Composite nitride, method of preparing the same, electrode active material including the composite nitride, electrode including the electrode active material, and lithium secondary battery including the electrode

Patent metadata

Field	Value
Publication number	US-9337482-B2
Application number	US-201213688469-A
Country	US
Kind code	B2
Filing date	Nov 29, 2012
Priority date	Nov 29, 2011
Publication date	May 10, 2016
Grant date	May 10, 2016

Abstract

A composite nitride, a method of preparing the composite nitride, an electrode active material including the composite nitride, an electrode including the electrode active material, and a lithium secondary battery including the electrode, the composite nitride including a core material including a bronze-phase titanium oxide; and a nitrogen atom doped on at least part of the core material.

First claim

What is claimed is:

1. A composite nitride, comprising:
a core material including a bronze-phase titanium oxide; and
a nitrogen atom doped on at least part of the core material,
wherein the composite nitride is formed by thermally treating a core material including a bronze-phase titanium oxide in contact with a nitrogen precursor gas at a temperature of about 300° C. to about 400° C.

2. The composite nitride as claimed in claim 1 , wherein the composite nitride is a compound represented by Formula 1, below:
TiO x N y H z   [Formula 1]

wherein, in Formula, 1.0≦x≦2.0, 0<y≦1.0, and 0≦z≦1.0.

3. The composite nitride of claim 1 , wherein the bronze-phase titanium oxide is a compound represented by Formula 2 below:
Ti 1+x O 2+y   [Formula 2]

wherein, in Formula 2, −0.2≦x≦0.2 and −0.2≦y≦0.2.

4. The composite nitride as claimed in claim 1 , wherein:
the core material further includes a lithium titanium oxide, and
the core material is a composite material of the bronze-phase titanium oxide and the lithium titanium oxide.

5. The composite nitride as claimed in claim 4 , wherein the composite nitride is a compound represented by Formula 3 below:
Li x TiO y N z H u   [Formula 3]

wherein, in Formula 3, 0<x≦2.0, 1.0≦y≦2.5, 0<z≦1.0, and 0≦u≦1.0.

6. The composite nitride as claimed in claim 4 , wherein the lithium titanium oxide is a compound represented by Formula 4 below:
Li 4+a Ti 5−b M c O 12−d   [Formula 4]

wherein, in Formula 4, −0.2≦a≦0.2, −0.3≦b≦0.3, 0≦c≦0.3, and −0.3≦d≦0.3; and
M is at least one selected from among metals of Groups 1-6, Group 8, and Groups 12-15 of the periodic table of elements.

7. The composite nitride as claimed in claim 6 , wherein M in Formula 4 is at least one selected from the group of lithium (Li), sodium (Na), magnesium (Mg), aluminum (Al), calcium (Ca), strontium (Sr), chromium (Cr), vanadium (V), iron (Fe), cobalt (Co), nickel (Ni), zirconium (Zr), zinc (Zn), silicon (Si), yttrium (Y), niobium (Nb), gallium (Ga), tin (Sn), molybdenum (Mo), tungsten (W), barium (Ba), lanthanum (La), cerium (Ce), silver (Ag), tantalum (Ta), hafnium (Hf), ruthenium (Ru), bismuth (Bi), antimony (Sb), and arsenic (As).

8. The composite nitride as claimed in claim 4 , wherein the composite material of the bronze-phase titanium oxide and the lithium titanium oxide has an atomic ratio of lithium to titanium of about from 0.3 to about 1.8.

9. The composite nitride as claimed in claim 1 , wherein:
an X-ray photoelectron spectrum (XPS) of the composite nitride includes a nitrogen peak with a binding energy of from about 397 eV to about 402 eV and a titanium peak with a binding energy of from about 457 eV to about 461 eV and from about 463 eV to about 467 eV, and
a composition ratio of nitrogen to titanium that is calculated from areas of the nitrogen peak with the binding energy of from about 397 eV to about 402 eV and the titanium peak with the binding energy of from about 457 eV to about 461 eV is from about 1:220 to about 1:350.

10. The composite nitride as claimed in claim 1 , wherein:
an X-ray photoelectron spectrum (XPS) of the composite nitride includes a nitrogen peak with a binding energy of from about 397 eV to about 402 eV, and an oxygen peak with a binding energy of from about 529 eV to about 532 eV, and
a composition ratio of nitrogen to oxygen that is calculated from areas of the nitrogen peak and the oxygen peak is from about 1:140 to about 1:150.

11. The composite nitride as claimed in claim 1 , wherein an X-ray diffraction spectrum of the composite nitride with a CuK-α X-ray wavelength of 1.541 Å includes a peak with a Bragg angle 2θ of from about 23° to about 27°.

12. The composite nitride as claimed in claim 1 , wherein the composite nitride is a compound represented by TiO x N y H z (x=1.98, y=0.01, and z=0.01), a compound represented by TiO x N y H z (x=1.99, y=0.01, and z=0), a compound represented by Li x TiO y N z H u (x=0.33, y=2.23, z=0.05, and u=0.05), or a compound represented by Li x TiO y N z H u (x=0.33, y=2.32, z=0.01, and u=0).

13. An electrode active material comprising the composite nitride as claimed in claim 1 .

14. An electrode comprising the electrode active material as claimed in claim 13 .

15. A lithium secondary battery comprising the electrode as claimed in claim 14 .

16. A method of preparing a composite nitride, the method comprising thermally treating a core material including a bronze-phase titanium oxide in contact with a nitrogen precursor gas at a temperature of about 300° C. to about 400° C.

17. The method as claimed in claim 16 , wherein:
the core material further includes a lithium titanium oxide, and
the core material is a composite material of the bronze-phase titanium oxide and the lithium titanium oxide.

18. The method as claimed in claim 17 , wherein the composite material of the bronze-phase titanium nitride and the lithium titanium oxide is prepared by:
mixing the bronze-phase titanium nitride and the lithium titanium oxide to obtain a mixture; and
thermally treating the mixture.

19. The method as claimed in claim 17 , wherein the lithium titanium oxide is included in an amount of from about 0.01 moles to about 99 moles, based on 1 mole of the bronze-phase titanium oxide.

20. The method as claimed in claim 16 , wherein the bronze-phase titanium oxide is prepared by:
mixing anatase TiO 2 and a 10 M to 18 M sodium hydroxide aqueous solution to form a mixture,
performing a hydrothermal synthesis reaction on the mixture at a temperature of about 150° C. to about 180° C. to form a sodium titanate,
subjecting the sodium titanate to a proton exchange reaction in an acidic solution to form hydrogen titanate,
thermally treating the hydrogen titanate under an air or oxygen atmosphere at about 300 ° C. to about 400° C. for about 3 to about 7 hours.

Assignees

• Kim Ryoung-Hee
• Song Min-Sang
• Kim Gue-Sung
• Kim So-Yeon
• Choi Young-Min
• Choi Won-Chang
• Samsung Sdi Co Ltd

Inventors

• Kim Ryoung-Hee
• Song Min-Sang
• Kim Gue-Sung
• Kim So-Yeon
• Choi Young-Min
• Choi Won-Chang

Classifications

• C01B21/0821

  Oxynitrides of metals, boron or silicon · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• H01M4/58

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title