Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

• US 8,722,246 B2
• Filed: 04/01/2010
• Issued: 05/13/2014
• Est. Priority Date: 09/25/2006
• Status: Expired due to Fees

• Current Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Manthiram, Arumugam, Choi, Wonchang
• Primary Examiner(s): KOPEC, MARK T
• Application Number:
  US12/752,779
• Publication Number:
  US 20100183925A1
• Time in Patent Office: 1,503 Days
• Field of Search: 252/500, 252/518.1, 252/521.2, 429/218.1, 429/231.95
• US Class Current: 429/218.1
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/362 Composites
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn_2−y−zLi_yM_zO₄ oxide with NH₄HF₂ at low temperatures of between about 300 and 700° C. for 2 to 8 hours and a η of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

Claims

1. A cathode, comprising:

a LiMn<sub>2−

y−

z</sub>Li_yM_zO<sub>4−

η</sub>

F_η

cation-substituted spinel oxide material, wherein y is from about 0 to about 0.3, z is from about 0 to about 1.0, M is a metal, and η

is greater than 0 and less than about 0.5; and

one or more layered oxide materials comprising Li[Ni,Mn,Co,Li]O₂,

wherein the one or more layered oxide materials are in contact with the cation-substituted spinel oxide material.

2. The cathode of claim 1, wherein M is selected from the group consisting of Mg, Al, V, Cr, Fe, Ti, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ga, Sn and combinations thereof.

3. The cathode of claim 1, wherein the cathode comprises from about 20 wt % to about 95 wt % of the cation-substituted spinel oxide material and the cathode comprises from about 5 wt % to about 80 wt % of the one or more layered oxide materials.

4. The cathode of claim 1, wherein:

the cathode comprises from about 70 wt % to about 80 wt % of the LiMn<sub>2−

y−

z</sub>Li_yM_zO<sub>4−

η</sub>

F_η

cation-substituted spinel oxide material,

the LiMn<sub>2−

y−

z</sub>Li_yM_zO<sub>4−

η</sub>

F_η

cation-substituted spinel oxide material is selected from the group consisting of LiMn_1.8Li_0.1Ni_0.1O_3.8F_0.2, LiMn_1.8Li_0.2O_3.88F_0.12, LiMn_1.8Li_0.2O_3.79F_0.21, LiMn_1.8Li_0.1Ti_0.1O_3.9F_0.1, LiMn_1.8Li_0.1Cu_0.1O_3.9F_0.1, LiMn_1.8Li_0.1Ni_0.1O_3.9F_0.1, and combinations thereof,

the cathode comprises from about 20 wt % to about 30 wt % of the one or more layered oxide materials, and

the one or more layered oxide materials are selected from the group consisting of LiCoO₂, LiNi_0.5Mn_0.5O₂, and combinations thereof.

5. The cathode of claim 1, wherein the cation-substituted spinel oxide material is selected from the group consisting of LiMn_1.8Li_0.2O_3.88F_0.12, LiMn_1.8Li_0.2O_3.79F_0.21, LiMn_1.8Li_0.1Ti_0.1O_3.9F_0.1, LiMn_1.8Li_0.1Cu_0.1O_3.9F_0.1, LiMn_1.8Li_0.1Ni_0.1O_3.9F_0.1, LiMn_1.8Li_0.1Ni_0.1O_3.8F_0.2, and combinations thereof.

6. The cathode of claim 1, wherein the one more layered oxide materials are selected from the group consisting of LiCoO₂, LiNi_0.5Mn_0.5O₂ and combinations thereof.

7. The cathode of claim 1, wherein the cathode comprises from about 20 wt % to about 95 wt % of the cation-substituted spinel oxide material.

8. The cathode of claim 1, wherein the cathode comprises from about 70 wt % to about 80 wt % of the cation-substituted spinel oxide material.

9. The cathode of claim 1, wherein the cathode comprises from about 5 wt % to about 80 wt % of the one or more layered oxide materials.

10. The cathode of claim 1, wherein the cathode comprises from 20 wt % to about 30 wt % of the one or more layered oxide materials.