CN115799612A - Double-layer oxide solid electrolyte and preparation method and application thereof - Google Patents

Double-layer oxide solid electrolyte and preparation method and application thereof Download PDF

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CN115799612A
CN115799612A CN202211266893.5A CN202211266893A CN115799612A CN 115799612 A CN115799612 A CN 115799612A CN 202211266893 A CN202211266893 A CN 202211266893A CN 115799612 A CN115799612 A CN 115799612A
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solid electrolyte
oxide solid
garnet
thin layer
double
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李亚迪
胡恒广
刘文渊
王博
张广涛
闫冬成
郝艺
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Tunghsu Technology Group Co Ltd
Hebei Guangxing Semiconductor Technology Co Ltd
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Tunghsu Technology Group Co Ltd
Hebei Guangxing Semiconductor Technology Co Ltd
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Abstract

The invention relates to the technical field of electrolytes, and discloses a preparation method of a double-layer oxide solid electrolyte. The preparation method comprises the following steps: calcining a precursor powder of garnet-type oxide solid electrolyte B in a state of being in contact with one side of a thin sheet of solid electrolyte a to obtain a double-layer oxide solid electrolyte containing a thin layer of solid electrolyte a and a thin layer of garnet-type oxide solid electrolyte B; the solid electrolyte A is selected from at least one of NASICON structure oxide solid electrolyte, LISICON structure oxide solid electrolyte and perovskite structure oxide solid electrolyte. The electrolyte prepared by the preparation method can effectively prevent the LATP from being reduced by lithium metal, and the method is simple and has higher production efficiency.

Description

Double-layer oxide solid electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a double-layer oxide solid electrolyte and a preparation method and application thereof.
Background
As a clean energy storage device with high energy density, a lithium ion battery has been widely used in the fields of various portable electronic products, electric vehicles, power grid energy storage, and the like. Most of the lithium ion batteries used today are made of graphite (specific capacity 372mAh g) -1 ) For the negative electrode, the energy storage material with higher energy density is urgently sought because the lower energy density of the material can not meet the social demand more and more.
Meanwhile, with the wide use of lithium ion batteries, the safety accidents such as fire, explosion and the like of various products such as mobile phones and electric vehicles due to battery reasons are increasing, and the safety problem becomes a main factor restricting the further application of the lithium ion batteries. The main liquid electrolyte of the current lithium ion battery contains a large amount of organic solvents, and the main liquid electrolyte is easy to burn and ignite at a high temperature and is easy to cause accidents such as liquid leakage and the like, so that the main liquid electrolyte is an important factor of potential safety hazards of the lithium ion battery.
Lithium metal has been attracting attention as a negative electrode material for lithium secondary batteries having high energy density due to its extremely high theoretical specific capacity (3860 mAh g) -1 ) Lowest redox equilibrium potential (-3.04V relative to standard hydrogen electrode) and relatively low density (0.534 g-cm) -3 ) Considered to be one of the most promising anode materials. However, when the electrolyte is matched with a liquid electrolyte, dendritic crystals are generated in the circulation process, and the dendritic crystals grow continuously, so that short circuit and even explosion inside the battery are easily caused. The presence of dendrites also causes a sharp increase in the surface of the lithium electrode, which greatly accelerates the reaction of lithium with the electrolyte, consumes lithium and reduces the electrode capacity, and also reduces the cyclic coulombic efficiency. Therefore, the matching of the organic electrolyte and the lithium metal cathode has great potential safety hazard.
The solid electrolyte adopted by the solid battery has the advantages of high safety, high energy density, excellent high-temperature performance and the like. It has high strength to prevent penetration of lithium dendrites and can be matched with a lithium metal negative electrode with higher energy density. Meanwhile, the safety valve has the characteristics of non-volatility, no leakage and non-flammability, radically avoids the possibility of burning and has high safety performance.
Therefore, the solid electrolyte is a core component of the solid battery, and is mainly classified into a polymer electrolyte, a sulfide electrolyte, and an oxide electrolyte. The polymer electrolyte has the advantages of easy processing and good elasticity, but the ionic conductivity is low, the operation temperature is high, and the chemical window is narrow; sulfide electrolytes, although having high ionic conductivity, are sensitive to air, are easily oxidized, and readily react with water to produce H 2 S, the requirement on the production environment is strict; the oxide electrolyte has high ionic conductivity, high chemical stability and excellent comprehensive performance, and is widely concerned.
The oxide solid electrolyte is mainly classified into a LiPON thin film, a NaSICON type structure, a LISICON type structure, a Perovskite (Perovskite) type structure, a Garnet (Garnet) type structure, and the like. Wherein the NaSICON type has the advantages of high ionic conductivity, abundant raw material source and low cost, such as lithium aluminum titanium phosphate (Li) 1+x Al x Ti 2-x( PO 4 ) 3 I.e. LATP), lithium aluminum germanium phosphate (Li) 1+x Al x Ge 2-x( PO 4 ) 3 I.e., LAGP), etc. However, in the presence of a process in the battery, ti in LATP 4+ And Ge in LAGP 4+ And Li 3x La 2/3-x TiO 3 Ti of (1) 4+ The electrochemical properties are unstable and affect the stability of the entire battery. Therefore, the surface of the material needs to be treated for application.
CN113140784A discloses a modified solid electrolyte, and a preparation method and an application thereof, wherein an evaporation-grade lithium salt is plated on the surface of an oxide electrolyte sheet by a vacuum evaporation method to form an interface protection layer, and the protection layer has good chemical and electrochemical stability to lithium metal, and improves the stability to lithium. However, the patent adds an additional vacuum evaporation step in the normal production process, which reduces the production efficiency.
Disclosure of Invention
The invention aims to solve the problems that LATP is easy to be reduced by lithium metal and an interface protection layer is low in production efficiency in the prior art, and provides a double-layer oxide solid electrolyte, a preparation method and application thereof.
In order to achieve the above object, an aspect of the present invention provides a method for preparing a double-layered oxide solid electrolyte, the method comprising the steps of:
calcining the precursor powder of the garnet-type oxide solid electrolyte B in a state of being in contact with one side of the thin sheet of the solid electrolyte a to obtain a double-layer oxide solid electrolyte containing a thin layer of the solid electrolyte a and a thin layer of the garnet-type oxide solid electrolyte B;
wherein the solid electrolyte A is at least one selected from NASICON structure oxide solid electrolyte, LISICON structure oxide solid electrolyte and perovskite structure oxide solid electrolyte.
Preferably, the NASICON structure oxide solid electrolyte is Li 1+x M x N 2-x( PO 4 ) 3 The oxide solid electrolyte with the LISICON structure is Li 4-y Ge 1-y P y S 4 The perovskite structure oxide solid electrolyte is Li 3z La 2/3- z TiO 3 ；
Wherein M is Al, cr, ga, fe, sc, in, lu, Y or La, N is Ti or Ge, x is more than or equal to 0.2 and less than or equal to 0.6, Y is more than or equal to 0.4 and less than or equal to 0.6, and z is more than 0.04 and less than or equal to 0.17.
Further preferably, the solid electrolyte a is selected from Li 1+x Al x Ti 2-x( PO 4 ) 3 、Li 1+x Al x Ge 2-x( PO 4 ) 3 And Li 3z La 2/3-z TiO 3 At least one of (1).
Preferably, the precursor powder of the garnet-type oxide solid electrolyte B contains Li 2 CO 3 、La 2 O 3 And ZrO 2 ；
The Li 2 CO 3 、La 2 O 3 And ZrO 2 The molar ratio of (A) is 1.
Further preferably, the garnet-type oxide solid electrolyte B is Li 7 La 3 Zr 2 O 12 。
Preferably, the conditions of the calcination include: the temperature is 500-1200 ℃ and the time is 2-60 h.
Further preferably, the conditions of the calcination include: the temperature is 800-1200 ℃, and the time is 8-15 h.
Preferably, the preparation method further comprises polishing the thin layer of garnet-type oxide solid electrolyte B in the double-layer oxide solid electrolyte.
Preferably, the ratio of the thickness of the thin layer of the solid electrolyte a to the thickness of the thin layer of the garnet-type oxide solid electrolyte B is 1000.
Further preferably, the thickness ratio of the thin layer of the solid electrolyte a and the thin layer of the garnet-type oxide solid electrolyte B is 1000.
Preferably, the thickness of the thin layer of garnet-type oxide solid electrolyte B is 1 μm to 50 μm, and the thickness of the thin layer of solid electrolyte A is 0.5mm to 3mm.
In a second aspect, the present invention provides a double-layered oxide solid electrolyte prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a lithium ion battery, which includes the double-layer oxide solid electrolyte described in the second aspect, a lithium battery positive electrode plate, and a lithium battery negative electrode plate, wherein a thin layer of solid electrolyte a in the double-layer oxide solid electrolyte is disposed toward the lithium battery positive electrode plate, and a thin layer of garnet-type oxide solid electrolyte B in the oxide solid electrolyte is disposed toward the lithium ion negative electrode plate.
According to the invention, at least one slice of NASICON structure oxide solid electrolyte, LISICON structure oxide solid electrolyte and perovskite structure oxide solid electrolyte is used as a solid electrolyte A slice, and then mixed precursor powder of garnet type oxide solid electrolyte B is laid on one side of the solid electrolyte A slice, so that the solid electrolyte A thin layer structure of the obtained double-layer oxide solid electrolyte can be more compact after calcination, the chemical stability of the solid electrolyte A can be improved, and the solid electrolyte A is prevented from being in direct contact with a lithium battery cathode material, and further the charge and discharge stability of the lithium battery is effectively improved. Moreover, the preparation method of the oxide solid electrolyte has simpler and more convenient steps. In addition, the solid electrolyte has lower preparation cost.
Drawings
FIG. 1 is a schematic diagram of a lithium ion battery according to the present invention;
fig. 2 is a graph showing cycle performance tests of the solid electrolytes prepared in example 1 of the present invention and comparative example 1 applied to a lithium ion battery.
Reference numerals
11 a thin layer of solid electrolyte a; a thin layer of 12 garnet-type oxide solid electrolyte B; 2, a positive electrode plate of the lithium battery; and 3, a negative pole plate of the lithium battery.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
According to the present invention, there is provided in a first aspect a method for producing a double-layer oxide solid electrolyte, comprising the steps of:
calcining a precursor powder of garnet-type oxide solid electrolyte B in a state of being in contact with one side of a thin sheet of solid electrolyte a to obtain a double-layer oxide solid electrolyte containing a thin layer of solid electrolyte a and a thin layer of garnet-type oxide solid electrolyte B;
wherein the solid electrolyte A is selected from at least one of NASICON structure oxide solid electrolyte, LISICON structure oxide solid electrolyte and perovskite structure oxide solid electrolyte.
Specifically, the solid electrolyte a sheet may be obtained by purchase or may be prepared, and preferably, the solid electrolyte a sheet is prepared by a sheet preparation method disclosed in the prior art, for example, by die tableting. The conditions for tableting can be determined as appropriate by the person skilled in the art. Preferably, the tabletting conditions include: the pressure intensity is 100-300MPa, and specifically can be 100MPa, 150MPa, 200MPa, 250MPa, 300MPa, or any value between the above values; the time is 1-30min, specifically 1min, 5min, 10min, 15min, 20min, 25min, 30min, or any value therebetween. The tabletting time is preferably 5-15min.
In the present invention, the precursor powder of garnet-type oxide solid electrolyte B may be contacted with one side of the solid electrolyte a flake in any feasible manner, such as: the precursor powder of garnet-type oxide solid electrolyte B can be laid in a container, and then the solid electrolyte A flake is added on the powder; or the precursor powder of the garnet-type oxide solid electrolyte B is directly laid on one side surface of the sheet of the solid electrolyte a.
In the research process of the inventor, the inventor finds that the solid electrolyte A thin layer structure of the double-layer oxide solid electrolyte can be more compact after the solid electrolyte A thin layer structure is calcined under the condition that precursor powder of mixed garnet-type oxide solid electrolyte B is in contact with one side of the solid electrolyte A thin layer, the chemical stability of the solid electrolyte A can be improved, meanwhile, the solid electrolyte A can be prevented from being in direct contact with a lithium battery cathode material, and further, the charging and discharging stability of the lithium battery can be effectively improved. Moreover, the double-layer oxide solid electrolyte only needs one-step calcination, the preparation method has simpler and more convenient steps, and the preparation cost can be reduced. In addition, the double-layer electrolyte takes the solid electrolyte A as a substrate, and the garnet-type oxide solid electrolyte B is arranged on the solid electrolyte A, so that the using amount of the garnet-type oxide solid electrolyte B is effectively reduced, and the preparation cost of the solid electrolyte is further reduced.
The NASICON structure oxide solid electrolyte contains Ti or Ge and has a structure of MO 6 Octahedron and PO 4 The tetrahedra share an angle to form [ M 2 (PO 4 ) 3 ]A rigid structure. From the viewpoint of further improving the performance of a battery to which the solid electrolyte is applied, it is preferable that the NASICON-structure oxide solid electrolyte is Li 1+x M x N 2-x( PO 4 ) 3 Wherein M is Al, cr, ga, fe, sc, in, lu, Y or La, N is Ti or Ge, x is more than or equal to 0.2 and less than or equal to 0.6, and x can be 0.2, 0.3, 0.4, 0.5, 0.6 or any value In between. Preferably, M is Al or La. The solid-state electrolyte of the oxide with the LISICON structure is Li 3+n Y 1-n X n O 4 Or other oxide solid electrolytes containing a LISICON structure, wherein X is P, as, V or Cr, and Y is Ti or Ge. From the viewpoint of further improving the performance of a battery to which the solid electrolyte is applied, it is preferable that the LISICON-structure oxide solid electrolyte is Li 4-y Ge 1-y P y S 4 0.4. Ltoreq. Y.ltoreq.0.6, further preferably y =0.4 or y =0.6. The perovskite-type structure oxide solid-state electrolyte may be an oxide solid-state electrolyte having a perovskite-type structure disclosed in the prior art. From the viewpoint of further improving the performance of a battery to which the solid electrolyte is applied, it is preferable that the perovskite-type structure oxide solid electrolyte Li 3z La 2/3-z TiO 3 ，0.04＜z＜0.17。
Preferably, the solid electrolyte A is selected from Li 1+x Al x Ti 2-x( PO 4 ) 3 、Li 1+x Al x Ge 2-x( PO 4 ) 3 And Li 3z La 2/3- x TiO 3 At least one of (a). By adopting the solid electrolyte A as the solid electrolyte A, the electrical performance of the battery with the solid electrolyte can be effectively improved.
Further preferably, the solid electrolyte a is selected from Li 1.3 Al 0.3 Ti 1.7( PO 4 ) 3 、Li 1.3 Al 0.3 Ge 1.7( PO 4 ) 3 、Li 1.4 Al 0.4 Ti 1.6( PO 4 ) 3 And Li 1.4 Al 0.4 Ge 1.6( PO 4 ) 3 At least one of (1).
The precursor powder of the garnet-type oxide solid electrolyte B may be any powder mixture capable of forming a garnet-type oxide solid electrolyte by calcination. Preferably, the precursor powder of the garnet-type oxide solid electrolyte B contains Li 2 CO 3 、La 2 O 3 And ZrO 2 (ii) a The Li 2 CO 3 、La 2 O 3 And ZrO 2 The molar ratio of (A) is 1. Li in the above molar ratio 2 CO 3 、La 2 O 3 And ZrO 2 The mixed powder can effectively improve the stability of the battery with the double-layer solid electrolyte and prolong the service life of the battery. From the viewpoint of further improving the stability of the battery having the double-layer solid electrolyte, it is preferable that the garnet-type oxide solid electrolyte B is Li 7 La 3 Zr 2 O 12 。
The temperature and time of the calcination can be determined by those skilled in the art as the case may be. Preferably, the conditions of the calcination include: the temperature is 500-1200 ℃ and the time is 2-60 h. Under this calcination condition, the solid electrolyte a and the garnet-type oxide solid electrolyte B are more tightly bonded, and the compactness of the solid electrolyte a can be significantly improved. The conditions of the calcination include, in view of further improving the compactness of the solid electrolyte a and the effect of combining the solid electrolyte a and the garnet-type oxide solid electrolyte B: the temperature is 800-1200 ℃, and the time is 8-15 h.
Preferably, the preparation method further comprises polishing the thin layer of garnet-type oxide solid electrolyte B in the double-layer oxide solid electrolyte. The garnet type oxide solid electrolyte B thin layer formed by calcination is polished to be flat, so that the contact between the double-layer oxide solid electrolyte and the battery can be more tight during battery preparation, and the electrical property and the stability of the battery are further improved.
Preferably, the ratio of the thickness of the thin layer of the solid electrolyte a to the thickness of the thin layer of the garnet-type oxide solid electrolyte B is 1000. Under the condition of the thickness ratio, the electrical performance of the battery with the double-layer solid electrolyte can be improved, the stability of the battery can be improved, and the service life of the battery can be prolonged. From the viewpoint of further improving the electrical properties of the battery and extending the service life of the battery, it is preferable that the thickness ratio of the thin layer of the solid electrolyte a and the thin layer of the garnet-type oxide solid electrolyte B is 1000. More preferably, the thickness of the thin layer of garnet-type oxide solid electrolyte B is 1 μm to 50 μm. Specifically, the thickness may be 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or any value between the foregoing values. Under the condition, the damage rate of the double-layer solid electrolyte can be reduced while the cost is reduced, and the stability of the battery in the using process is further improved. Preferably, the thickness of the thin layer of solid electrolyte a is 0.5-3mm. Specifically, it may be 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm or any value therebetween. The double-layer solid electrolyte under the condition has better electrical property.
In a second aspect, the present invention provides a double-layered oxide solid electrolyte prepared by the method of the first aspect. The double-layer oxide solid electrolyte can be applied to a lithium ion battery, and the service life of the battery can be effectively prolonged.
In a third aspect, the present invention provides a lithium ion battery, referring to fig. 1, comprising the double-layer oxide solid electrolyte of the second aspect, a lithium battery positive electrode plate 2 and a lithium battery negative electrode plate 3, wherein a thin layer 11 of the solid electrolyte a in the double-layer oxide solid electrolyte is disposed toward the lithium battery positive electrode plate 2, and a thin layer 12 of the garnet-type oxide solid electrolyte B in the oxide solid electrolyte is disposed toward the lithium ion negative electrode plate 3. The lithium ion battery has a long service life.
According to a particularly preferred embodiment of the present invention, there is provided a method for producing a double-layer oxide solid electrolyte, the method comprising the steps of:
(1) Pressing the solid electrolyte A powder under 100-300MPa for 1-30min to obtain solid electrolyte A sheet with thickness of 0.5-3 mm;
(2) Mixing Li 2 CO 3 、La 2 O 3 And ZrO 2 Uniformly mixing the materials according to a molar ratio of 1:0.2-0.8, paving the mixture on one side of a solid electrolyte A thin sheet, calcining the mixture for 8-15 h at the temperature of 800-1200 ℃ to obtain a double-layer oxide solid electrolyte containing a solid electrolyte A thin layer and a garnet-type oxide solid electrolyte B thin layer, and polishing the garnet-type oxide solid electrolyte B thin layer in the double-layer oxide solid electrolyte to enable the thickness of the garnet-type oxide solid electrolyte B thin layer to be 1-50 mu m;
wherein the thickness ratio of the thin layer of the solid electrolyte A to the thin layer of the garnet-type oxide solid electrolyte B is 1000:10-30 parts of; the solid electrolyte A is selected from Li 1+x Al x Ti 2-x( PO 4 ) 3 、Li 1+x Al x Ge 2-x( PO 4 ) 3 And Li 3z La 2/3-z TiO 3 X is more than or equal to 0.2 and less than or equal to 0.6, and z is more than 0.04 and less than 0.17.
The double-layered oxide solid electrolyte prepared according to the above preferred embodiment can prevent reduction of titanium ions and germanium ions in the solid electrolyte a, and improve and thus improve the stability of a battery having the double-layered oxide solid electrolyte.
The present invention will be described in detail below by way of examples.
Wherein, li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 、Li 0.14 La 0.62 TiO 3 、Li 0.11 La 0.63 TiO 3 、Li 7 La 3 Zr 2 O 12 、Li 2 CO 3 、La 2 O 3 And ZrO 2 Lithium cobaltate, conductive agent Super P and binder PVDF are all purchased products.
Example 1
(1) Mixing solid electrolyte A powder (Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) Pressing under 200MPa for 5min to obtain solid electrolyte A sheet with diameter of 16mm and thickness of 1 mm;
(2) Mixing Li 2 CO 3 、La 2 O 3 And ZrO 2 According to a molar ratio of 7:3: and 4, uniformly mixing, paving on one side of the solid electrolyte A thin layer, heating to 950 ℃ at the speed of 5 ℃/min, calcining for 12 hours at the temperature, cooling to obtain a double-layer oxide solid electrolyte containing a solid electrolyte A thin layer and a garnet-type oxide solid electrolyte B thin layer, and polishing the garnet-type oxide solid electrolyte B thin layer in the double-layer oxide solid electrolyte to enable the thickness of the garnet-type oxide solid electrolyte B thin layer to be 20 microns.
Example 2
(1) Mixing solid electrolyte A powder (Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) Pressing under 100MPa for 20min to obtain solid electrolyte A sheet with diameter of 16mm and thickness of 3 mm;
(2) Mixing Li 2 CO 3 、La 2 O 3 And ZrO 2 According to a molar ratio of 7:4:1 spreading on solid electrolyte A sheet after mixing uniformlyAnd heating to 600 ℃ at the speed of 5 ℃/min, calcining for 20h at the temperature, cooling to obtain a double-layer oxide solid electrolyte containing a thin layer of a solid electrolyte A and a thin layer of a garnet-type oxide solid electrolyte B, and polishing the thin layer of the garnet-type oxide solid electrolyte B in the double-layer oxide solid electrolyte to enable the thickness of the garnet-type oxide solid electrolyte B to be 50 microns.
Example 3
(1) Mixing solid electrolyte A powder (Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) Pressing under 300MPa for 2min to obtain solid electrolyte A sheet with diameter of 16mm and thickness of 0.5 mm;
(2) Mixing Li 2 CO 3 、La 2 O 3 And ZrO 2 According to a molar ratio of 7:1: and 4, uniformly mixing, paving the mixture on one side of the solid electrolyte A thin layer, heating to 1200 ℃ at the speed of 5 ℃/min, calcining for 4 hours at the temperature, cooling to obtain a double-layer oxide solid electrolyte containing the solid electrolyte A thin layer and the garnet-type oxide solid electrolyte B thin layer, and polishing the garnet-type oxide solid electrolyte B thin layer in the double-layer oxide solid electrolyte to enable the thickness of the garnet-type oxide solid electrolyte B thin layer to be 50 microns.
Example 4
A double-layered oxide solid electrolyte was prepared as described in example 2, except that: the solid electrolyte A powder is Li 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 And Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The mixing mass ratio of (1): 1.
example 5
A double-layered oxide solid electrolyte was prepared as described in example 2, except that: the solid electrolyte A powder is Li 0.14 La 0.62 TiO 3 。
Example 6
A double-layered oxide solid electrolyte was prepared as described in example 2, except that:the solid electrolyte A powder is Li 0.11 La 0.63 TiO 3 。
Comparative example 1
(1) Mixing solid electrolyte A powder (Li) 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ) Pressing under 200MPa for 5min to obtain solid electrolyte A sheet with diameter of 16mm and thickness of 1 mm;
(2) And heating the solid electrolyte A slice to 950 ℃ at the speed of 5 ℃/min, calcining for 12 hours at the temperature, and cooling to obtain the solid electrolyte.
Comparative example 2
(1) A garnet-type oxide solid electrolyte B (Li) 7 La 3 Zr 2 O 12 ) Pressing under 200MPa for 5min to obtain solid electrolyte B sheet with diameter of 16mm and thickness of 1 mm;
mixing solid electrolyte A powder (Li) 1.3 Al 0.3 Ti 1.7( PO 4 ) 3 ) Starch, PVDF and N-methylpyrrolidone (NMP) according to a mass ratio of 1:1:1:28, evenly coating the mixture on the surface of the solid electrolyte B slice, heating to 950 ℃ at the speed of 5 ℃/min, calcining for 12 hours at the temperature, and cooling to obtain the solid electrolyte.
Test example
A solid-state battery was fabricated with lithium cobaltate as the positive electrode and metallic lithium as the negative electrode to evaluate the cycle performance of the oxide solid-state electrolyte. The specific method comprises the following steps: mixing lithium cobaltate, a conductive agent Super P and a binder PVDF according to the mass ratio of 9.5. The solid electrolyte sheets obtained in the examples and comparative examples were assembled into CR2032 type button cells in the order of positive electrode sheet-solid electrolyte sheet-lithium foil, respectively. Then, a battery cycle performance test was performed. The operating voltage range of the above all-solid-state lithium secondary battery was set to 3V to 4.2V at 0.2C (current density of 0.15 mA/cm) 2 ) Current constant current charging to 4.2V and then constant voltage to 0.05C cut off for 100 cycles, table 1 was obtained, wherein the cycle data of example 1 and comparative example 1 are shown in the figure2, respectively.
Table 1 results of cycle performance testing of lithium ion batteries having solid electrolytes of examples
Figure BDA0003893710550000121
Figure BDA0003893710550000131
From the data, when the solid electrolyte prepared by the method is applied to a battery, the capacity retention rate is higher after 100 cycles, which indicates that the cycling stability is better.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method for preparing a double-layer oxide solid electrolyte is characterized by comprising the following steps:
calcining the precursor powder of the garnet-type oxide solid electrolyte B in a state of being in contact with one side of the thin sheet of the solid electrolyte a to obtain a double-layer oxide solid electrolyte containing a thin layer of the solid electrolyte a and a thin layer of the garnet-type oxide solid electrolyte B;
wherein the solid electrolyte A is selected from at least one of NASICON structure oxide solid electrolyte, LISICON structure oxide solid electrolyte and perovskite structure oxide solid electrolyte.
2. The production method according to claim 1, wherein the NASICON-structure oxide solid electrolyte is Li 1+x M x N 2-x( PO 4 ) 3 The oxide solid electrolyte with the LISICON structure is Li 4-y Ge 1-y P y S 4 The perovskite structure oxide solid electrolyte is Li 3z La 2/3-z TiO 3 ；
Wherein M is Al, cr, ga, fe, sc, in, lu, Y or La, N is Ti or Ge, x is more than or equal to 0.2 and less than or equal to 0.6, Y is more than or equal to 0.4 and less than or equal to 0.6, and z is more than 0.04 and less than or equal to 0.17.
3. The production method according to claim 2, wherein the solid electrolyte A is selected from Li 1+x Al x Ti 2-x ( PO 4 ) 3 、Li 1+x Al x Ge 2-x( PO 4 ) 3 And Li 3z La 2/3-z TiO 3 At least one of (1).
4. The production method according to any one of claims 1 to 3, wherein the precursor powder of the garnet-type oxide solid electrolyte B contains Li 2 CO 3 、La 2 O 3 And ZrO 2 ；
The Li 2 CO 3 、La 2 O 3 And ZrO 2 The molar ratio of (A) is 1.
5. The production method according to claim 4, wherein the garnet-type oxide solid electrolyte B is Li 7 La 3 Zr 2 O 12 。
6. The method according to any one of claims 1 to 3, wherein the calcination conditions include: the temperature is 500-1200 ℃, and the time is 2-60 h;
preferably, the conditions of the calcination include: the temperature is 800-1200 ℃, and the time is 8-15 h.
7. The production method according to any one of claims 1 to 3, further comprising subjecting the thin layer of garnet-type oxide solid electrolyte B in the double-layer oxide solid electrolyte to a polishing treatment.
8. The production method according to claim 7, wherein the thickness ratio of the thin layer of the solid electrolyte A to the thin layer of the garnet-type oxide solid electrolyte B is 1000;
preferably, the thickness ratio of the thin layer of the solid electrolyte a to the thin layer of the garnet-type oxide solid electrolyte B is 1000;
preferably, the thickness of the thin layer of garnet-type oxide solid electrolyte B is 1 μm to 50 μm, and the thickness of the thin layer of solid electrolyte A is 0.5mm to 3mm.
9. A double-layer oxide solid-state electrolyte, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. A lithium ion battery, characterized in that it comprises a double oxide solid electrolyte according to claim 9, a lithium battery positive electrode plate (2) and a lithium battery negative electrode plate (3), a thin layer of solid electrolyte a (11) in the double oxide solid electrolyte being arranged towards the lithium battery positive electrode plate (2), and a thin layer of garnet type oxide solid electrolyte B (12) in the oxide solid electrolyte being arranged towards the lithium ion negative electrode plate (3).
CN202211266893.5A 2022-10-17 2022-10-17 Double-layer oxide solid electrolyte and preparation method and application thereof Pending CN115799612A (en)

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