressure of 130MPa to prepare a ceramic electrolyte biscuit;
(2) polyacrylic acid was used as a dispersant to prepare a 5 wt.% aqueous solution. alpha-Al with D50 of 2 mu m2O3Preparing slurry with solid content of 10% in a dispersing agent, adjusting the pH value of the solution to 9 by using ammonia water, and then carrying out ultrasonic treatment for 1 h.
Preparing Al on the surface of the ceramic biscuit prepared in the step (1) by using a coating method through the prepared slurry2O3A film. The specific method comprises the following steps: placing the prepared electrolyte sheet in the container with concave holeOn the coating plate, the radius of the concave hole is equal to that of the electrolyte ceramic plate. Then pouring the slurry on a coating plate, uniformly pulling a coating rod at a pulling speed of 15mm/min, and preparing Al on the surface of the electrolyte sheet2O3A film, the thickness of the prepared film is 3 μm;
(3) lithium nitrate is used as lithium salt, polyacrylic acid is used as a dispersing agent, acetone is used as a solvent, and a slurry with the solid content of 5% is prepared, wherein the content of the dispersing agent is 1 wt.%.
Spraying the prepared slurry to the alpha-Al prepared in the previous step by using a spray gun2O3On the coating layer, on alpha-Al2O3A lithium nitrate layer is formed on the surface of the substrate. The specific method comprises the following steps: and (3) using air pressure of 1Mpa, enabling the muzzle of the spray gun to be vertical to the ceramic plate, enabling the muzzle to be 10cm away from the electrolyte plate, enabling the caliber of the spray gun nozzle to be 0.5mm, and preparing a lithium salt layer on the surface of the ceramic plate.
(4) The composite electrolyte prepared in the above step is placed in a drying oven at 100 ℃ for drying for 12 h. Taking out the dried sample, sintering the dried sample in a muffle furnace at 650 ℃ for 12h to form a layer of alpha-Al on the surface of the ceramic electrolyte2O3And LiAlO2Thereby preparing an inorganic composite electrolyte.
Example 2
The embodiment provides a composite solid electrolyte material, which comprises a ceramic matrix layer and a composite film layer formed on the surface of the ceramic matrix layer, wherein the ceramic matrix layer is Li0.5La0.5TiO3。
The preparation method of the composite solid electrolyte material comprises the following steps:
(1) preparing 5 wt.% of PVA aqueous solution, adding a certain amount of electrolyte powder with D50 of 1 μm and D90 of 2 μm into a mortar according to the mass ratio of 95:5 of the electrolyte ceramic powder to the PVA solution, uniformly grinding for 30min, and pressing the ground electrolyte powder into a ceramic electrolyte biscuit under the pressure of 130 MPa;
(2) polyacrylic acid was used as a dispersant to prepare a 5 wt.% aqueous solution. alpha-Al with D50 of 3 mu m2O3Preparing slurry with solid content of 10% in dispersant, and regulating with ammonia waterThe solution was sonicated for 1h after pH 9.
Preparing Al on the surface of the ceramic biscuit prepared in the step (1) by using a coating method through the prepared slurry2O3A film. The specific method comprises the following steps: and (3) placing the prepared electrolyte sheet on a coating plate with concave holes, wherein the radius of the concave holes is equal to that of the electrolyte ceramic sheet. Then pouring the slurry on a coating plate, uniformly pulling a coating rod at a pulling speed of 30mm/min, and preparing Al on the surface of the electrolyte sheet2O3A film, the thickness of the prepared film is 4 μm;
(3) lithium nitrate is used as lithium salt, polyacrylic acid is used as a dispersing agent, acetone is used as a solvent, and a slurry with the solid content of 5% is prepared, wherein the content of the dispersing agent is 1 wt.%.
Spraying the prepared slurry to the alpha-Al prepared in the previous step by using a spray gun2O3On the coating layer, on alpha-Al2O3A lithium nitrate layer is formed on the surface of the substrate. The specific method comprises the following steps: and (3) using air pressure of 1Mpa, enabling the muzzle of the spray gun to be vertical to the ceramic plate, enabling the muzzle to be 10cm away from the electrolyte plate, enabling the caliber of the spray gun nozzle to be 0.5mm, and preparing a lithium salt layer on the surface of the ceramic plate.
(4) The composite electrolyte prepared in the above step is placed in a drying oven at 100 ℃ for drying for 12 h. Taking out the dried sample, sintering the dried sample in a muffle furnace at 680 ℃ for 12h to form a layer of alpha-Al on the surface of the ceramic electrolyte2O3And LiAlO2Thereby preparing an inorganic composite electrolyte.
Example 3
The embodiment provides a composite solid electrolyte material, which comprises a ceramic matrix layer and a composite film layer formed on the surface of the ceramic matrix layer, wherein the ceramic matrix layer is Li1.3Al0.3Ti1.7(PO4)3。
The preparation method of the composite solid electrolyte material comprises the following steps:
(1) preparing 5 wt.% of PVA aqueous solution, adding a certain amount of electrolyte powder with D50 of 0.5 mu m and D90 of 1.5 mu m into a mortar according to the mass ratio of 95:5 of the electrolyte ceramic powder to the PVA solution, uniformly grinding for 30min, and pressing the ground electrolyte powder under the pressure of 130MPa to prepare a ceramic electrolyte biscuit;
(2) polymethacrylic acid was used as a dispersant to prepare a 5 wt.% aqueous solution. alpha-Al with D50 of 2 mu m2O3Preparing slurry with solid content of 10% in a dispersing agent, adjusting the pH value of the solution to 9 by using ammonia water, and then carrying out ultrasonic treatment for 1 h.
Preparing Al on the surface of the ceramic biscuit prepared in the step (1) by using a coating method through the prepared slurry2O3A film. The specific method comprises the following steps: and (3) placing the prepared electrolyte sheet on a coating plate with concave holes, wherein the radius of the concave holes is equal to that of the electrolyte ceramic sheet. Then pouring the slurry on a coating plate, uniformly pulling a coating rod at a pulling speed of 50mm/min, and preparing Al on the surface of the electrolyte sheet2O3A film, the thickness of the prepared film is 5 μm;
(3) lithium carbonate is used as lithium salt, polyacrylic acid is used as a dispersing agent, ethanol is used as a solvent, and a slurry with the solid content of 5% is prepared, wherein the content of the dispersing agent is 3 wt.%.
Spraying the prepared slurry to the alpha-Al prepared in the previous step by using a spray gun2O3On the coating layer, on alpha-Al2O3A lithium carbonate layer is formed on the surface of the substrate. The specific method comprises the following steps: and (3) using air pressure of 1Mpa, enabling the muzzle of the spray gun to be vertical to the ceramic plate, enabling the muzzle to be 15cm away from the electrolyte plate, enabling the caliber of the spray gun nozzle to be 0.5mm, and preparing a lithium salt layer on the surface of the ceramic plate.
(4) The composite electrolyte prepared in the above step is placed in a drying oven at 100 ℃ for drying for 12 h. Taking out the dried sample, sintering the dried sample in a muffle furnace at 750 ℃ for 12h to form a layer of alpha-Al on the surface of the ceramic electrolyte2O3And LiAlO2Thereby preparing an inorganic composite electrolyte.
Example 4
The embodiment provides a composite solid electrolyte material, which comprises a ceramic matrix layer and a composite film layer formed on the surface of the ceramic matrix layer, wherein the ceramic matrix layer is Li1.3Al0.3Ti1.7(PO4)3。
The preparation method of the composite solid electrolyte material comprises the following steps:
(1) preparing 5 wt.% of PVA aqueous solution, adding a certain amount of electrolyte powder with D50 of 0.5 mu m and D90 of 2 mu m into a mortar according to the mass ratio of 95:5 of the electrolyte ceramic powder to the PVA solution, uniformly grinding for 30min, and pressing the ground electrolyte powder under the pressure of 100MPa to prepare a ceramic electrolyte biscuit;
(2) polymethacrylic acid was used as a dispersant to prepare a 3 wt.% aqueous solution. alpha-Al with D50 of 3 mu m2O3Preparing slurry with the solid content of 15% in a dispersing agent, adjusting the pH value of the solution to 9 by using ammonia water, and then carrying out ultrasonic treatment for 1.5 h.
Preparing Al on the surface of the ceramic biscuit prepared in the step (1) by using a coating method through the prepared slurry2O3A film. The specific method comprises the following steps: and (3) placing the prepared electrolyte sheet on a coating plate with concave holes, wherein the radius of the concave holes is equal to that of the electrolyte ceramic sheet. Then pouring the slurry on a coating plate, uniformly pulling a coating rod at a pulling speed of 40mm/min, and preparing Al on the surface of the electrolyte sheet2O3A film, the thickness of the prepared film is 6 μm;
(3) lithium carbonate is used as lithium salt, polyacrylic acid is used as a dispersing agent, ethanol is used as a solvent, and a slurry with the solid content of 5% is prepared, wherein the content of the dispersing agent is 3 wt.%.
Spraying the prepared slurry to the alpha-Al prepared in the previous step by using a spray gun2O3On the coating layer, on alpha-Al2O3A lithium carbonate layer is formed on the surface of the substrate. The specific method comprises the following steps: and (3) using air pressure of 1Mpa, enabling the muzzle of the spray gun to be vertical to the ceramic plate, enabling the muzzle to be 15cm away from the electrolyte plate, enabling the caliber of the spray gun nozzle to be 0.5mm, and preparing a lithium salt layer on the surface of the ceramic plate.
(4) The composite electrolyte prepared in the above step is placed in a drying oven at 100 ℃ for drying for 12 h. Taking out the dried sample, sintering the dried sample in a muffle furnace at 750 ℃ for 12h to form a layer of alpha-Al on the surface of the ceramic electrolyte2O3And LiAlO2Thereby preparing an inorganic composite electrolyte.
Example 5
The preparation method and conditions were the same as those of example 1 except that no dispersant was added in step (2) and step (3).
Example 6
The procedure and conditions were the same as in example 2 except that the solid content in step (2) was adjusted from 10% to 30%.
Example 7
The procedure and conditions were the same as in example 1 except that the solid content in step (3) was adjusted from 5% to 20%.
Comparative example 1
This example provides a solid electrolyte with a ceramic matrix layer of Li1.3Al0.3Ti1.7(PO4)3。
The preparation method of the solid electrolyte comprises the following steps:
(1) preparing 5 wt.% PVA aqueous solution, taking a certain amount of electrolyte powder with the grain diameter D50 of 0.5 mu m, adding the electrolyte powder and the PVA solution into a mortar according to the mass ratio of 95:5, and uniformly grinding for 30 min. Pressing the grinded electrolyte powder under the pressure of 130MPa to prepare a ceramic electrolyte biscuit;
(2) the dried sample was taken out and sintered at 650 ℃ for 12 hours in a muffle furnace to prepare a solid electrolyte.
Comparative example 2
This example provides a solid electrolyte with a ceramic matrix layer of Li0.5La0.5TiO3。
The preparation method comprises the following steps of:
the preparation method of the solid electrolyte comprises the following steps:
(1) preparing 5 wt.% of PVA aqueous solution, taking a certain amount of electrolyte powder with the diameter of 1 mu m, adding the electrolyte powder and the PVA aqueous solution into a mortar according to the mass ratio of 90:10, and uniformly grinding for 30 min. Pressing the grinded electrolyte powder under the pressure of 100MPa to prepare a ceramic electrolyte biscuit;
(2) the dried sample was taken out and sintered at 850 ℃ for 10 hours in a muffle furnace to prepare a solid electrolyte.
Comparative example 3
The method and conditions were the same as in example 1 except that the sintering temperature in step (3) was adjusted to 1200 ℃.
The solid electrolyte materials prepared in examples 1 to 7 and comparative examples 1 to 3 were tested for room temperature (25 ℃) ionic conductivity and mechanical strength and thickness of the composite membrane. The method of test characterization is as follows:
ionic conductivity: the test conditions were room temperature (25 ℃ C.), and the ionic conductivity was measured using an electrochemical AC impedance method.
Mechanical strength: the ceramic electrolyte sheet prepared by sintering is subjected to a mechanical strength test on the ceramic material by using a strength tester of an XLS205 type, and the mechanical strength is characterized by a formula F ═ P/V, wherein F is the mechanical strength of the electrolyte sheet, P is the maximum breaking load, and V is the volume of the electrolyte sheet.
Thickness of the composite film: measured using a scanning electron microscope.
The test results are shown in table 1.
TABLE 1 data for each example and comparative example
Figure BDA0002336309450000181
From the above data analysis it can be seen that:
the thicker the thickness of the composite thin film is, the more unfavorable the improvement of the lithium ion conductivity is. And the increase of the solid content of the aluminum oxide in the composite membrane can increase the thickness of the aluminum oxide film, improve the damage resistance of the material and be not beneficial to the transmission of lithium ions.
Secondly, the thickness of the thin film obtained by the samples sintered at different temperatures is different, which indicates that the aluminum oxide layer and the lithium salt layer participate in the reaction during the sintering process in the later sintering process, and a non-base electrolyte layer (LiAlO) is generated2)。
Comparing the analysis examples and the comparative examples, the electrolyte having the composite thin film layer not only improves the ionic conductivity, but also improves the mechanical properties of the material, thus being able to resist the penetration of lithium dendrites and obtaining higher mechanical properties.
The main steps and main parameters of the invention are described above, but the invention is not limited to the above steps and the materials used, the core of the patent protection is to combine coating and spraying to prepare the composite solid electrolyte material, and the method for improving and reprocessing on the steps is also in the scope of the patent protection right.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The composite solid electrolyte material is characterized by comprising a first layer, a second layer and a third layer which are sequentially stacked, wherein the first layer is a ceramic matrix layer, the second layer and the third layer form a composite membrane layer, and the second layer is an electrolyte conductor wrapped with Al2O3A composite layer formed by particles, and the third layer is an electrolyte conductor layer.
2. The composite solid state electrolyte material of claim 1, wherein the composite film layer is formed by Al2O3Particles are formed by reaction with a lithium salt;
preferably, the thickness of the composite film layer is 0.1-50 μm, preferably 1-10 μm;
preferably, the electrolyte conductor is LiAlO2。
3. The composite solid state electrolyte material of claim 1 or 2, wherein the ceramic matrix layer is a solid fast ion ceramic matrix layer, chemically composed as a lithium ion conductor solid state electrolyte, preferably comprising: an NASICON-structured electrolyte and/or a perovskite-structured electrolyte;
preferably, the electrolyte of NASICON structure has a chemical composition of Li1+xAxB2-x(MO4)3Wherein x ranges from 0.05 to 0.7, A comprises any 1 or combination of at least 2 of Al, Ga, Sc, Y, Ca, Sr, Zn, Si, In, Lu, La, Fe or Cr, B comprises Ti and/or Ge, and M comprises P and/or Si;
preferably, the chemical composition of the perovskite-structured electrolyte is Li3xM1/3-2xLa2/3-xNO3Wherein x ranges from 0.01 to 0.17, M comprises any 1 or the combination of at least 2 of Ca, Sr, Zn, Mg, Al, Sc, Y, In or Cr, and N comprises any one or two of Ti or Ge;
preferably, the lithium ion conductor solid electrolyte D50 is 0.1-10 μm, and D90 is 0.2-20 μm;
preferably, the lithium ion conductor solid electrolyte is Li with D50 of 2-3 μm and D90 of 1-10 μm1.3Al0.3Ti1.7(PO4)3And Li0.5La0.5TiO3；
Preferably, the Al2O3The chemical composition of the particles comprises alpha-Al2O3、β-Al2O3Or gamma-Al2O3Any one or a combination of at least 2 of (1), preferably alpha-Al2O3；
Preferably, the Al2O3The particle size D50 of the particles is 1-50 μm;
preferably, the Al2O3The particles are alpha-Al with the particle size D50 of 2-10 mu m2O3。
4. A method for producing the composite solid electrolyte material according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) preparing a ceramic matrix biscuit by adopting electrolyte powder through a molding process;
(2) preparation of a composition containing Al2O3By a coating process, applying the slurry to the slurry of step (1)Al is formed on the surface of the ceramic body2O3A layer;
(3) preparing lithium salt-containing slurry, and spraying the Al in the step (2)2O3Forming a lithium salt layer on the surface of the layer;
(4) and sintering to obtain the composite solid electrolyte material.
5. The method of claim 4, wherein the forming process of step (1) comprises any 1 of cold isostatic pressing, casting or calendering, preferably cold isostatic pressing;
preferably, the ceramic matrix biscuit is prepared by a cold isostatic pressing method in the step (1), and the pressure of a pressed sheet is controlled to be 50-150 MPa;
preferably, the D50 of the electrolyte powder in the step (1) is 0.1-10 μm, and the D90 is 0.2-20 μm;
preferably, the ceramic matrix biscuit prepared in the step (1) by adopting a cold isostatic pressing method has the diameter of preferably 2-15 mm and the thickness of preferably 1-5 mm;
preferably, the ceramic matrix biscuit of step (1) is a solid fast ion ceramic matrix biscuit.
6. The method according to claim 4 or 5, wherein the Al in step (2)2O3Comprises alpha-Al2O3、β-Al2O3Or gamma-Al2O3Any one or a combination of at least 1 and preferably alpha-Al2O3；
Preferably, Al in the step (2)2O3The particle diameter D50 is 1-50 μm, preferably 1-2 μm;
preferably, Al in the step (2)2O3alpha-Al having a particle size D50 of 1 to 2 μm2O3；
Preferably, Al in the step (2)2O3Is smaller than the particle size of the electrolyte powder;
preferably, the solvent used for preparing the slurry in step (2) comprises any 1 or a combination of at least 2 of deionized water, methanol, ethanol, isopropanol, acetone, butanone or trichloroethylene, preferably deionized water;
preferably, Al prepared by coating as described in step (2)2O3The thickness of the layer is 1 to 8 μm, and more preferably 1 to 5 μm;
preferably, the slurry in step (2) is formulated with a dispersant, wherein the dispersant comprises any 1 or at least 2 of polyethylene glycol, polymethacrylic acid, polyacrylic acid, acrylic acid-acrylate copolymer or polyvinylpyrrolidone;
preferably, the dispersant is contained in an amount of 0.5 to 10 wt.%, preferably 2 to 6 wt.%, based on 100 wt.% of the total mass of the slurry in the step (2);
preferably, the solid content of the slurry in the step (2) is 5-30%, and preferably 10-15%.
7. The method of any one of claims 4 to 6, wherein the lithium salt of step (3) comprises any 1 or a combination of at least 2 of lithium carbonate, lithium nitrate, lithium oxalate, lithium acetate, or lithium citrate;
preferably, the solvent used in the slurry preparation in step (3) comprises any 1 or a combination of at least 2 of deionized water, methanol, ethanol, isopropanol or butanone, preferably acetone;
preferably, the slurry in step (3) is prepared by further comprising a dispersant, wherein the dispersant comprises any 1 or at least 2 of polyethylene glycol, polymethacrylic acid, polyacrylic acid, acrylic acid-acrylate copolymer or polyvinylpyrrolidone;
preferably, the dispersant is contained in an amount of 0.5 to 8 wt.%, preferably 3 to 5 wt.%, based on 100 wt.% of the total mass of the slurry in the step (3);
preferably, the solid content of the slurry in the step (3) is 0.1-50%, preferably 5-13%;
preferably, the thickness of the lithium salt layer in the step (3) is 1-3 μm, and preferably 1-2 μm.
8. The method according to any one of claims 4 to 7, wherein the apparatus used in the sintering in step (4) comprises any 1 or a combination of at least 2 of a muffle furnace, a tube furnace, a box furnace or a rotary furnace;
preferably, the sintering temperature in the step (4) is 600-900 ℃;
preferably, the sintering time in the step (4) is 3-12 h;
preferably, the heating rate of heating to the sintering temperature is 1-10 ℃/min;
preferably, the atmosphere for sintering in step (4) is any 1 or a combination of at least 2 of air, oxygen, nitrogen, helium or neon;
preferably, the method further comprises a step of drying after step (3) and before step (4).
9. Method according to any of claims 4-8, characterized in that the method comprises the steps of:
(1) preparing a PVA aqueous solution, adding electrolyte powder, grinding, and pressing the ground electrolyte powder into a ceramic matrix biscuit by adopting a cold isostatic pressing method under the pressure of 50-150 MPa;
(2) polyacrylic acid is used as a dispersing agent to prepare an aqueous solution. Taking alpha-Al with D50 of 1-2 mu m2O3Preparing slurry with the solid content of 10-30% in the aqueous solution, adjusting the pH value of the solution to 8-9 by using ammonia water, and coating the prepared slurry on the surface of the ceramic biscuit prepared in the step (1) by using a coating method;
(3) lithium salt, a dispersing agent and acetone are adopted to prepare slurry with the solid content of 5-13%, wherein the dispersing agent is polyacrylic acid, the content of the polyacrylic acid accounts for 1 wt% of the slurry, and the prepared slurry is sprayed to the alpha-Al prepared in the step (2) by using a spray gun2O3On the coating layer, on alpha-Al2O3A layer of lithium salt is formed on the surface of the lithium ion battery;
(4) sintering the composite electrolyte prepared in the step (3) for 3-12 hours at the temperature of 600-900 ℃, and forming a layer of alpha-Al on the surface of the ceramic electrolyte2O3And LiAlO2Composite layer ofAnd preparing the composite solid electrolyte material.
10. A lithium ion battery comprising the composite solid state electrolyte material of any one of claims 1-3;
preferably, the lithium ion battery is a lithium ion all-solid-state battery;
preferably, the lithium ion battery uses metal lithium as a negative electrode.
CN201911357394.5A 2019-12-25 2019-12-25 Composite solid electrolyte material, preparation method thereof and application thereof in lithium ion battery Pending CN113036213A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113725486A (en) * 2021-08-30 2021-11-30 慈溪斯昂尼电池有限公司 Flame-retardant explosion-proof solid battery with stable polymer and ceramic electrolyte components
CN114512711A (en) * 2022-04-18 2022-05-17 北京卫蓝新能源科技有限公司 Inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for battery and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113725486A (en) * 2021-08-30 2021-11-30 慈溪斯昂尼电池有限公司 Flame-retardant explosion-proof solid battery with stable polymer and ceramic electrolyte components
CN114512711A (en) * 2022-04-18 2022-05-17 北京卫蓝新能源科技有限公司 Inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for battery and preparation method thereof

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