Electrode active material, preparation method thereof, and electrode and lithium battery containing the same

Patent metadata

Field	Value
Publication number	US-10147940-B2
Application number	US-201213461311-A
Country	US
Kind code	B2
Filing date	May 1, 2012
Priority date	May 4, 2011
Publication date	Dec 4, 2018
Grant date	Dec 4, 2018

Abstract

An electrode active material, a method of manufacturing the same, and an electrode and a lithium battery adopting the same. The electrode active material includes a core capable of occluding and emitting lithium; and a surface treatment layer formed on at least a portion of a surface of the core, wherein the surface treatment layer includes a lithium-free oxide having a spinel structure.

First claim

What is claimed is:

1. An electrode active material, comprising:
a core capable of occluding and emitting lithium; and
a surface treatment layer formed on at least a portion of a surface of the core, wherein the surface treatment layer comprises a lithium-free oxide having a spinel structure, wherein the lithium-free oxide is one or more oxides selected from the group consisting of SnMg 2 O 4 , SnZn 2 O 4 , MoAl 2 O 4 , CuAl 2 O 4 , ZnV 2 O 4 , TiMn 2 O 4 , NiAl 2 O 4 , ZnGa 2 O 4 , CaGa 2 O 4 , TiMg 2 O 4 , VMg 2 O 4 , FeV 2 O 4 , ZnV 2 O 4 , MgCr 2 O 4 , FeCr 2 O 4 , CoCr 2 O 4 , NiCr 2 O 4 , CuCr 2 O 4 , CdCr 2 O 4 , TiMn 2 O 4 , TiFe 2 O 4 , CoFe 2 O 4 , CdFe 2 O 4 , AlFe 2 O 4 , PbFe 2 O 4 , TiCo 2 O 4 , ZnCo 2 O 4 , SnCo 2 O 4 , FeNi 2 O 4 , GeNi 2 O 4 , ZnRh 2 O 4 , TiZn 2 O 4 , SrAl 2 O 4 , CrAl 2 O 4 , MoAl 2 O 4 , FeAl 2 O 4 , CoAl 2 O 4 , ZnGa 2 O 4 , CaIn 2 O 4 , FeIn 2 O 4 , CoIn 2 O 4 , NiIn 204 , CdIn 2 O 4 , and HgIn 2 O 4 .

2. The electrode active material of claim 1 , wherein the lithium-free oxide does not occlude and emit lithium.

3. The electrode active material of claim 1 , wherein in an X-ray diffraction spectrum of the electrode active material, I(111)/I(311), which is a ratio of peak intensity of a (111) crystal face to peak intensity of a (311) crystal face, is about 0.3 or more.

4. The electrode active material of claim 1 , wherein in an X-ray diffraction spectrum of the electrode active material, I(111)/I(400), which is a ratio of peak intensity of a (111) crystal face to peak intensity of a (400) crystal face, is about 0.6 or more.

5. The electrode active material of claim 1 , wherein the content of the lithium-free oxide is less than about 10 wt % on a basis of a total weight of the electrode active material.

6. The electrode active material of claim 1 , wherein the content of the lithium-free oxide is less than about 5 wt % on a basis of a total weight of the electrode active material.

7. The electrode active material of claim 1 , wherein the surface treatment layer comprises two or more elements selected from the group consisting of a metal and a metalloid with an atomic weight of 9 or more.

8. The electrode active material of claim 7 , wherein the elements are selected from the group consisting of Sn, Mg, Mo, Cu, Zn, Ti, Ni, Ca, Al, V, Mn, Ga, Fe, Cr, Rh, In, Pb, Co, Ge, Cd, Hg, Sr, W and Be.

9. The electrode active material of claim 1 , wherein the composition ratio of oxygen to the two or more elements selected from the group consisting of metal and metalloid with an atomic weight of 9 or more is about 4:2.1 to about 4:3.9 in the surface treatment layer.

10. The electrode active material of claim 1 , wherein the thickness of the surface treatment layer is about 1 Å to about 1 μm.

11. The electrode active material of claim 1 , wherein the core further comprises a cathode active material.

12. The electrode active material of claim 1 , wherein the core further comprises a lithium transition metal oxide.

13. The electrode active material of claim 1 , wherein the core further comprises compounds expressed as Chemical formulas 2 and 3:
Li[Li a Me 1−a ]O 2+d   <Chemical formula 2>

Li[Li b Me c M′ e ]O 2+d ,  <Chemical formula 3>

where 0<a<1, b+c+e=1; 0<b<1, 0<e<0.1; 0≤d≤0.1,
Me is one or more metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, and B, and
M′ is one or more metals selected from the group consisting of Mo, W, Ir, Ni, and Mg.

14. The electrode active material of claim 1 , wherein the core further comprises compounds expressed as Chemical formulae 4 to 8:
Li x Co 1−y M y O 2−α X α   <Chemical formula 4>

Li x Co 1−y−z Ni y M z O 2−α X α   <Chemical formula 5>

Li x Mn 2−y M y O 4−α X α   <Chemical formula 6>

Li x Co 2−y M y O 4−α X α   <Chemical formula 7>

Li x Me y M z PO 4−α X α ,  <Chemical formula 8>

where 0.90≤x≤1.1, 0≤y≤0.9, 0≤z≤0.5, 1−y−z>0, 0≤α≤2,
Me is one or more metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, and B,
M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, Si, Ni, Mn, Cr, Fe, Mg, Sr, V, and rare-earth elements, and
X is an element selected from the group consisting of O, F, S, and P.

15. The electrode active material of claim 1 , wherein the core further comprises compounds expressed as Chemical formulas 9 and 10:
p Li 2 MO 3 -(1- p )LiMeO 2   <Chemical formula 9>

x Li 2 MO 3−y LiMeO 2 - z Li 1+d M′ 2−d O 4 ,  <Chemical formula 10>

where 0<p<1, x+y+z=1; 0<x<1, 0<y<1, 0<z<1; 0≤d≤0.33,
M is one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, Si, Ni, Mn, Cr, Fe, Mg, Sr, V, and rare-earth elements,
Me is one or more metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, and B, and
M′ is one or more metals selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, and B.

16. The electrode active material of claim 1 , wherein the core further comprises an anode active material.

17. The electrode active material of claim 1 , wherein the core further comprises one or more materials selected from the group consisting of lithium metal, metal which is alloyable with lithium, transition metal oxide, non-transition metal oxide, and carbon material.

18. The electrode active material of claim 1 , wherein the core further comprise one or more materials selected from the group consisting of Si, Sn, Al, Ge, Pb, Bi, Sb, Si-T alloy, Sn—Z alloy, lithium titanium oxide, vanadium oxide, lithium vanadium oxide, SnO 2 , SiO x (o<x<2), natural graphite, artificial graphite, soft carbon, hard carbon, mesophase pitch carbide, and fired coke, wherein T and Z are Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or a combination thereof.

19. The electrode active material of claim 1 , wherein the surface treatment layer is formed by contacting a spinel-structured lithium-free oxide or a precursor thereof with the core.

20. An electrode comprising an electrode active material according to claim 1 .

21. The electrode of claim 20 , wherein the electrode is a cathode.

22. The electrode of claim 20 , wherein the electrode is an anode.

Assignees

• Choi Won Chang
• Park Jin Hwan
• Samsung Electronics Co Ltd

Inventors

• Choi Won-Chang
• Park Jin-Hwan

Classifications

• H01M10/052

  Li-accumulators · CPC title

• C01G45/1228

  of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2 · CPC title

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• H01M4/366 Primary

  as layered products · CPC title

• H01M4/131

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