Method of preparing inorganic particles and inorganic particles prepared using the same

Patent metadata

Field	Value
Publication number	US-9722246-B2
Application number	US-201314440202-A
Country	US
Kind code	B2
Filing date	Nov 26, 2013
Priority date	Nov 26, 2012
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

Disclosed is a method of preparing inorganic particles using a hydrothermal synthesis device, including introducing a precursor liquid or slurry stream including a reaction precursor for preparation of an inorganic material into a hydrothermal synthesis reactor, introducing a supercritical liquid stream including water into the hydrothermal synthesis reactor, preparing an inorganic slurry by hydrothermal reaction in the hydrothermal synthesis reactor and discharging the inorganic slurry therefrom, and filtering the discharged inorganic slurry, wherein the precursor liquid or slurry stream includes an NH 3 source at a high temperature of the supercritical liquid stream and thus clogging of the stream in the hydrothermal synthesis reactor is inhibited by pH changes in the hydrothermal reaction.

First claim

The invention claimed is:

1. A method of preparing inorganic particles using a hydrothermal synthesis device, the method comprising:
introducing a precursor liquid or slurry stream comprising a reaction precursor for preparation of an inorganic material into a hydrothermal synthesis reactor;
introducing at least one supercritical liquid stream comprising high temperature and high pressure water into the hydrothermal synthesis reactor;
preparing an inorganic slurry by hydrothermal reaction in the hydrothermal synthesis reactor and discharging the inorganic slurry therefrom; and
filtering the discharged inorganic slurry to obtain a filtrate,
wherein the precursor liquid or slurry stream comprises an NH 3 source at the high temperature of the supercritical liquid stream and the NH 3 source adjusts the pH of the inorganic slurry to within a range of 3.5 to 8 to inhibit clogging of the stream in the hydrothermal synthesis reactor.

2. The method according to claim 1 , wherein the hydrothermal synthesis device comprises a structure in which a precursor liquid or slurry stream containing a precursor for preparation of an inorganic material is included, and a supercritical liquid stream containing high-temperature and high-pressure water is included, and the precursor liquid or slurry stream and the supercritical liquid stream are introduced into the hydrothermal synthesis reactor to undergo hydrothermal reaction and an inorganic slurry as a reaction product is discharged therefrom.

3. The method according to claim 1 , wherein an inorganic material of the inorganic slurry is at least one selected from the group consisting of CO 2 O 3 , Fe 2 O 3 , LiMn 2 O 4 , MO x where M is Fe, Ni, Co, Mn, or Al and x is a number satisfying electroneutrality, MOOH where M is at least one selected from the group consisting of Fe, Ni, Co, Mn, and Al, and A a M m X x O o S s N n F f where A is at least one selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba; M comprises at least one transition metal and optionally comprises at least one selected from the group consisting of B, Al, Ga, and In; X is at least one selected from the group consisting of P, As, Si, Ge, Se, Te, and C; O is oxygen; S is sulfur; N is nitrogen; F is fluorine; and a, m, x, o, s, n, and f are each independently a number of 0 or more, satisfying electroneutrality.

4. The method according to claim 3 , wherein the inorganic material is Li a M b M′ c PO 4 where M is at least one selected from the group consisting of Fe, Ni, Co, and Mn; M′ is at least one selected from the group consisting of Ca, Ti, S, C, and Mg; and a, b, and c are each independently a number of 0 or more, satisfying electroneutrality.

5. The method according to claim 4 , wherein the inorganic material is LiFePO 4 .

6. The method according to claim 1 , wherein a material causing the clogging is γ-Fe 2 O 3 .

7. The method according to claim 1 , wherein the NH 3 source is urea.

8. The method according to claim 1 , wherein the hydrothermal synthesis device further comprises a pre-mixer for preparation of a precursor to provide the precursor liquid or slurry stream.

9. The method according to claim 1 , wherein an injection direction of the precursor liquid or slurry stream into the reactor forms an angle of 0° to 60° based on a discharge direction of an inorganic slurry stream comprising the inorganic slurry.

10. The method according to claim 9 , wherein the injection direction of the precursor liquid or slurry stream forms an angle of 0° to 45° based on the discharge direction of the inorganic slurry stream comprising the inorganic slurry.

11. The method according to claim 1 , wherein a ratio of flow rates per hour of the precursor liquid or slurry stream and the supercritical liquid stream is 1:2 to 1:50 (precursor liquid or slurry stream: supercritical liquid stream) on a weight ratio basis.

12. The method according to claim 1 , wherein the supercritical liquid stream comprising high-temperature and high-pressure water has a temperature of 100° C. to 700° C. and a pressure of 10 to 550 bar.

13. The method according to claim 1 , wherein the introducing at least one supercritical liquid stream comprising high temperature and high pressure water into the hydrothermal synthesis reactor comprises:
introducing a first supercritical liquid stream in a first injection direction; and
introducing a second supercritical liquid stream in a second injection direction.

14. The method according to claim 13 , wherein the first injection direction is facing the second injection direction with respect to an injection direction of the precursor liquid or slurry stream.

15. The method according to claim 13 , wherein the first and second injection directions of the first supercritical liquid stream and the second supercritical liquid stream forms an angle of greater than 0° to less than 180° based on a discharge direction of the inorganic slurry stream.

16. The method according to claim 15 , wherein each injection direction forms an angle of 10° to 170° based on the discharge direction of the inorganic slurry stream.

17. The method according to claim 1 , wherein an injection direction of the precursor liquid or slurry stream and a discharge direction of the inorganic slurry stream are arranged in a straight line.

18. The method according to claim 1 , wherein an injection direction of the precursor liquid or slurry stream and a discharge direction of an inorganic slurry stream are not arranged in a straight line.

19. An inorganic slurry prepared using the method according to claim 1 .

20. An inorganic material obtained by drying the inorganic slurry according to claim 19 .

21. The inorganic material according to claim 20 , wherein the inorganic material is used as a cathode active material for a secondary battery.

22. A method of preparing inorganic particles using a hydrothermal synthesis device, the method comprising:
introducing a precursor liquid or slurry stream comprising LiOH, FeSO 4 , phosphoric acid and an NH3 source
introducing at least one supercritical liquid stream comprising high-temperature and high-pressure water into the hydrothermal synthesis reactor;
preparing an inorganic slurry by hydrothermal reaction in the hydrothermal synthesis reactor and discharging the inorganic slurry therefrom; and
filtering the discharged inorganic slurry;
adding sucrose to the filtered discharged inorganic slurry;
spray-drying the filtered discharged inorganic slurry to obtain a sucrose-coated LiFePO4 powder;
heat treating the sucrose-coated powder to obtain carbon-coated LiFePO 4 that has a substantially pure LiFePO 4 crystal structure;
wherein the NH 3 source is at a high temperature of the supercritical liquid stream and adjusts the slurry to a pH between 4 and 9.

23. The method according to claim 1 , wherein the NH 3 source adjusts the pH of the inorganic slurry to within a range of 3.5 to 7.8.

Assignees

• Lg Chemical Ltd

Inventors

• Noh Hyun Kuk
• Park Hong Kyu
• Ryu Ji Hoon
• Jung Wang Mo
• Oh Sang Seung
• Jo Chi Ho

Classifications

• H01M4/049

  Manufacturing of an active layer by chemical means · CPC title

• H01M4/5825 Primary

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

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• C01B25/45

  containing plural metal, or metal and ammonium · CPC title