CN115275328A - Composite electrolyte material and preparation method and application thereof - Google Patents

Composite electrolyte material and preparation method and application thereof Download PDF

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Publication number
CN115275328A
CN115275328A CN202210645825.3A CN202210645825A CN115275328A CN 115275328 A CN115275328 A CN 115275328A CN 202210645825 A CN202210645825 A CN 202210645825A CN 115275328 A CN115275328 A CN 115275328A
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China
Prior art keywords
composite electrolyte
llzo
electrolyte material
lithium
zirconium
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CN202210645825.3A
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Chinese (zh)
Inventor
田冰冰
李潇逸
黄晓
周永建
赵思湸
李真棠
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Guangdong Carriage Power Technology Co ltd
Shenzhen University
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Guangdong Carriage Power Technology Co ltd
Shenzhen University
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Priority to CN202210645825.3A priority Critical patent/CN115275328A/en
Publication of CN115275328A publication Critical patent/CN115275328A/en
Pending legal-status Critical Current

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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
    • 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
    • H01M2300/0085—Immobilising or gelification of 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
    • H01M2300/0088—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

Abstract

The invention discloses a composite electrolyte material and a preparation method and application thereof, wherein the composite electrolyte material consists of an LLZO material and lithium zirconium phosphate coated on the surface of the LLZO material. In the invention, the composite electrolyte material takes an LLZO material as a core, and zirconium lithium phosphate LiZr2(PO4)3As a coating layer, coating the surface of the LLZO material. Because of LiZr2(PO4)3Low alkalinity in electrolyte and coated with LiZr2(PO4)3The LLZO is low in alkalinity in the electrolyte, and meanwhile, the existence of the coating layer reduces the contact of the LLZO material and the outside air and reduces the pH value in the electrolyte, so that the stability of the composite electrolyte material to the electrolyte and the air is improved. And lithium zirconium phosphate LiZr2(PO4)3Has higher ionic conductivity, so the ionic conductivity of the composite electrolyte material is not reduced.

Description

Composite electrolyte material and preparation method and application thereof
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a composite electrolyte material and a preparation method and application thereof.
Background
Garnet-type oxide solid electrolyte Li7La3Zr2O12(LLZO) has been receiving much attention because it has advantages of high chemical stability and wide potential window, and is applied to batteries to replace organic electrolytes, thereby improving the safety of batteries. However, because the interface contact with the electrode is poor, a certain amount of electrolyte needs to be added to improve the contact effect. However, when LLZO is used together with an electrolyte, the composition and structure of the electrolyte are damaged due to the strong alkalinity of LLZO, and the battery performance is deteriorated.
At present, the improvement method aiming at the LLZO surface with stronger alkalinity mainly comprises a coating method: the LLZO surface is coated with a layer of metal oxide, such as alumina, which generally reduces the ionic conductivity of the material. In addition, some coating methods use complex coating means, so that the material processing cost is increased, the material consistency is reduced, and the batch production is difficult.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a composite electrolyte material, a preparation method and an application thereof, and aims to solve the problem that the stability of the solid electrolyte LLZO in the existing battery is poor to the electrolyte and the air.
The technical scheme of the invention is as follows:
a composite electrolyte material comprises a LLZO material and zirconium lithium phosphate coated on the surface of the LLZO material.
The composite electrolyte material is characterized in that the LLZO material is a pure LLZO material or a LLZO material doped with at least one element of tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium and barium.
The composite electrolyte material is characterized in that the mass ratio of the zirconium lithium phosphate in the composite electrolyte material is 0.1-10wt%.
The composite electrolyte material is characterized in that the lithium zirconium phosphate forms a coating layer on the surface of the LLZO material, and the thickness of the coating layer is 50-300nm.
The composite electrolyte material, wherein the LLZO material is particles with the particle size of 5-15 μm.
A method for producing a composite electrolyte material, comprising the steps of:
adding a zirconium source, a phosphorus source and a lithium source into a dispersion medium, mechanically stirring to obtain uniform slurry, then transferring the slurry into an oven for drying, placing the obtained powder into a muffle furnace, and sintering under the air condition to obtain zirconium lithium phosphate;
and mixing the lithium zirconium phosphate with the LLZO material and grinding to obtain the composite electrolyte material.
The preparation method of the composite electrolyte material comprises the steps of preparing a zirconium source, a phosphorus source, a lithium source and a dispersion medium, wherein the zirconium source is nano-zirconia, the phosphorus source is ammonium dihydrogen phosphate, the lithium source is lithium hydroxide, and the dispersion medium is one or more of absolute ethyl alcohol, isopropanol and ethylene glycol.
The preparation method of the composite electrolyte material comprises the step of transferring the composite electrolyte material into an oven for drying, wherein the drying temperature is 50-70 ℃, and the drying time is 0.5-3 h.
The preparation method of the composite electrolyte material comprises the following steps of grinding the composite electrolyte material by one or more of manual grinding, ball milling and roller milling.
The invention relates to application of a composite electrolyte material, wherein the composite electrolyte material is used for preparing a lithium ion battery.
Has the beneficial effects that: the composite electrolyte material provided by the invention comprises a LLZO material and lithium zirconium phosphate LiZr coated on the surface of the LLZO material2(PO4)3And (4) forming. Because of LiZr2(PO4)3Low alkalinity in electrolyte, bagCoated with LiZr2(PO4)3The LLZO is also low in alkalinity in the electrolyte, and simultaneously reduces the contact of the LLZO material with the outside air, thereby improving the stability of the LLZO material to the electrolyte and the air.
Drawings
FIG. 1 is an SEM image of the obtained lithium zirconium phosphate coated LLZO material as a fast ion conductor prepared in example 1 of the present invention.
FIG. 2 is an XRD pattern of the lithium zirconium phosphate coated LLZO material as a fast ion conductor obtained in example 1 of the present invention.
Detailed Description
The invention provides a composite electrolyte material, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a composite electrolyte material which is composed of a LLZO material and lithium zirconium phosphate coated on the surface of the LLZO material.
In the invention, the composite electrolyte material takes an LLZO material as a core, and zirconium lithium phosphate LiZr2(PO4)3As a coating layer, coating the surface of the LLZO material. Because of LiZr2(PO4)3Low alkalinity in electrolyte, coated with LiZr2(PO4)3The LLZO is low in alkalinity in the electrolyte, and the existence of the coating layer reduces the contact of the LLZO material and the outside air and reduces the pH value in the electrolyte, thereby improving the stability of the composite electrolyte material to the electrolyte and the air. And lithium zirconium phosphate LiZr2(PO4)3Has higher ionic conductivity, so the ionic conductivity of the composite electrolyte material is not reduced.
In some embodiments, the LLZO material is a pure LLZO material or an LLZO material doped with at least one element of tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium, barium; the LLZO material is particles with the particle size of 5-15 μm.
In some embodiments, the mass percentage of the lithium zirconium phosphate in the composite electrolyte material is 0.1-10wt%, the lithium zirconium phosphate forms a coating layer on the surface of the LLZO material, and the thickness of the coating layer is 50-300nm.
In some embodiments, there is also provided a method of preparing a composite electrolyte material, comprising the steps of: adding a zirconium source, a phosphorus source and a lithium source into a dispersion medium, mechanically stirring to obtain uniform slurry, then transferring the slurry into an oven for drying, placing the obtained powder into a muffle furnace, and sintering under the air condition to obtain zirconium lithium phosphate; and mixing the lithium zirconium phosphate with the LLZO material and grinding to obtain the composite electrolyte material.
The preparation method of the composite electrolyte material provided by the embodiment is simple in process, suitable for industrial large-scale production and low in cost.
In this embodiment, the zirconium source is nano-zirconia, the phosphorus source is ammonium dihydrogen phosphate, the lithium source is lithium hydroxide, and the dispersion medium is one or more of absolute ethyl alcohol, isopropyl alcohol, and ethylene glycol, but is not limited thereto.
In the step of transferring to the oven for drying in the embodiment, the drying temperature is 50-70 ℃, and the drying time is 0.5-3 h.
In the embodiment, the ball-to-material ratio of mechanical stirring is 30-10:1, the diameter of the sphere is 2-20mm, the rotation speed of mechanical stirring is 100-300r/min, and the time is 1-48h.
In the step of sintering under air condition in the embodiment, the temperature is raised to 1000 ℃ at the speed of 2 ℃/min, and the temperature is kept for 5-12h.
In some embodiments, the grinding process is one or more of hand milling, ball milling, and roller milling.
In some embodiments, the invention also provides an application of the composite electrolyte material, and the composite electrolyte material is used for preparing a lithium ion battery.
The invention is further illustrated by the following specific examples:
example 1
(1) Weighing 9.858g (0.08 mol) of zirconium dioxide (123.22 relative molecular mass), 0.959g (0.04 mol) of lithium hydroxide (23.95 relative molecular mass) and 11.885 (0.12 mol) of ammonium dihydrogen phosphate (99.03 relative molecular mass), adding 100g of absolute ethyl alcohol, mechanically stirring to obtain uniformly mixed slurry, placing the slurry in a drying oven to dry to obtain powder, wherein the drying temperature is 60 ℃ and the drying time is 2h, sintering in a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 8h to obtain the fast ion conductor zirconium lithium phosphate powder.
(2) And (3) taking 10g of the obtained zirconium lithium phosphate powder and 100g of LLZO powder, carrying out ball milling and mixing uniformly, wherein the tank body is a nylon tank, the diameter of a sphere is 5mm, and the ratio of the spheres to the materials is 10:1, ball milling at the rotating speed of 200r/min for 12h to obtain the lithium zirconium phosphate coated LLZO material with the fast ion conductor.
Example 2
(1) Weighing 9.858g (0.08 mol) of zirconium dioxide (123.22 relative molecular mass), 0.959g (0.04 mol) of lithium hydroxide (23.95 relative molecular mass) and 11.885 (0.12 mol) of ammonium dihydrogen phosphate (99.03 relative molecular mass), adding 100g of absolute ethyl alcohol, mechanically stirring to obtain uniformly mixed slurry, placing the slurry in a drying oven to dry to obtain powder, wherein the drying temperature is 50 ℃ and the drying time is 3h, sintering in a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 5 to obtain the fast ion conductor zirconium phosphate lithium powder.
(2) Taking 5g of the obtained zirconium lithium phosphate powder and 100g of LLZO powder, and uniformly mixing by using a roller mill, wherein the tank body is a polyurethane tank, the diameter of the ball body is 5mm, and the ball material ratio is 10:1, ball milling at the rotating speed of 200r/min for 12h to obtain the lithium zirconium phosphate coated LLZO material with the fast ion conductor.
Example 3
(1) Weighing 9.858g (0.08 mol) of zirconium dioxide (123.22 relative molecular mass), 0.959g (0.04 mol) of lithium hydroxide (23.95 relative molecular mass) and 11.885 (0.12 mol) of ammonium dihydrogen phosphate (99.03 relative molecular mass), adding 100g of absolute ethyl alcohol, mechanically stirring to obtain uniformly mixed slurry, placing the slurry in a drying oven to dry to obtain powder, wherein the rotation speed of the mechanical stirring is 300r/min and the time is 1h, the drying temperature is 70 ℃, the drying time is 1h, sintering in a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 12h to obtain the fast ion conductor lithium zirconium phosphate powder.
(2) And taking 1g of the obtained zirconium lithium phosphate powder and 100g of LLZO powder, and carrying out sand grinding and uniform mixing on the zirconium lithium phosphate powder and the 100g of LLZO powder, wherein the diameter of a sphere is 0.5mm, and the ratio of the sphere to the material is 10:1, sanding for 0.5h to obtain the LLZO material coated by the fast ion conductor lithium zirconium phosphate.
Comparative example 1
Comparative example 1 differs from example 1 only in that: except that the LLZO material was uncoated, i.e., uncoated in step (2), and was not subjected to the treatment of step (1).
The LLZO powder material prepared in example 1 of the present invention was subjected to morphology observation by scanning electron microscopy, as shown in FIG. 1.
The LLZO material prepared in example 1 of the present invention was structurally characterized by X-ray diffraction as shown in FIG. 2.
The LLZO materials prepared in examples 1 to 3 according to the present invention and comparative example 1 were immersed in an electrolyte to measure pH, and the powder tablets were subjected to the test, with the results shown in table 1 below.
TABLE 1 test results
Sample (I) pH value Ionic conductivity (S.cm)-1)
Example 1 7.5 5.62×10-4
Example 2 8.4 4.52×10-4
Example 3 9.2 3.02×10-4
Comparative example 1 10.1 1.34×10-4
As can be seen from Table 1, the pH of the lithium zirconium phosphate coated LLZO materials for fast ion conductors prepared in examples 1-3 was lower than that of comparative example 1, and the ionic conductivities were all higher.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. The composite electrolyte material is characterized by consisting of an LLZO material and lithium zirconium phosphate coated on the surface of the LLZO material.
2. The composite electrolyte material of claim 1, wherein the LLZO material is a pure LLZO material or an LLZO material doped with at least one element of tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium, barium.
3. The composite electrolyte material according to claim 1, characterized in that the mass proportion of the lithium zirconium phosphate in the composite electrolyte material is 0.1 to 10wt%.
4. The composite electrolyte material of claim 1, wherein the lithium zirconium phosphate forms a coating layer on the surface of the LLZO material, and the coating layer has a thickness of 50-300nm.
5. The composite electrolyte material of claim 1, wherein the LLZO material is particles having a particle size of 5-15 μ ι η.
6. A method for producing the composite electrolyte material according to claim 1, comprising the steps of:
adding a zirconium source, a phosphorus source and a lithium source into a dispersion medium, mechanically stirring to obtain uniform slurry, then transferring the slurry into an oven for drying, placing the obtained powder into a muffle furnace, and sintering under the air condition to obtain zirconium lithium phosphate;
and mixing the lithium zirconium phosphate with an LLZO material and grinding to obtain the composite electrolyte material.
7. The method for producing the composite electrolyte material according to claim 6, wherein the zirconium source is nano-zirconia, the phosphorus source is ammonium dihydrogen phosphate, the lithium source is lithium hydroxide, and the dispersion medium is one or more of absolute ethyl alcohol, isopropyl alcohol, and ethylene glycol.
8. The preparation method of the composite electrolyte material according to claim 6, characterized in that the step of transferring to an oven for drying is carried out, wherein the drying temperature is 50 ℃ to 70 ℃, and the drying time is 0.5h to 3h.
9. The method for producing the composite electrolyte material according to claim 6, wherein the grinding treatment is one or more of a manual grinding, a ball milling, and a roll milling.
10. Use of the composite electrolyte material according to claim 1 for the preparation of a lithium ion battery.
CN202210645825.3A 2022-06-09 2022-06-09 Composite electrolyte material and preparation method and application thereof Pending CN115275328A (en)

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Application Number Priority Date Filing Date Title
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Publications (1)

Publication Number Publication Date
CN115275328A true CN115275328A (en) 2022-11-01

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