CN115472902A - Solid electrolyte material and preparation thereof, lithium ion solid battery and application - Google Patents
Solid electrolyte material and preparation thereof, lithium ion solid battery and application Download PDFInfo
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 provides a solid electrolyte material and preparation thereof, a lithium ion solid battery and application thereof, wherein the solid electrolyte material comprises a matrix material and a coating layer coated on the outer surface of the matrix material; wherein the structural formula of the matrix material is Li 1+x Al x Ti 2‑x (PO 4 ) 3 X is more than or equal to 0.1 and less than or equal to 0.5; the material of the coating layer is ZnZr 4 (PO 4 ) 6 . The solid electrolyte material has higher ionic conductivity and density, and the ternary cathode material coated by the solid electrolyte material also shows excellent thermal stability.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a solid electrolyte material and preparation thereof, a lithium ion solid battery and application thereof.
Background
The liquid electrolyte in the traditional lithium ion battery has the problems of poor cycle performance, potential safety hazards and the like, while the solid electrolyte has the characteristics of higher safety and stability, capability of continuously and normally working in a wider temperature range, and wide application prospect in the aspects of power and energy storage. Therefore, more and more researchers are working on technical methods of replacing liquid electrolytes with solid electrolytes, and are beginning to focus on the development and application of all-solid lithium ion batteries.
Lithium aluminium titanium phosphate (Li) 1+x Al x Ti 2-x (PO 4 ) 3 LATP) solid electrolyte, which has received much attention because of its high ionic conductivity. At present, the most applied methods for preparing the LATP solid electrolyte are a sol-gel method, a molten salt quenching method, a hydrothermal method and a high-temperature solid phase method. Among them, al is generally used in the solid phase method 2 O 3 As an aluminum source; in the solution preparation methods such as sol-gel method and hydrothermal method, aluminum nitrate and the like are generally used as an aluminum source. The ceramic body sintered by the LATP powder prepared by the sol-gel method has the ion conductivity of 10 -4 S/cm, the ion conductivity of the nano LATP obtained by the high-energy ball milling solid phase method after heat treatment can also reach 10 -4 S/cm。
Solid-state electrolytes typically rely primarily on the migration of conductive ions to perform the conductive function. As the ion transfer rate is faster, the conductivity of the electrolyte is better. The ion mobility is closely related to the degree of crystal arrangement inside the lithium ion conductor. However, the LATP materials mentioned above all suffer from a problem of poor tightness, which results in a low ionic conductivity, which affects the electrochemical performance of the cell. Therefore, a new solid electrolyte material is urgently needed to be provided to solve the problems of low ionic conductivity and the like of the titanium aluminum lithium phosphate material in the prior art.
Disclosure of Invention
The invention mainly aims to provide a solid electrolyte material, a preparation method thereof, a lithium ion solid-state battery and an application thereof, and aims to solve the problems of low ionic conductivity and the like of a titanium aluminum lithium phosphate material in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a solid state electrolyte material including a base material and a clad layer clad on an outer surface of the base material; wherein the structural formula of the matrix material is Li 1+x Al x Ti 2-x (PO 4 ) 3 X is more than or equal to 0.1 and less than or equal to 0.5; the material of the coating layer is ZnZr 4 (PO 4 ) 6 。
Further, the air conditioner is characterized in that,in the structural formula of the matrix material, x is more than or equal to 0.2 and less than or equal to 0.4; znZr in the clad layer is preferable 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio of (0.001-0.02) to (1).
Furthermore, the density of the solid electrolyte material is 95-98%.
In order to achieve the above object, according to one aspect of the present invention, there is provided a production method of a solid electrolyte material, the production method including the steps of: step S1, carrying out first calcination on a first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 (ii) a Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with ZnZr 4 (PO 4 ) 6 Mixing and carrying out secondary calcination to obtain the solid electrolyte material.
Further, the pH value of the first dispersion liquid is 8-10; preferably, the dispersant of the first dispersion is one or more of absolute ethyl alcohol, absolute methyl alcohol or ethyl acetate; preferably the zinc source is selected from one or more of zinc sulphide, zinc carbonate or zinc chloride; preferably the zirconium source is selected from one or more of zirconyl chloride, zirconium hydroxide or zirconium chloride; preferably, the first source of phosphoric acid is selected from one or more of monoammonium phosphate, phosphoric acid or diammonium phosphate.
Further, before the first calcination, the preparation method of the solid electrolyte material further comprises the steps of sequentially performing first ball milling and first drying on the first dispersion liquid; preferably, the processing rotating speed of the first ball mill is 150-400 rpm, and the processing time is 2-5 h; preferably, the treatment temperature of the first drying is 90-110 ℃, and the treatment time is 1-4 h; the treatment temperature of the first calcination is preferably 300 to 700 ℃ and the treatment time is preferably 6 to 12 hours.
Further, the dispersant of the second dispersion liquid is one or more of absolute ethyl alcohol, absolute methanol or ethyl acetate; preferred is ZnZr 4 (PO 4 ) 6 The mol ratio of the phosphoric acid to the second phosphoric acid source is (0.001-0.02) to 3; preferably the lithium source is selected from one or more of lithium carbonate, lithium hydroxide or lithium oxide; preferred aluminium sourcesOne or more selected from aluminum oxide, aluminum hydroxide or aluminum chloride; preferably the titanium source is selected from one or more of titanium oxide, titanium chloride or titanium hydroxide; preferably, the second source of phosphoric acid is selected from one or more of monoammonium phosphate, phosphoric acid or diammonium phosphate.
Further, before the second calcination, the preparation method of the solid electrolyte material further comprises the steps of sequentially performing second ball milling and second drying on the second dispersion liquid; the processing speed of the second ball mill is 200-500 rpm, and the processing time is 2-10 h; the treatment temperature of the second drying is 60-100 ℃, and the treatment time is 4-8 h; the treatment temperature of the second calcination is 850-950 ℃, and the treatment time is 8-12 h.
According to another aspect of the present invention, there is provided a lithium ion solid-state battery including the above solid electrolyte material, or a solid electrolyte material produced by the above method for producing a solid electrolyte material.
According to another aspect of the present invention, there is provided a use of a lithium ion solid-state battery for an electric vehicle or an electric bicycle.
The solid electrolyte material prepared by the method has higher ionic conductivity and density, and the ternary cathode material coated by the solid electrolyte material also shows excellent thermal stability.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background of the invention section, the problem of low ionic conductivity of the prior art lithium titanium aluminum phosphate materials is present. In order to solve the problem, the invention provides a solid electrolyte material which comprises a matrix material and a coating layer coated on the outer surface of the matrix material; wherein the structural formula of the matrix material is Li 1+x Al x Ti 2-x (PO 4 ) 3 X is more than or equal to 0.1 and less than or equal to 0.5, and the material of the coating layer is ZnZr 4 (PO 4 ) 6 。
The invention coats ZnZr on the surface of a base material 4 (PO 4 ) 6 In one aspect, znZr 4 (PO 4 ) 6 The introduction of the composite material can improve the differential scanning calorimetry peak temperature of the solid electrolyte material, so that the thermal stability and the safety performance of the material are better. On the other hand, znZr 4 (PO 4 ) 6 The introduction of the composite material can also reduce holes and gaps of the matrix, thereby increasing the density of the solid electrolyte material and further improving the ionic conductivity of the solid electrolyte material.
In a preferred embodiment, the matrix material has a structural formula in which 0.2. Ltoreq. X.ltoreq.0.4. For example, the matrix material may be Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Or Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 . Coating ZnZr on the surface of the base material 4 (PO 4 ) 6 The obtained electrolyte material has better thermal stability and safety performance, and the ionic conductivity of the solid electrolyte material can be further improved.
Preferably, znZr in the coating layer 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio of (0.001-0.02) to (1). For example, can be. ZnZr in the coating layer 4 (PO 4 ) 6 With Li in the matrix material 1+ x Al x Ti 2-x (PO 4 ) 3 The molar ratio is preferably within the above range, so that the stability of the matrix material can be further improved, and the number of holes and gaps of the matrix material can be further effectively reduced, thereby further improving the density of the solid electrolyte material and further improving the ionic conductivity of the solid electrolyte material.
In order to further promote the increase of the ionic conductivity of the solid electrolyte material, in a preferred embodiment, the density of the solid electrolyte material is 95 to 98%.
Another aspect of the present invention also provides a preparation method of the above solid electrolyte material, including the steps of: step S1, carrying out first calcination on a first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 (ii) a Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 Mixing and carrying out secondary calcination to obtain the solid electrolyte material.
In the preparation method of the solid electrolyte material provided by the invention, a person skilled in the art can firstly perform first calcination on a first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Then, a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source is mixed with the ZnZr 4 (PO 4 ) 6 Mixing and carrying out secondary calcination to finally obtain the solid electrolyte material. Wherein the matrix material Li 1+x Al x Ti 2-x (PO 4 ) 3 Li, al, ti, P source and ZnZr in 4 (PO 4 ) 6 Partial deposition occurs, thereby ZnZr 4 (PO 4 ) 6 Introduced onto the outer surface of the base material. Thus, on the one hand, znZr 4 (PO 4 ) 6 The introduction of the composite material can improve the differential scanning calorimetry peak temperature of the solid electrolyte material, so that the thermal stability and the safety performance of the material are better. On the other hand, znZr 4 (PO 4 ) 6 The introduction of the composite material can also reduce holes and gaps of the matrix, thereby increasing the density of the solid electrolyte material and further improving the ionic conductivity of the solid electrolyte material. In addition, the preparation method is convenient to operate, simple in process, suitable for large-scale production and wide in application prospect.
In a preferred embodiment, in the solid state electrolyte materialIn the preparation step S1 of the material, for obtaining ZnZr 4 (PO 4 ) 6 Has better stability and higher activity, thereby better leading ZnZr 4 (PO 4 ) 6 The pH value of the first dispersion is preferably 8 to 10 when introduced into the LATP matrix material to increase the compactness of the solid electrolyte material. In order to promote the above-mentioned zinc source, zirconium source and first phosphoric acid source to have more excellent stability and uniformity in the first dispersion, it is preferable that the dispersant of the first dispersion is one or more of absolute ethyl alcohol, absolute methanol or ethyl acetate; further preferably, the zinc source is selected from one or more of zinc sulfide, zinc carbonate or zinc chloride; further preferably, the zirconium source is selected from one or more of zirconyl chloride, zirconium hydroxide or zirconium chloride; it is further preferred that the first source of phosphoric acid is selected from one or more of monoammonium phosphate, phosphoric acid or diammonium phosphate.
Further preferably, in the preparation process of the solid electrolyte material, in order to obtain ZnZr with better stability and higher activity 4 (PO 4 ) 6 Before the first calcination, the method further comprises the steps of sequentially carrying out first ball milling and first drying on the first dispersion liquid. Preferably, the processing rotating speed of the first ball mill is 150-400 rpm, and the processing time is 2-5 h; preferably, the first drying treatment temperature is 90-110 ℃, and the treatment time is 1-4 h; more preferably, the treatment temperature of the first calcination is 300 to 700 ℃ and the treatment time is 6 to 12 hours.
In a preferred embodiment, in the step S2 of preparing the solid electrolyte material, in order to promote better stability and uniformity of the lithium source, the aluminum source and the second phosphoric acid source in the second dispersion liquid, the matrix material Li is further facilitated 1+x Al x Ti 2-x (PO 4 ) 3 Li, al, ti, P source and ZnZr in 4 (PO 4 ) 6 Deposition occurs so that ZnZr 4 (PO 4 ) 6 The solid electrolyte material is introduced into the matrix material to better increase the density of the matrix material and further improve the ionic conductivity of the solid electrolyte material. Preferably, the dispersant of the second dispersion is one or more of absolute ethyl alcohol, absolute methyl alcohol or ethyl acetate; preferred is ZnZr 4 (PO 4 ) 6 The molar ratio of the phosphoric acid to the second phosphoric acid source is (0.001-0.02): 3. For example, can be 0.001. Preferably the lithium source is selected from one or more of lithium carbonate, lithium hydroxide or lithium oxide; the aluminum source is selected from one or more of aluminum oxide, aluminum hydroxide or aluminum chloride; preferably the titanium source is selected from one or more of titanium oxide, titanium chloride or titanium hydroxide; preferably, the second source of phosphoric acid is selected from one or more of monoammonium phosphate, phosphoric acid or diammonium phosphate. Based on the above, the stability of the solid electrolyte material is improved, and the density of the solid electrolyte material can be increased, so that the ionic conductivity of the solid electrolyte material is improved.
Further preferably, in the preparation process of the solid electrolyte material, in order to further increase the compactness of the solid electrolyte material, thereby improving the ionic conductivity of the solid electrolyte material. Before the second calcining, the preparation method further comprises the steps of carrying out second ball milling and second drying on the second dispersion liquid in sequence. Preferably, the processing rotating speed of the second ball mill is 200-500 rpm, and the processing time is 2-10 h; preferably, the treatment temperature of the second drying is 60-100 ℃, and the treatment time is 4-8 h; more preferably, the treatment temperature of the second calcination is 850 to 950 ℃ and the treatment time is 8 to 12 hours.
The invention also provides a lithium ion solid-state battery which comprises the solid electrolyte material or the solid electrolyte material prepared by the preparation method of the solid electrolyte material. The lithium ion solid-state battery has higher conductivity and better electrochemical performance.
The invention also provides application of the lithium ion solid-state battery, and the lithium ion solid-state battery has a very wide application prospect in electric automobiles or electric bicycles.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, the mol ratio of Zn, zr, P in the zinc source, the zirconium source and the first phosphoric acid source is 1. The processing speed of the first ball milling is 150rpm, the processing time is 2h, the processing temperature of the first drying is 90 ℃, and the processing time is 1h; the treatment temperature of the first calcination was 300 ℃ and the treatment time was 6 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, in the lithium source, the aluminum source, the titanium source and the second phosphoric acid source, the molar ratio of Li, al, ti and P is 1.1 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source was 0.001. The processing speed of the second ball milling is 200rpm, the processing time is 2h, the processing temperature of the second drying is 60 ℃, and the processing time is 4h; the treatment temperature of the second calcination was 850 ℃ and the treatment time was 8 hours. ZnZr in the solid electrolyte material and the coating layer finally obtained 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.001 1.1 Al 0.1 Ti 1.9 (PO 4 ) 3 The compactness is 95.36%.
Example 2
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, in the zinc source, the zirconium source and the first phosphoric acid source, zn,The molar ratio of Zr to P is 1. The processing speed of the first ball milling is 200rpm, the processing time is 3h, the processing temperature of the first drying is 95 ℃, and the processing time is 3.5h; the treatment temperature of the first calcination was 400 ℃ and the treatment time was 8 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, the molar ratio of Li, al, ti, P in the lithium source, the aluminum source, the titanium source, and the second phosphoric acid source is 1.2 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source was 0.0015. The processing speed of the second ball milling is 350rpm, the processing time is 4h, the processing temperature of the second drying is 80 ℃, and the processing time is 5h; the treatment temperature of the second calcination is 870 ℃, and the treatment time is 9h. ZnZr in the solid electrolyte material, coating layer, obtained finally 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.0015, and the structural formula of the solid electrolyte material is Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 The density was 95.51%.
Example 3
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, in the zinc source, the zirconium source and the first phosphoric acid source, the molar ratio of Zn, zr and P is 1. The processing speed of the first ball mill is 250rpm, the processing time is 3h, the first ball millThe drying treatment temperature is 100 ℃, and the treatment time is 2h; the treatment temperature of the first calcination was 500 ℃ and the treatment time was 9 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, the molar ratio of Li, al, ti, P in the lithium source, the aluminum source, the titanium source, and the second phosphoric acid source is 1.3 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source was 0.0015. The processing speed of the second ball milling is 350rpm, the processing time is 6h, the processing temperature of the second drying is 80 ℃, and the processing time is 6h; the treatment temperature of the second calcination is 900 ℃, and the treatment time is 10h. ZnZr in the solid electrolyte material, coating layer, obtained finally 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.0015, and the structural formula of the solid electrolyte material is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The compactness is 96.87%.
Example 4
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, in the zinc source, the zirconium source and the first phosphoric acid source, the molar ratio of Zn, zr and P is 1. The processing speed of the first ball milling is 300rpm, the processing time is 5h, the processing temperature of the first drying is 105 ℃, and the processing time is 2h; the treatment temperature of the first calcination was 500 ℃ and the treatment time was 8 hours.
Step S2, mixing the second dispersion liquid containing lithium source, aluminum source, titanium source and second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, in the lithium source, the aluminum source, the titanium source and the second phosphoric acid source, the molar ratio of Li, al, ti and P is 1.4 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source was 0.0019. The processing speed of the second ball milling is 500rpm, the processing time is 8h, the processing temperature of the second drying is 80 ℃, and the processing time is 7h; the treatment temperature of the second calcination was 920 ℃ and the treatment time was 10 hours. ZnZr in the solid electrolyte material, coating layer, obtained finally 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.0019 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The compactness is 96.41 percent.
Example 5
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, the molar ratio of Zn, zr, and P in the zinc source, the zirconium source, and the first phosphoric acid source is 1. The processing speed of the first ball milling is 300rpm, the processing time is 5h, the processing temperature of the first drying is 105 ℃, and the processing time is 1h; the treatment temperature of the first calcination was 380 ℃ and the treatment time was 10 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, the molar ratio of Li, al, ti and P in the lithium source, the aluminum source, the titanium source and the second phosphoric acid source is 1.2The dispersing agent of the dispersion liquid is absolute ethyl alcohol, the lithium source is lithium carbonate, the aluminum source is aluminum oxychloride, the titanium source is titanium chloride, the second phosphoric acid source is phosphoric acid, and ZnZr 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source was 0.0015. The processing speed of the second ball milling is 400rpm, the processing time is 7h, the processing temperature of the second drying is 100 ℃, and the processing time is 7h; the treatment temperature of the second calcination was 850 ℃ and the treatment time was 10 hours. ZnZr in the solid electrolyte material, coating layer, obtained finally 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.0015, and the structural formula of the solid electrolyte material is Li 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 The compactness is 96.21%.
Example 6
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, in the zinc source, the zirconium source and the first phosphoric acid source, the molar ratio of Zn, zr and P is 1. The processing speed of the first ball milling is 400rpm, the processing time is 5h, the processing temperature of the first drying is 110 ℃, and the processing time is 4h; the treatment temperature of the first calcination was 700 ℃ and the treatment time was 12 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, in the lithium source, the aluminum source, the titanium source and the second phosphoric acid source, the molar ratio of Li, al, ti and P is 1.5 4 (PO 4 ) 6 Molar ratio to the second phosphoric acid source is 0.02. Second ball milledThe processing speed is 500rpm, the processing time is 10h, the processing temperature of the second drying is 100 ℃, and the processing time is 8h; the treatment temperature of the second calcination was 950 ℃ and the treatment time was 12 hours. ZnZr in the solid electrolyte material, coating layer, obtained finally 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.02 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 The density is 95.41%.
Comparative example 1
And S2, carrying out second ball milling, second drying and second calcining on a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source to obtain the solid electrolyte material. Wherein, the molar ratio of Li, al, ti, and P in the lithium source, the aluminum source, the titanium source, and the second phosphoric acid source is 1.3. The processing speed of the second ball milling is 350rpm, the processing time is 6h, the processing temperature of the second drying is 80 ℃, and the processing time is 6h; the treatment temperature of the second calcination is 900 ℃ and the treatment time is 10h. The structural formula of the solid electrolyte material is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 And the compactness is 86.40 percent.
Comparative example 2
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, the mol ratio of Zn, zr, and P in the zinc source, the zirconium source, and the first phosphoric acid source is 1. The processing speed of the first ball milling is 250rpm, the processing time is 3h, the processing temperature of the first drying is 100 ℃, and the processing time is 2h; the treatment temperature of the first calcination was 500 ℃ and the treatment time was 9 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 And mixing, and performing second ball milling, second drying and second calcining to obtain the solid electrolyte material. Wherein, the molar ratio of Li, al, ti, P in the lithium source, the aluminum source, the titanium source, and the second phosphoric acid source is 1.3 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source is 0.0005. The processing speed of the second ball milling is 350rpm, the processing time is 6h, the processing temperature of the second drying is 80 ℃, and the processing time is 6h; the treatment temperature of the second calcination is 900 ℃, and the treatment time is 10h. ZnZr in the solid electrolyte material and the coating layer finally obtained 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.0005 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The compactness is 90.20%.
Comparative example 3
Step S1, carrying out first ball milling, first drying and first calcining on first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 . Wherein, in the zinc source, the zirconium source and the first phosphoric acid source, the molar ratio of Zn, zr and P is 1. The processing speed of the first ball milling is 250rpm, the processing time is 3h, the processing temperature of the first drying is 100 ℃, and the processing time is 2h; the treatment temperature of the first calcination was 500 ℃ and the treatment time was 9 hours.
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 Mixing, performing second ball milling, second drying and second calcining to obtain the solid electrolyte materialAnd (4) feeding. Wherein, the molar ratio of Li, al, ti, P in the lithium source, the aluminum source, the titanium source, and the second phosphoric acid source is 1.3 4 (PO 4 ) 6 The molar ratio to the second phosphoric acid source was 0.025. The processing speed of the second ball milling is 350rpm, the processing time is 6h, the processing temperature of the second drying is 80 ℃, and the processing time is 6h; the treatment temperature of the second calcination is 900 ℃, and the treatment time is 10h. ZnZr in the solid electrolyte material, coating layer, obtained finally 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio is 0.025 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The compactness is 91.20%.
And (3) performance testing:
(1) Compactness degree
The density is tested by adopting an Archimedes drainage method, and particularly, the mass of the solid electrolyte material before and after the Archimedes drainage method is tested is measured by using an electronic balance, so that the actual density of the sample is measured, and the density is calculated.
(2) Ionic conductivity
Preparing a wafer sample to be detected from the solid electrolyte material, recording alternating current impedances of different response frequencies by using an electrochemical workstation, analyzing different electrode processes with different reaction time constants, and obtaining the ionic conductivity of the solid electrolyte material through fitting, analysis and calculation.
(3) Differential scanning calorimetry peak temperature
The peak temperature of differential scanning calorimetry is that the ternary cathode material coated with the solid electrolyte material is tested under the following conditions: the temperature is increased from room temperature to 400 ℃, the temperature increasing rate is 10 ℃/min, and the test is carried out in the compressed air atmosphere.
The solid electrolytes prepared in the above examples and comparative examples were tested and the results are shown in table 1 below:
TABLE 1
| Density/% | Ionic conductivity X10 -4 /S/cm | Differential scanning calorimetry peak temperature/. Deg.C | |
| Example 1 | 95.36 | 2.41 | 216.5 |
| Example 2 | 95.51 | 2.71 | 217.4 |
| Example 3 | 96.87 | 3.62 | 220.1 |
| Example 4 | 96.41 | 3.41 | 219.8 |
| Example 5 | 96.21 | 2.75 | 217.6 |
| Example 6 | 95.41 | 2.45 | 218.5 |
| Comparative example 1 | 86.4 | 0.87 | 201.4 |
| Comparative example 2 | 90.2 | 1.04 | 204.3 |
| Comparative example 3 | 91.2 | 1.08 | 203.2 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
from the data of examples 1, 2, 3, 4, 5, 6 and comparative example 1, it can be seen that when the solid electrolyte material provided by the present invention is used, the solid electrolyte material includes a base material and a coating layer coated on the outer surface of the base material; wherein the structural formula of the matrix material is Li 1+x Al x Ti 2-x (PO 4 ) 3 X is more than or equal to 0.1 and less than or equal to 0.5, and the material of the coating layer is ZnZr 4 (PO 4 ) 6 When used, the resulting solid electrolyte has a higher degree of compactness (e.g., 95.36% for example 1, 95.51% for example 2, 96.87% for example 3, 96.41% for example 4, 96.21% for example 5, or 95.41% for example 6), andalso has higher ion conductivity (for example, 2.41X 10 of example 1) -4 S/cm, 2.71X 10 of example 2 -4 (S/cm), 3.62X 10 of example 3 -4 (S/cm), 3.41X 10 of example 4 -4 (S/cm), 2.75X 10 of example 5 -4 2.45X 10,/S/cm or example 6 -4 S/cm) and also has excellent thermal stability. When the solid electrolyte material is not modified, the compactness of the solid electrolyte is poor (for example, 86.4% of comparative example 1), and the corresponding ionic conductivity is low (for example, 0.87 × 10% of comparative example 1) -4 /S/cm), the heat stability performance is also poor.
From the data of examples 1, 2, 3, 4, 5, 6 and comparative examples 2, 3, it can be found that ZnZr in the coating layer thereof when the solid electrolyte of the present invention is used 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 When the molar ratio is in the range of (0.001 to 0.02): 1, the solid electrolyte has a high degree of compactness (for example, 95.36% in example 1, 95.51% in example 2, 96.87% in example 3, 96.41% in example 4, 96.21% in example 5, or 95.41% in example 6), and ZnZr 4 (PO 4 ) 6 The molar ratio of the phosphoric acid to the second phosphoric acid source is (0.001-0.02): 3. Based on this, the ionic conductivity is also high (for example, 2.41X 10 of example 1) -4 S/cm, 2.71X 10 of example 2 -4 (S/cm), 3.62X 10 of example 3 -4 S/cm, 3.41X 10 of example 4 -4 S/cm, 2.75X 10 of example 5 -4 2.45X 10,/S/cm or example 6 -4 S/cm) and also has excellent thermal stability. When ZnZr is contained in the coating layer 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 When the molar ratio is outside the range of (0.001 to 0.02): 1 (e.g., 0.0005 of comparative example 2 or 0.025 of comparative example 3 4 (PO 4 ) 6 When the molar ratio to the second phosphoric acid source is outside the range of (0.001 to 0.02): 3 (e.g., 0.0005 of comparative example 2% or 91.2% of comparative example 3), which in turn leads to a reduction in the ionic conductivity (e.g. 1.04X 10 of comparative example 2) -4 S/cm or 1.08X 10 of comparative example 3 -4 /S/cm), the thermal stability is also poor.
From the data of examples 2, 3, 4, 5 and examples 1, 6, it can be found that when the solid electrolyte of the present invention is used, the matrix material has the formula of Li 1+x Al x Ti 2-x (PO 4 ) 3 And 0.2. Ltoreq. X.ltoreq.0.4, the solid-state electrolyte has a higher compactness (95.51% for example 2, 96.87% for example 3, 96.41% for example 4, 96.21% for example 5), and on the basis thereof also a higher ionic conductivity (e.g. 2.71X 10 for example 2) -4 S/cm, 3.62X 10 of example 3 -4 S/cm, 3.41X 10 of example 4 -4 S/cm, 2.75X 10 of example 5 -4 /S/cm) and also has more excellent thermal stability. When the structural formula of the matrix material is Li 1+x Al x Ti 2-x (PO 4 ) 3 And x is out of the range of 0.2 ≦ x ≦ 0.4 (e.g., 0.1 for example 1 or 0.5 for example 6), the solid electrolyte has a higher density (e.g., 95.36% for example 1 or 95.41% for example 6), and on the basis thereof also has a higher ionic conductivity (e.g., 2.41 × 10 for example 1) -4 2.45X 10 of/S/cm or example 6 -4 /S/cm) and also has excellent thermal stability.
In conclusion, the solid electrolyte material prepared by the method has higher ionic conductivity and density, and the ternary cathode material coated by the solid electrolyte material also shows excellent thermal stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The solid electrolyte material is characterized by comprising a matrix material and a coating layer coated on the outer surface of the matrix material; wherein the content of the first and second substances,
the structural formula of the matrix material is Li 1+x Al x Ti 2-x (PO 4 ) 3 ，0.1≤x≤0.5；
The material of the coating layer is ZnZr 4 (PO 4 ) 6 。
2. The solid electrolyte material according to claim 1, wherein in the structural formula of the matrix material, x is 0.2. Ltoreq. X.ltoreq.0.4;
preferably, znZr in said cladding layer 4 (PO 4 ) 6 With Li in the matrix material 1+x Al x Ti 2-x (PO 4 ) 3 The molar ratio of (0.001-0.02) to (1).
3. The solid state electrolyte material according to any one of claims 1 or 2, wherein the density of the solid state electrolyte material is 95 to 98%.
4. A production method for the solid state electrolyte material according to any one of claims 1 to 3, characterized by comprising the steps of:
step S1, carrying out first calcination on a first dispersion liquid containing a zinc source, a zirconium source and a first phosphoric acid source to obtain ZnZr 4 (PO 4 ) 6 ；
Step S2, mixing a second dispersion liquid containing a lithium source, an aluminum source, a titanium source and a second phosphoric acid source with the ZnZr 4 (PO 4 ) 6 Mixing and carrying out secondary calcination to obtain the solid electrolyte material.
5. The method for producing a solid electrolyte material according to claim 4, characterized in that the first dispersion liquid has a pH value of 8 to 10;
preferably, the dispersant of the first dispersion is one or more of absolute ethyl alcohol, absolute methyl alcohol or ethyl acetate;
preferably, the zinc source is selected from one or more of zinc sulphide, zinc carbonate or zinc chloride;
preferably, the zirconium source is selected from one or more of zirconyl chloride, zirconium hydroxide or zirconium chloride;
preferably, the first source of phosphoric acid is selected from one or more of monoammonium phosphate, phosphoric acid or diammonium phosphate.
6. The method for producing a solid electrolyte material according to any one of claims 4 or 5, characterized in that, prior to the first calcination, the production method further comprises the steps of subjecting the first dispersion to first ball milling and first drying in this order;
preferably, the processing rotating speed of the first ball mill is 150-400 rpm, and the processing time is 2-5 h;
preferably, the treatment temperature of the first drying is 90-110 ℃, and the treatment time is 1-4 h;
preferably, the treatment temperature of the first calcination is 300-700 ℃, and the treatment time is 6-12 h.
7. The method for producing a solid electrolyte material according to claim 4, characterized in that the dispersant of the second dispersion is one or more of absolute ethanol, absolute methanol, or ethyl acetate;
preferably, the ZnZr 4 (PO 4 ) 6 The molar ratio of the phosphoric acid to the second phosphoric acid source is (0.001-0.02) 3;
preferably, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide or lithium oxide;
preferably, the aluminium source is selected from one or more of aluminium oxide, aluminium hydroxide or aluminium chloride;
preferably, the titanium source is selected from one or more of titanium oxide, titanium chloride or titanium hydroxide;
preferably, the second source of phosphoric acid is selected from one or more of monoammonium phosphate, phosphoric acid or diammonium phosphate.
8. The method for producing a solid electrolyte material according to any one of claims 4 or 7, characterized in that, prior to the second calcination, the production method further comprises the steps of subjecting the second dispersion to second ball milling and second drying in this order;
preferably, the processing rotating speed of the second ball mill is 200-500 rpm, and the processing time is 2-10 h;
preferably, the treatment temperature of the second drying is 60-100 ℃, and the treatment time is 4-8 h;
preferably, the treatment temperature of the second calcination is 850-950 ℃, and the treatment time is 8-12 h.
9. A lithium-ion solid-state battery characterized by comprising the solid-state electrolyte material of any one of claims 1 to 3, or a solid-state electrolyte material produced by the production method of the solid-state electrolyte material of any one of claims 4 to 8.
10. The application of the lithium ion solid-state battery is characterized in that the lithium ion solid-state battery is applied to an electric automobile or an electric bicycle.
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| CN117174996B (en) * | 2023-11-02 | 2024-03-05 | 合肥国轩高科动力能源有限公司 | Modified titanium aluminum lithium phosphate, preparation method thereof and lithium ion solid-state battery |
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