CN109065946B - Preparation method of solid electrolyte - Google Patents

Preparation method of solid electrolyte Download PDF

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CN109065946B
CN109065946B CN201811080709.1A CN201811080709A CN109065946B CN 109065946 B CN109065946 B CN 109065946B CN 201811080709 A CN201811080709 A CN 201811080709A CN 109065946 B CN109065946 B CN 109065946B
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solid electrolyte
lithium
hours
ball milling
preparing
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CN109065946A (en
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刘芳洋
赖延清
孙振
徐向群
蒋良兴
贾明
李劼
刘业翔
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Guangzhou Boyue New Material Technology Co ltd
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Central South University
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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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a solid electrolyte, which comprises the following steps: (1) weighing lithium salt, zirconium salt and phosphoric acid according to the required stoichiometric ratioSalt, and mixing uniformly; (2) pre-burning the uniformly mixed mixture for 2-6 hours at 400-800 ℃ by microwave; (3) grinding the pre-sintered mixture uniformly, tabletting, and then sintering at 800-1000 ℃ for 2-6 hours by microwave to obtain LiZr2(PO4)3A solid electrolyte. Compared with the prior art, the method has low sintering temperature and short production period, and can obtain the stable rhombic LiZr at room temperature2(PO4)3The ionic conductance reaches 1.0 × 10 at normal temperature‑6～8.0×10‑5S/cm。

Description

Preparation method of solid electrolyte
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a solid electrolyte.
Background
The lithium ion battery has the advantages of high energy density, large output power, high voltage, small self-discharge, wide working temperature range, no memory effect, environmental friendliness and the like, and is applied to the fields of electric vehicles, rail transit, large-scale energy storage, aerospace and the like. At present, the commercial lithium ion battery adopts an organic liquid electrolyte, the electrolyte and an electrode material are easy to generate side reactions in the charging and discharging processes, so that the battery capacity is subjected to irreversible attenuation, and meanwhile, the organic liquid electrolyte can volatilize, dry, leak and the like in the long-term service process of the battery, so that the service life of the battery is influenced. On the other hand, the conventional lithium ion battery cannot use the metal lithium with high energy density as a negative electrode material, and during the battery cycle, due to factors such as the surface current density of the metal lithium and the uneven distribution of lithium ions, the metal lithium electrode is repeatedly dissolved and deposited to easily form uneven holes and dendrites. The dendrites can pierce through the diaphragm and reach the positive electrode of the battery, so that a series of potential safety hazards such as short circuit, thermal runaway, ignition and explosion of the battery are caused. Replacing liquid electrolytes with solid electrolytes is the fundamental approach to obtain all-solid-state lithium batteries with high energy density, safety and long cycle life.
Commercially available NASICON solid electrolyte Li1.3Al0.3Ti1.7(PO4)3Lithium ion conductivity at σLi>10- 4S/cm, and when metallic lithium is used as an electrode, Ti4+Is reduced to Ti3+Limit Li1.3Al0.3Ti1.7(PO4)3The range of use of (c). To LiZr2(PO4)3Solid electrolyte, LiZr due to the stability of zirconium and phosphorus ions2(PO4)3Would be a better choice in lithium batteries, but LiZr2(PO4)3Triclinic phase at room temperature and an ionic conductivity of 10-8S/cm; at more than 50 ℃, LiZr2(PO4)3Converted into rhombohedral phase with an ionic conductivity of 10-5S/cm, how to stabilize LiZr of lithium ion electrolyte2(PO4)3It would be very interesting to keep the rhombohedral phase at room temperature.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a solid electrolyte of an all-solid-state lithium ion battery, and aims to solve the problem of LiZr prepared by the existing method2(PO4)3Cannot be stabilized into rhombohedral phase at room temperature.
In order to achieve the above object, the present invention provides a method for preparing a solid electrolyte, comprising the steps of:
(1) weighing lithium salt, zirconium salt and phosphate according to the required stoichiometric ratio, and uniformly mixing;
(2) pre-burning the uniformly mixed mixture for 2-6 hours at 400-800 ℃ by microwave;
(3) grinding the pre-sintered mixture uniformly, tabletting, and then sintering at 800-1000 ℃ for 2-6 hours by microwaveTo obtain LiZr2(PO4)3A solid electrolyte.
Preferably, the stoichiometric ratio in the step (1) is Li+:Zr4+:PO4 3-＝1:1.5-2.5:2.5-3.5。
Preferably, the lithium salt in step (1) includes one or more of lithium nitrate, lithium carbonate, lithium hydroxide and lithium oxide.
Preferably, the zirconium salt in step (1) comprises one or more of zirconium nitrate and zirconium oxide.
Preferably, the phosphate in step (1) includes one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium hydrogen phosphite.
Preferably, doping metal salt is further added in the step (1), the doping metal comprises at least one of Ca, Al, Sr, Ba and Y, and the Li obtained in the step (3)xMyZrz(PO4)3Solid electrolytes in which x, y, z ∈ [1,2 ]]。
Preferably, the step (1) is to mix uniformly by ball milling, wherein one or more of isopropanol, ethanol, acetone and n-butanol is/are used as a ball milling agent, a zirconia pot and zirconia balls are used, and the ball milling speed is 100-.
Preferably, the temperature in the step (2) is increased to 400-800 ℃ at a temperature increase rate of 5-40 ℃/min.
Preferably, the uniformly ground tabletting in the step (3) is uniformly ground by using an agate mortar, and then the ground product is pressed by using a press, wherein the pressure of the press is 50-200Mpa, and the pressure maintaining time is 1-30 min.
Preferably, the temperature in the step (3) is increased to 800-1000 ℃ at a temperature increase rate of 5-40 ℃/min.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the invention adopts the microwave sintering technology to sinter the LiZr at low temperature (800-2(PO4)3Solid electrolyte of ionic electricity at normal temperatureLead 1.0 × 10-6～8.0×10- 5S/cm；
(2) After doping, the rhombohedral phase Li is obtainedxMyZrz(PO4)3The solid electrolyte has higher ionic conductivity, and compared with undoped electrolyte, the sintering temperature is lower, and the production period is shorter.
Drawings
Fig. 1 is a physical diagram of a solid electrolyte sheet obtained in example 1;
FIG. 2 is LiZr tested at room temperature after sintering in example 12(PO4)3XRD pattern of (A), and conventionally sintered LiZr2(PO4)3XRD pattern of (a);
fig. 3 is a graph of impedance measured at room temperature of the solid electrolyte sheet obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1:
weighing 2N pure reagent Li according to the required stoichiometric ratio2CO3、ZrO2And NH4H2PO4And mixing, putting into a zirconia ball milling tank, ball milling by zirconia balls with ethanol as a ball milling agent at the ball milling rotation speed of 400rpm for 3 hours, and drying to obtain uniformly mixed raw materials.
Placing the raw materials in a microwave device, heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 6h, pressing the obtained powder under 200Mpa, maintaining the pressure for 10min, placing the obtained solid electrolyte sheet in a microwave device, heating to 800 deg.C at a speed of 10 deg.C/min, maintaining the temperature for 6h to form a compact electrolyte sheet, and cooling to obtain the solid electrolyte as shown in FIG. 1.
Referring to FIG. 2, the bottom is a rhombohedral phase standard card, and LiZr sintered by the method2(PO4)3Is stable rhombohedral phase at room temperature, and is obtained by the traditional sintering methodTo LiZr2(PO4)3Triclinic at room temperature.
Referring to fig. 3, the ion conductivity is calculated by the formula of σ L/(a × Z) with the unit of S/cm, where L is the thickness (0.3cm) and a is the area (1.34 cm)2) Z is impedance (60K Ω), and the lithium electrical conductivity σ of the solid electrolyte sheet at room temperature was calculated to be 0.3/(1.34 × 60000) 3.7 × 10-6S cm-1。
Example 2:
weighing lithium oxide, zirconium oxide and diammonium hydrogen phosphate according to a required stoichiometric ratio, mixing, putting into a ball milling tank of zirconium oxide, ball milling by adopting isopropanol as a ball milling agent, ball milling zirconium oxide balls at a ball milling rotation speed of 100rpm for 24 hours, drying to obtain uniformly mixed raw materials, putting the raw materials into microwave equipment, heating to 400 ℃ at a speed of 5 ℃/min, preserving heat for 6 hours, pressing the cooled powder under a pressure of 200Mpa, maintaining the pressure for 10 minutes, putting the obtained solid electrolyte sheet into the microwave equipment, heating to 1000 ℃ at a speed of 20 ℃/min, preserving heat for 2 hours, cooling with a furnace to obtain the solid electrolyte sheet, wherein the lithium electrical conductivity of the solid electrolyte sheet is 7.4 × 10 at room temperature-5S cm-1。
Example 3:
weighing lithium hydroxide, zirconium oxide and ammonium hydrogen phosphite according to a required stoichiometric ratio, mixing, putting into a ball milling tank of zirconium oxide, ball milling the zirconium oxide by using isopropanol as a ball milling agent at a ball milling rotation speed of 1200rpm for 1 hour, drying to obtain a uniformly mixed raw material, putting the raw material into microwave equipment, heating to 600 ℃ at a speed of 30 ℃/min, preserving heat for 2 hours, pressing the cooled powder under a pressure of 50MPa, maintaining the pressure for 30 minutes, putting the obtained solid electrolyte sheet into the microwave equipment, heating to 900 ℃ at a speed of 30 ℃/min, preserving heat for 4 hours, cooling with a furnace to obtain the solid electrolyte sheet, wherein the lithium electrical conductivity of the solid electrolyte sheet is 8.4 × 10 at room temperature-6S cm-1。
Example 4:
weighing lithium hydroxide, zirconium oxide, calcium carbonate and ammonium hydrogen phosphite according to the required stoichiometric ratio, mixing and putting into a ball milling tank of zirconium oxide,putting the raw materials into microwave equipment, heating to 450 ℃ at the speed of 10 ℃/min, preserving heat for 3h, pressing the cooled powder under the pressure of 100Mpa, maintaining the pressure for 20min, putting the obtained solid electrolyte sheet into the microwave equipment, heating to 850 ℃ at the speed of 10 ℃/min, preserving heat for 3h, cooling with a furnace to obtain the solid electrolyte sheet, wherein the lithium electrical conductivity of the solid electrolyte sheet at room temperature is 2 × 10-4S cm-1。
Example 5:
weighing lithium hydroxide, zirconium oxide, aluminum oxide and ammonium hydrogen phosphite according to a required stoichiometric ratio, mixing, putting into a ball milling tank of zirconium oxide, ball milling zirconium oxide balls by adopting isopropanol as a ball milling agent at a ball milling rotation speed of 1000rpm for 2 hours, drying to obtain uniformly mixed raw materials, putting the raw materials into microwave equipment, heating to 500 ℃ at a speed of 10 ℃/min, preserving heat for 2.5 hours, pressing the cooled powder under a pressure of 100MPa, maintaining the pressure for 20 minutes, putting the obtained solid electrolyte sheet into the microwave equipment, heating to 900 ℃ at a speed of 10 ℃/min, preserving heat for 2.5 hours, cooling with a furnace to obtain the solid electrolyte sheet, wherein the lithium electrical conductivity of the solid electrolyte sheet at room temperature is 1.5 × 10-4S cm-1。

Claims (7)

1. A method for producing a solid electrolyte, characterized by comprising the steps of:
(1) weighing a lithium source, a zirconium source and a phosphoric acid source according to the required stoichiometric ratio, and uniformly mixing;
(2) pre-burning the uniformly mixed mixture for 2-6 hours at 400-800 ℃ by microwave;
(3) grinding the pre-sintered mixture uniformly, tabletting, and then sintering at 800-1000 ℃ for 2-6 hours by microwave to obtain LiZr2(PO4)3A solid electrolyte; wherein the content of the first and second substances,
in the step (2), the temperature is increased to 400-800 ℃ at the temperature increase rate of 5-40 ℃/min; the tabletting after the uniform grinding in the step (3) is to use an agate mortar for uniform grinding, and then press the ground product by using a press machine, wherein the pressure of the press machine is 50-200Mpa, and the pressure maintaining time is 1-30 min; in the step (3), the temperature is increased to 800-1000 ℃ at a temperature increase rate of 5-40 ℃/min.
2. The method for producing a solid electrolyte according to claim 1, wherein the stoichiometric ratio in the step (1) is Li+:Zr4+:PO4 3-＝1:1.5-2.5:2.5-3.5。
3. The method for preparing a solid electrolyte according to claim 1, wherein the lithium source in the step (1) comprises one or more of lithium nitrate, lithium carbonate, lithium hydroxide and lithium oxide.
4. The method for preparing a solid electrolyte according to claim 1, wherein the zirconium source in step (1) comprises one or more of zirconium nitrate and zirconium oxide.
5. The method for preparing a solid electrolyte according to claim 1, wherein the phosphoric acid source in step (1) comprises one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium hydrogen phosphite.
6. The method for preparing a solid electrolyte according to claim 1, wherein the doping metal salt is further added in the step (1), the doping metal comprises at least one of Ca, Al, Sr, Ba and Y, and the step (3) is to obtain LixMyZrz(PO4)3Solid electrolytes in which x, y, z ∈ [1,2 ]]。
7. The method for preparing a solid electrolyte according to any one of claims 1 to 6, wherein the step (1) of uniformly mixing is performed by ball milling using one or more of isopropanol, ethanol, acetone and n-butanol as a ball milling agent, a zirconia pot and zirconia balls at a ball milling speed of 100-1200rpm for 1-24 hours.
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JP2002110227A (en) * 2000-09-29 2002-04-12 National Institute For Materials Science Method for manufacturing lithium ion conductive solid electrolyte thin film
WO2017197406A1 (en) * 2016-05-13 2017-11-16 Quantumscape Corporation Solid electrolyte separator bonding agent

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CN107895813A (en) * 2017-12-06 2018-04-10 贵州梅岭电源有限公司 A kind of preparation method of high conductance lithium ion solid electrolyte
CN108155413A (en) * 2018-01-12 2018-06-12 北京科技大学 The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method

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Publication number Priority date Publication date Assignee Title
JP2002110227A (en) * 2000-09-29 2002-04-12 National Institute For Materials Science Method for manufacturing lithium ion conductive solid electrolyte thin film
WO2017197406A1 (en) * 2016-05-13 2017-11-16 Quantumscape Corporation Solid electrolyte separator bonding agent

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