Composite materials for cathode materials in secondary battery, method of manufacturing the same, and lithium secondary battery including the same

Patent metadata

Field	Value
Publication number	US-11043666-B2
Application number	US-201715410122-A
Country	US
Kind code	B2
Filing date	Jan 19, 2017
Priority date	Jan 19, 2016
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

Disclosed are a composite material for cathode materials in a secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same. A composite material for cathode materials in a secondary battery includes: a charge carrier ion compound-carbon composite including a carbon particle and a charge carrier ion compound particle represented by general formula of AxDy and dispersed on a surface of the carbon particle; and a transition metal compound represented by a general formula of MzRw. In the general formulae of AxDy and MzRw, A, D, M, R, x, y, z, and w are as defined in the detailed description.

First claim

What is claimed is:

1. A composite material for a cathode material in a secondary battery, comprising:
a charge carrier ion compound-carbon composite comprising a carbon particle and a charge carrier ion compound particle represented by a general formula of A x D y and dispersed on a surface of the carbon particle, wherein the charge carrier ion compound-carbon composite is prepared by mechanochemically mixing a precursor of the charge carrier ion compound and a precursor of the carbon, wherein each of the charge carrier ion compound particle and the carbon particle has a particle diameter of about 1 nm to about 100 nm, and the charge carrier ion compound particle is uniformly mixed with the carbon particle in the charge carrier ion compound-carbon composite; and
a transition metal compound represented by a general formula of M z R w , the transition metal compound is physically mixed with the charge carrier ion compound-carbon composite,
wherein the A is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba,
the D is selected from F, N, Cl, S, P, Br, Se, I, and (OH),
the M is selected from Fe, Mn, V, Co, Ni, Ti, Nb, Mo, Y, Ag, Hf, and Ta,
the R is selected from O,
provided that when M is Fe, 0<x≤3, 0<y≤2, 0<z≤4, and 0<w≤6,
wherein, the charge carrier ion compound-carbon composite and the transition metal compound have phases that are distinguished from each other; and
the transition metal compound has granularity or a crystal phase.

2. The composite material for the cathode materials in a secondary battery of claim 1 , wherein the precursor of the charge carrier ion compound and the precursor of the carbon are mechanochemically mixed in a weight ratio of 1:0.3 to 1:3.

3. The composite material for the cathode materials in a secondary battery of claim 1 , wherein
the charge carrier ion compound-carbon composite is distributed at least adjacent to the surface of the transition metal compound.

4. The composite material for the cathode materials in a secondary battery of claim 1 , wherein
the carbon particle is an amorphous carbon particle.

5. The composite material for the cathode materials in a secondary battery of claim 1 , wherein
the carbon particle has a particle diameter of about 10 nm to about 100 nm.

6. The composite material for the cathode materials in a secondary battery of claim 1 , wherein
the charge carrier ion compound particle comprises a crystalline first particle and an amorphous second particle.

7. The composite material for the cathode materials in a secondary battery of claim 1 , wherein
the charge carrier ion compound particle has a particle diameter of about 5 nm to about 100 nm.

8. The composite material for the cathode materials in a secondary battery of claim 1 , wherein the charge carrier ion compound particle includes at least one selected from the group consisting of LiF, Li 3 N, LiI, LiCl, Li 2 S, LiOH, Li 2 CO 3 , LiBr, Li 3 PO 4 , Li 4 P 2 O 7 , Li 2 SO 4 , Li 2 CO 3 , Li 4 SiO 4 , KF, and NaF.

9. The composite material for the cathode materials in a secondary battery of claim 1 , wherein the transition metal compound having crystallinity.

10. The composite material for the cathode material in a secondary battery of claim 1 , wherein the transition metal compound includes at least one selected from the group consisting of MnO, Mn 2 O 3 , Mn 3 O 4 , CoO, Co 3 O 4 , FeO, Fe 2 O 3 , Fe 3 O 4 , V 2 O 5 , NiO, Nb 2 O 5 , and MoO 3 .

11. The composite material for a cathode material in a secondary battery of claim 1 , wherein
the transition metal compound has an average particle diameter of about 6 nm.

12. A method of manufacturing composite materials for cathode materials in a secondary battery of claim 1 , comprising:
mixing a charge carrier ion compound precursor and a carbon precursor using a mechanochemical reaction to provide the charge carrier ion compound-carbon composite; and
adding the transition metal compound into the charge carrier ion compound-carbon composite.

13. The method of manufacturing composite materials for cathode materials in a secondary battery of claim 12 , wherein
the mechanochemical reaction is performed using a high energy ball mill.

14. The method of manufacturing composite materials for cathode materials in a secondary battery of claim 12 , comprising
further adding at least one of a binder, a conductive material, and a solvent when adding the transition metal compound.

15. The method of manufacturing composite materials for cathode materials in a secondary battery of claim 12 , comprising
mixing the charge carrier ion compound-carbon composite and the transition metal compound using physical agitation.

16. A lithium secondary battery comprising:
an electrolyte;
an anode;
a cathode; and
a separator;
wherein the cathode comprising a composite material, the composite material comprising a charge carrier ion compound-carbon composite comprising a carbon particle and a charge carrier ion compound particle represented by a general formula of A x D y and dispersed on a surface of the carbon particle, wherein the charge carrier ion compound-carbon composite is prepared by mechanochemically mixing a precursor of the charge carrier ion compound and a precursor of carbon, wherein each of the charge carrier ion compound particle and the carbon particle has a particle diameter of about 1 nm to about 100 nm, and the charge carrier ion compound particle is uniformly mixed with the carbon particle in the charge carrier ion compound-carbon composite, and a transition metal compound represented by a general formula of M z R w , the transition metal compound is physically mixed with the charge carrier ion compound-carbon composite;
wherein the A is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba,
the D is selected from F, N, Cl, S, P, Br, Se, I, (OH), and (CO 3 ),
the M is selected from Fe, Mn, V, Co, Ni, Ti, Nb, Mo, Y, Ag, Hf, and Ta,
the R is O,
provided that when M is Fe, 0<x≤3, 0<y≤2, 0<z≤4, and 0<w≤6,
wherein, the charge carrier ion compound-carbon composite and the transition metal compound have phases that are distinguished from each other; and
the transition metal compound have granularity or a crystal phase.

17. The lithium secondary battery of claim 16 , wherein
the charge carrier ion is oxidized and reduced on the surface of the transition metal compound in the cathode.

18. The lithium secondary battery of claim 16 , wherein
in a state that the lithium secondary battery is charged,
the charge carrier ion compound is separated into a charge carrier ion and an anion, and the anion is chemically bonded with the transition metal compound.

Assignees

• Seoul Nat Univ R&Db Foundation

Inventors

• Kang Kisuk
• Jung Sungkyun
• Hyeon Taeghwan
• Oh Myounghwan
• CHO Min Gee

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M4/523

  for non-aqueous cells (H01M4/525 takes precedence) · CPC title

• H01M4/362 Primary

  Composites · CPC title

• H01M4/364 Primary

  as mixtures · CPC title

• H01M4/583

  Carbonaceous material, e.g. graphite-intercalation compounds or CFx · CPC title