Solid-state lithium ion conductor

Patent metadata

Field	Value
Publication number	US-12255306-B2
Application number	US-202117244043-A
Country	US
Kind code	B2
Filing date	Apr 29, 2021
Priority date	Apr 29, 2020
Publication date	Mar 18, 2025
Grant date	Mar 18, 2025

Abstract

The disclosure relates to a method for producing a solid-state lithium ion conductor material in which the use of water and/or steam is a medium when the obtained intermediate product is cooled or quenched and, if needed, comminution of the intermediate product and/or carrying out of a cooling process with the production of a powder in one comminution step or in a plurality of comminution steps leads or lead to especially advantageous production products. The subject of the disclosure is also the solid-state lithium ion conductor material that has an ion conductivity of at least 10 −5 S/cm at room temperature as well as a water content of <1.0 wt %. The disclosure further relates to the use of the solid-state lithium ion conductor material in the form of a powder in batteries or rechargeable batteries, preferably lithium batteries or rechargeable lithium batteries, in particular, separators, cathodes, anodes, or solid-state electrolytes.

First claim

What is claimed is:

1. A method for producing a solid-state lithium ion conductor material, the method comprising the following steps:
(1) providing starting products of a solid-state lithium ion conductor material based on a lithium lanthanum zirconium oxide (LLZO),
wherein the starting products have an excess of lithium in comparison to a stochiometric composition to compensate for loss due to contact with water;
(2) carrying out at least one heating process with the starting products of the solid-state lithium ion conductor material to obtain an intermediate product, wherein the heating process is selected from the group consisting of a melting process, a sintering process, a ceramization process, a calcination of a sol-gel precursor, and a bottom-up synthesis in the pulsation reactor;
(3) feeding the intermediate product onto a channel of a water chute that has an entire bottom surface covered with flowing cold water to cool or quench the intermediate product by contact with the cold water and to form droplets of the intermediate material and controlling a diameter of the droplets by adjusting: a flow rate of the cold water, a feed distance from the water chute, and an angle of inclination of the water chute; and
(4) processing the intermediate product to produce a powder in at least one comminution step.

2. The method according to claim 1 , wherein the starting products have an excess of lithium in a molar range of 2% to 100% compared to a stochiometric composition.

3. The method according to claim 1 , wherein, in step (3), when the intermediate product is cooled or quenched, the intermediate product is comminuted at the same time.

4. The method according to claim 3 , wherein the comminution in step (3) is an atomization of the intermediate product to form droplets or the separation of the intermediate product into particles.

5. The method according to claim 1 , wherein, in step (3), the intermediate product is in a liquid state and comes into contact with cold water, and is atomized into droplets with the use of the water chute.

6. The method according to claim 5 , and wherein the angle of inclination of the water chute in the range of 10-75°, and the adjusted amount of water flow is in the range of 0.1-3 m 3 /min, and the adjusted diameter of the droplets is less than 20 mm.

7. The method according to claim 6 , wherein the adjusted diameter of the droplets is between 0.5 mm and 1 mm.

8. The method according to claim 1 , wherein, after step (3) and prior to step (4), an intermediate step is carried out, the intermediate step comprising the annealing of the cooled intermediate product for adjustment of a desired crystal structure with a defined temperature-time program comprising a heating, a holding, and a cooling step and for the heating, holding, and cooling step in each case intermediate holding steps if needed.

9. The method according to claim 8 , wherein the intermediate step is carried out repeatedly to adjust a desired crystal phase composition and the crystal fraction.

10. The method according to claim 1 , further comprising a method step (5) after step (4), wherein step (5) comprises the carrying out of a thermal treatment for removal of residual water remaining in the intermediate product, wherein the thermal treatment is at a temperature of at least 200° C., wherein the thermal treatment is carried out in the absence of CO 2 in an ambient atmosphere, and wherein the thermal treatment results a powder of a solid-state lithium ion conductor material with a water content of <1.0 wt %.

11. The method according to claim 10 , wherein step (5) is carried out at a temperature of at least 300° C.

12. The method according to claim 1 , wherein, in the cooling process of step (4), the raw product is transformed into powder form with a desired particle size and particle size distribution, the transformation comprising at least one of the following steps:
comminution with hammer and chisel;
comminution with roller crusher and/or jaw crusher;
comminution with ball mill and/or hammer mill;
comminution with ball mill, impact mill, and/or planetary mill;
comminution with vibrating disc mill;
comminution with counterjet mill, spiral jet mill, and/or steam-jet mill;
comminution with dry ball mill and/or wet ball mill;
comminution with dry agitator ball mill and/or wet agitator ball mill; and
comminution by high-energy grinding in high-kinetic rotary ball mill.

13. The method according to claim 1 , further comprising, in step (4), contacting the intermediate product with cold water while processing the intermediate product, and subsequently drying the intermediate product.

14. The method according to claim 1 , further comprising, in step (3), drying the intermediate product after the cooling or quenching the intermediate product, and in step (4), contacting the intermediate product with cold water during the processing the intermediate product, and subsequently drying the intermediate product.

15. The method according to claim 1 , wherein the at least one comminution step in step (4) comprises a plurality of comminution steps.

16. The method according to claim 1 , wherein the diameter is controlled so that the droplets have a diameter of less than 20 mm.

17. The method according to claim 1 , wherein the water flow rate is adjusted in a range of 0.1 to 3 m 3 /min.

18. The method according to claim 1 , wherein the angle of inclination is adjusted from 10° to 75°.

19. The method according to claim 1 , wherein step (4) comprises creating small frit particles directly supplied to a fine grinding process, without a multistage coarse comminution process.

20. The method according to claim 19 , wherein the fine grinding process is performed while the intermediate product is in contact with water.

21. A method for producing a solid-state lithium ion conductor material, the method comprising the following steps:
(1) providing starting products of lithium aluminum titanium phosphate (LATP), wherein the starting products have an excess of lithium in comparison to a stochiometric composition;
(2) carrying out at least one heating process with the starting products of the solid-state lithium ion conductor material to obtain an intermediate product, wherein the heating process is selected from the group consisting of a melting process, a sintering process, a ceramization process, a calcination of a sol-gel precursor, and a bottom-up synthesis in the pulsation reactor;
(3) cooling or quenching the intermediate product by contact with cold water while the intermediate product is in a liquid state when contacted with the cold water so that the intermediate product is atomized into droplets, and
wherein the cold water is provided by a water chute and after an initial contact with the cold water, the droplets are produced from a cushion of vapor resulting from the initial contact so that further contact of the droplets with the water is prevented; and
(4) processing the intermediate product to produce a powder in at least one comminution step.

22. The method according to claim 21 , wherein, after step (3) and prior to step (4), an intermediate step of annealing the droplets is carried out with a defined temperature-time program to adjust a desired crystal phase composition and the crystal fraction of the droplets.

23. The method according to claim 21 , wherein step (3) comprises:
feeding the intermediate product onto a channel of a water chute that has an entire bo

Assignees

• Schott Ag

Inventors

• Schumacher Jörg
• Treis Philipp
• Stöhr Ulrike
• Kirsch Thomas
• Schmidbauer Wolfgang
• Roters Andreas

Classifications

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• C01P2006/82

  water content · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01P2004/60

  Particles characterised by their size · CPC title