Sodium ion batteries

• US 20020192553A1
• Filed: 04/04/2002
• Published: 12/19/2002
• Est. Priority Date: 04/06/2001
• Status: Active Grant

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Saidi, M. Yazid, Swoyer, Jeffrey L.
• Granted Patent: US 6,872,492 B2
• Time in Patent Office: Days
• US Class Current: 429/224
• CPC Class Codes: C01B 25/455 containing halogen completely halogenated alkali metal phosphates C01D, e.g. lithium hexafluorophosphate C01D15/005
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0564 the electrolyte being constituted of organic materials only
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/40 Alloys based on alkali metals
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/582 Halogenides
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Sodium ion batteries are based on sodium based active materials selected among compounds of the general formula:

A_aM_b(XY₄)_cZ_d,

wherein A comprises sodium, M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, Z is OH or halogen, and XY₄ represents phosphate or a similar group. The anode of the battery includes a carbon material that is capable of inserting sodium ions. The carbon anode cycles reversibly at a specific capacity greater than 100 mAh/g.

Claims

1. A battery comprising a positive electrode, a negative electrode and an electrolyte wherein:

the positive electrode comprises an electrochemically active material that can reversibly cycle sodium ions; and

wherein

the negative electrode comprises a carbon capable of inserting sodium ions and that cycles reversibly at a specific capacity greater than 100 mAh/g.

2. A battery according to claim 1, wherein the negative electrode cycles reversibly at a specific capacity greater than 200 mAh/g.

3. A battery according to claim 1, wherein the negative electrode cycles reversibly at a specific capacity greater than 300 mAh/g.

4. A battery according to claim 1, wherein the carbon of the negative electrode is characterized by having an interlayer spacing d₀₀₂ greater than that found in crystalline graphite.

5. A battery according to claim 1, wherein the carbon is characterized by having an x-ray diffraction pattern having a 002 peak centered at about 24.2 degrees 2θ

and a 004 peak centered at about 43.3 degrees 2θ

.

6. A battery according to claim 1, wherein the electrochemically active material comprises a sodium transition metal phosphate.

7. A battery according to claim 6, wherein the transition metal comprises a transition metal selected from the group consisting of vanadium, manganese, iron, cobalt, copper, nickel, titanium, and mixtures thereof.

8. A battery according to claim 1, wherein the electrochemically active material comprises a sodium transition metal fluorophosphate.

9. A battery according to claim 8, wherein the transition metal comprises a transition metal selected from the group consisting of cobalt, iron, vanadium, manganese, copper, nickel, titanium, and mixtures thereof.

10. A battery according to claim 1, wherein the electrochemically active material comprises a sodium vanadium compound.

11. A battery according to claim 1 wherein the electrochemically active material comprises a material of formula Na_1+yMPO₄ F_1+y wherein y is from −

0.2 to 0.5 and M comprises a transition metal selected from the group consisting of V, Mn, Fe, Co, Cu, Ni, Ti, and mixtures thereof.

12. A battery according to claim 11, wherein M comprises vanadium.

13. A battery according to claim 1,wherein the electrochemically active material has general formula

Na₃M₂(PO₄)₃

wherein M comprises a transition metal group consisting of V, Mn, Fe, Co, Cu, Ni, Ti, and mixtures thereof.

14. A battery according to claim 13, wherein M comprises vanadium.

15. A battery according to claim 1, wherein the electrochemically active material comprises a compound of formula

NaFe_xMg₁₋

xPO₄

wherein 0<

x<

1.

16. A battery according to claim 1 wherein the electrochemically active material comprises a material of formula

Li₁₋

zNa_zMPO₄F

wherein 0<

z<

1, and M comprises a transition metal selected from the group consisting of V, Mn, Fe, Co, Cu, Ni, Ti, and mixtures thereof.

18. A battery according to claim 17 wherein XY₄ comprises phosphate.

19. A battery according to claim 17 wherein XY₄ comprises an anion selected from the group consisting of phosphate, silicate, sulfate, and mixtures thereof.

20. A battery according to claim 17, wherein XY₄ comprises an anion selected from the group consisting of X′

O<sub>4−

x</sub>Y′

_x with x greater than zero, X′

O<sub>4−

y</sub>Y′

_2y with y greater than zero, X″

S₄ and mixtures thereof.

21. A battery according to claim 17, wherein d=0.

22. A battery according to claim 17, wherein d>

0.

23. A battery according to claim 17, wherein b is about 2 and c is about 3.

24. A battery according to claim 17, wherein b is about 1 and c is about 1.

25. A battery according to claim 17, wherein the material of the negative electrode reversibly cycles sodium ions at a specific capacity greater than about 100 mAh/g.

26. A battery according to claim 17 wherein the material of the negative electrode reversibly cycles sodium ions at a specific capacity greater than about 200 mAh/g.

27. A battery according to claim 17 wherein the material of the negative electrode comprises carbon characterized by having an interlayer spacing d₀₀₂ greater than that found in crystalline graphite.

28. A battery according to claim 27, wherein the carbon is characterized as having an x-ray diffraction pattern with a 002 reflection centered at about 24.4°

2θ and

a 004 reflection centered at about 43.3°

2θ

.

30. A battery according to claim 29, wherein the active material has formula

Li₁₋

zNa_zMPO₄

wherein z is greater than 0.

31. A battery according to claim 30, wherein M comprises a metal selected from the group consisting of V, Mn, Fe, Co, Cu, Ni, Ti, and mixtures thereof.

32. A battery according to claim 29, wherein the negative electrode comprises a carbon material capable of cycling sodium ions at a specific capacity of 100 mAh/g or greater.

33. A battery according to claim 29, wherein the electrolyte comprises a source of mobile lithium ions.

34. A battery according to claim 29, wherein the positive electrode material cycles lithium ions and sodium ions.

35. A battery according to claim 29, wherein the negative electrode comprises an insertion material that cycles lithium and sodium ions.

17. A battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein

the positive electrode comprises an electrochemically active material that can reversibly cycle sodium ions;

and wherein

the negative electrode comprises a material capable of accepting and releasing sodium ions;

wherein the electrochemically active material comprises at least one compound of the formula;

A_aM_b(XY₄)_cZ_d,

wherein

(a) A is selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<

a≦

9;

(b) M comprises one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 1≦

b≦

3;

(c) 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, V, Ge, S, and mixtures thereof;

X″

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

Y′

is selected from the group consisting of halogen, S, N, and mixtures thereof;

0≦

x<

3; and

0<

y≦

2; and

0<

c≦

3;

(d) Z is OH, halogen, or mixtures thereof, and 0≦

d≦

6; and

wherein M, XY₄, Z, a, b, c, d, x and y are selected so as to maintain electroneutrality of said compound.

29. A battery comprising a positive electrode, a negative electrode, and an electrolyte, wherein the positive electrode comprises an active material of formula

A_aM_b(XY₄)_cZ_d,

wherein

(a) A is selected from the group consisting of Na and mixtures of Na and Li, and 0<

a≦

9;

(b) M comprises one or more metals, comprising at least one metal capable of undergoing oxidation to a higher valence state, and 1≦

b≦

3;

(c) 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, V, Ge, S, and mixtures thereof;

X″

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

Y′

is selected from the group consisting of halogen, S, N, and mixtures thereof;

0≦

x<

3; and

0<

y≦

2; and

0<

c≦

3;

(d) Z is OH, halogen, or mixtures thereof, and 0≦

d≦

6; and

wherein M, XY₄, Z, a, b, c, d, x and y are selected so as to maintain electroneutrality of said compound.