Hollow spherical lithium-transition metal-silicate composites, preparation method thereof, and cathode active material for lithium secondary batteries comprising the same

Patent metadata

Field	Value
Publication number	US-2018170762-A1
Application number	US-201715818595-A
Country	US
Kind code	A1
Filing date	Nov 20, 2017
Priority date	Dec 16, 2016
Publication date	Jun 21, 2018
Grant date	—

Abstract

The present disclosure relates to a lithium-transition metal-silicate complex that is formed into a sphere with a hollow, in which a radius of the hollow is in a range of 0.5 to 3.0 nm, and a diameter of the lithium-transition metal-silicate complex is in a range of 5 to 10 nm. The present disclosure enables to facilitate the mass production of a complex including a lithium-transition metal-silicate complex, having a micro-sized hollow, and having a spherical shape.
In addition, when using a lithium-transition metal-silicate complex of the present disclosure as a cathode active material for a lithium secondary battery, it is capable of providing a cathode active material for a lithium-ion battery excellent in charging and discharging characteristics as well as in high-rate characteristics.
In addition, a lithium-transition metal-silicate complex manufactured according to the present disclosure may implement properties of materials of lithium, transition metal, and silicate as well as its structural characteristics, and thus, it can be effectively applied in various industrial fields.

First claim

What is claimed is:

1 . A lithium-transition metal-silicate complex,
wherein the complex is formed into a sphere with a hollow, wherein a radius of the hollow is in a range of 0.5 to 3.0 nm, and wherein a diameter of the lithium-transition metal-silicate complex is in a range of 5 to 10 nm.

2 . The lithium-transition metal-silicate complex of claim 1 ,
wherein the transition metal comprises at least one selected from a group of manganese, cobalt, nickel, and titanium.

3 . The lithium-transition metal-silicate complex of claim 2 ,
wherein the transition metal comprises manganese or cobalt.

4 . The lithium-transition metal-silicate complex of claim 1 ,
wherein the transition metal-silicate and the lithium are in a mole ratio of 1:1 to 1:16 in the complex.

5 . The lithium-transition metal-silicate complex of claim 4 ,
wherein the transition metal and the silicate are in a mole ratio of 1:1 to 1:10 in the complex.

6 . A cathode active material for a secondary battery, comprising a lithium-transition metal-silicate complex,
wherein the lithium-transition metal-silicate complex is formed into a sphere with a hollow, wherein a radius of the hollow is in a range of 0.5 to 3.0 nm, and wherein a diameter of the lithium-transition metal-silicate complex is in a range of 5 to 10 nm.

7 . The cathode active material for the secondary battery of claim 6 ,
wherein the transition metal comprises at least one selected from a group of manganese, cobalt, nickel, and titanium.

8 . The cathode active material for the secondary battery of claim 7 ,
wherein the transition metal comprises manganese or cobalt.

9 . The cathode active material for the secondary battery of claim 6 ,
wherein the transition metal-silicate and the lithium are in a mole ratio of 1:1 to 1:16 in the complex.

10 . The cathode active material for the secondary battery of claim 6 ,
wherein the transition metal and the silicate are in a mole ratio of 1:1 to 1:10 in the complex.

11 . A method for manufacturing a lithium-transition metal-silicate complex, comprising:
mixing and crushing a transition metal-silicate and a lithium precursor; and dissolving the crushed mixture in an organic solvent and conducting a hydrothermal reaction to obtain a lithium-transition metal-silicate complex being formed into a sphere with a hollow, wherein a radius of the hollow is in a range of 0.5 to 3.0 nm, and wherein a diameter of the lithium-transition metal-silicate complex is in a range of 5 to 10 nm.

12 . The method for manufacturing the lithium-transition metal-silicate complex of claim 11 ,
wherein the transition metal-silicate is obtained by conducting: a first operation of adding the solvent to the transition metal precursor to prepare a solution including the transition metal and adding the solvent to a compound including silicon to prepare a solution including silicon; a second operation of reacting the solution including the transition metal and the solution including silicon prepared in the first operation at a temperature of 100 to 300° C. for 5 to 50 hours to form a transition metal silicate; and a third operation of heat treating the transition metal silicate formed via the second operation.

13 . The method for manufacturing the lithium-transition metal-silicate complex of claim 12 , wherein the transition metal precursor is one selected from a group of Mn(NO 3 ) 2 .4H 2 O, Mn(CH 3 CO 2 ) 2 , Mn(CH 3 CO 2 ) 2 .4H 2 O, Mn(ClO 4 ) 2 .6H 2 O, MnSO 4 .xH 2 O, MnSO 4 .H 2 O, Co(NO 3 ) 2 .4H 2 O, Co(CH 3 CO 2 ) 2 , Co(CH 3 CO 2 ) 2 .4H 2 O, CO(ClO 4 ) 2 .6H 2 O, COSO 4 .xH 2 O, COSO 4 .H 2 O, Ni(NO 3 ) 2 .4H 2 O, Ni(CH 3 CO 2 ) 2 , Ni(CH 3 CO 2 ) 2 .4H 2 O, Ni(ClO 4 ) 2 .6H 2 O, NiSO 4 .xH 2 O, NiSO 4 .H 2 O, Ti(NO 3 ) 2 .4H 2 O, Ti(CH 3 CO 2 ) 2 , Ti(CH 3 CO 2 ) 2 .4H 2 O, Ti(ClO 4 ) 2 .6H 2 O, TiSO 4 .xH 2 O, TiSO 4 .H 2 O, and a combination thereof, and
wherein the compound including silicon is one selected from a group of Na 2 SiO 3 , SiCl 4 , Si(OCOCH 3 ) 4 , SiI 4 , SiF 4 , SiC 32 H 8 O 2 , SiC 48 H 26 N 8 O 2 , SiC 32 H 18 N 2 O 2 , and a combination thereof.

14 . The method for manufacturing the lithium-transition metal-silicate complex of claim 12 , wherein the transition metal precursor and the compound including silicon are reacted in a mole ratio of 1:1 to 1:10.

15 . The method for manufacturing the lithium-transition metal-silicate complex of claim 11 ,
wherein the dissolving uses ultrasonic waves, and wherein the hydrothermal reaction is conducted at 150 to 240° C. for 10 to 40 hours.

16 . The method for manufacturing the lithium-transition metal-silicate complex of claim 11 ,
wherein the transition metal-silicate and the lithium precursor are mixed in a mole ratio of 1:1 to 1:16.

17 . The method for manufacturing the lithium-transition metal-silicate complex of claim 11 ,
wherein the lithium precursor includes at least one selected from a group of lithium chloride, lithium acetate, and lithium hydroxide.

Assignees

• Korea Basic Science Inst

Inventors

• Kim Yeon Ho
• Kim Hae Jin
• Lee Jin Bae
• Hong Won Gi
• Lee Sang Moon

Classifications

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/5825

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

• C01B33/32 Primary

  Alkali metal silicates ({C01B33/24} , C01B33/26 take precedence) · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title