Electrodes Comprising Mixed Active Particles

• US 20070141468A1
• Filed: 02/20/2007
• Published: 06/21/2007
• Est. Priority Date: 04/03/2003
• Status: Abandoned Application

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy
• Application Number:
  US11/676,707
• Publication Number:
  US 20070141468A1
• Time in Patent Office: Days
• US Class Current: 429/231.100
• 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 4/364 as mixtures
• 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: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A battery containing a first electrode and a second electrode, and an electrolyte for transferring ionic charge-carriers there between, wherein the first electrode contains a first electrode active material represented by the formula A²_eM⁴_kM⁵_mM⁶_nM⁷_oO_g, and at least one second electrode active material selected from the group consisting of active materials represented by the formula A¹_aM¹_b(XY₄)_cZ_d, active materials represented by the formula A³_hMn_iO₄, and mixtures thereof.

Claims

1. A battery, comprising:

a first electrode comprising a first electrode active material represented by the formula A²_eM⁴_kM⁵_mM⁶_nM⁷_oO_g, and further comprising at least one second electrode active material selected from the group consisting of active materials represented by the formula A¹_aM¹_b(XY₄)_cZ_d, active materials represented by the formula A³_hMn_iO₄, and mixtures thereof;

a second electrode which is a counter-electrode to the first electrode; and

an electrolyte;

wherein;

(1) A¹, A², and A³ are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<

a≦

8, 0<

e≦

6 and 0<

h≦

2;

(2) M¹ is one or more metals, comprising at least one metal which, when the active material is in its nascent state, is capable of undergoing oxidation to a higher valence state, and 0.8≦

b≦

3;

(3) M⁴, M⁵ and M⁶ are each independently selected from the group consisting of elements from Groups 4 through 11 of the Periodic Table and are different from one another, and k, m and n are each greater than 0;

(4) M⁷ is selected from the group consisting of elements from Groups 2, 3 and 12 thorugh 16 of the Periodic Table, and 0≦

o; and

(5) XY₄ is selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x, X′

O<sub>4−

y</sub>Y′

_2y, X″

S₄, and mixtures thereof, where X′

is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof;

X″

is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof;

Y′

is a halogen;

0≦

x<

3;

0<

y<

2; and

0<

c≦

3;

(6) Z is selected from the group consisting of OH, a halogen, and mixtures thereof, and 0≦

d≦

6; and

(7) 0<

g≦

15; and

wherein M¹, M⁴, M⁵, M⁶, M⁷, XY₄, Z, a, b, c, d, e, g, hi, k, m, n and o are selected so as to maintain electroneutrality of each electrode active material in its nascent state.

2. The battery of claim 1, wherein the second electrode active material is represented by the formula A¹_aM¹_b(XY₄)_cZ_d.

3. The battery of claim 2, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

n−

oCo_mMn_nM⁷_oO₂, wherein 0<

m,n<

1, 0<

m+n+o<

1 and 0≦

o<

1.

4. The battery of claim 2, wherein the first electrode active material is represented by the formula A²_eNi_kCo_mMn_nM⁷_oO₂, wherein 0.8≦

e≦

1.2, 0<

k, m, n<

1, 0<

o <

1, and 0.8≦

k+m+n+o≦

1.2.

5. The battery of claim 2, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

nCo_mMn_nO₂, wherein 0<

m,n<

1 and 0<

m+n<

1.

6. The battery of claim 2, wherein the second electrode active material is represented by the formula

Li_aM¹¹_b(PO₄)Z_d,

wherein

(i) 0.1<

a≦

4;

(ii) M¹¹ is one or more metals, comprising at least one metal which, when the second electrode active material is in its nascent state, is capable of undergoing oxidation to a higher valence state, and 0.8≦

b≦

1.2; and

(iii) Z is a halogen, and 0≦

d≦

4; and

wherein M¹¹, Z, a, b, and d are selected so as to maintain electroneutrality of the second active material in its nascent state.

7. The battery of claim 6, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

n−

oCo_mMn_nM⁷_oO₂, wherein 0<

m,n<

1, 0<

m+n+o<

1 and 0≦

o<

1.

8. The battery of claim 6, wherein the first electrode active material is represented by the formula A²_eNi_kCo_mMn_nM⁷_oO₂, wherein 0.8≦

e≦

1.2, 0<

k, m, n<

1, 0≦

o<

1, and 0.8≦

k+m+n+o≦

1.2.

9. The battery of claim 6, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

nCo_mMn_nO₂, wherein 0<

m,n<

1 and 0<

m+n<

1.

10. The battery of claim 6, wherein M¹¹ comprises at least one element from Groups 4 to 11 of the Periodic Table, and at least one element from Groups 2, 3, and 12 through 16 of the Periodic Table.

11. The battery of claim 10, wherein M¹¹ includes a metal selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof;

and further includes a metal selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.

12. The battery of claim 6, wherein 0<

d≦

4.

13. The battery of claim 2, wherein the second electrode active material is represented by the formula

A¹_aM¹_b(XY₄)₃Z_d,

wherein 2≦

a≦

8 and 1≦

b≦

3; and

wherein M¹, XY₄, Z, a, b, d, x and y are selected so as to maintain electroneutrality of the second active material in its nascent state.

14. The battery of claim 13, wherein M¹ is selected from the group consisting of Ti, V, Cr and Mn, and XY₄ is PO₄.

15. The battery of claim 13, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

n−

oCo_mMn_nM⁷_oO₂, wherein 0<

m,n<

1, 0<

m+n+o<

1 and o≦

o<

1.

16. The battery of claim 13, wherein the first electrode active material is represented by the formula A²_eNi_kCo_mMn_nM⁷_oO₂, wherein 0.8≦

e≦

1.2, 0<

k, m, n<

1, 0≦

o<

1, and 0.8≦

k+m+n+o≦

1.2.

17. The battery of claim 13, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

nCo_mMn_nO₂, wherein 0<

m,n<

1 and 0<

m+n<

1.

18. The battery of claim 1, wherein the second electrode active material is represented by the formula A³_hMn_iO₄.

19. The battery of claim 18, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

n−

oCo_mMn_nM⁷_oO₂, wherein 0<

m,n<

c 1, 0<

m+n+o<

1 and o≦

o<

1.

20. The battery of claim 18, wherein the first electrode active material is represented by the formula A²_eNi_kCo_mMn_nM⁷_oO₂, wherein 0.8≦

e≦

1.2, 0<

k, m, n<

1, 0≦

o<

1, and 0.8≦

k+m+n+o≦

1.2.

21. The battery of claim 18, wherein the first electrode active material is represented by the formula A²Ni₁₋

m−

nCo_mMn_nO₂, wherein 0<

m,n<

1 and 0<

m+n<

1.

22. The battery of claim 18, wherein the second electrode active material has an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn⁺⁴ relative to the inner region.

23. The battery of claim 1, wherein the second electrode comprises an intercalation material.

24. The battery of claim 23, wherein the intercalation material is carbon.