SECONDARY ELECTROCHEMICAL CELL WITH HIGH RATE CAPABILITY

• US 20080261113A1
• Filed: 11/14/2007
• Published: 10/23/2008
• Est. Priority Date: 11/15/2006
• Status: Abandoned Application

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Huang, Haitao, Saidi, M. Yazid
• Application Number:
  US11/939,837
• Publication Number:
  US 20080261113A1
• Time in Patent Office: Days
• US Class Current: 429/221
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 4/1315 containing halogen atoms, e.g. LiCoOxFy
• 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 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The invention provides an electrochemical cell which includes a first electrode having a electrode active material, a second electrode which is a counter electrode to the first electrode, and an electrolyte. The negative electrode active material is represented by the general formula E_fTi_gD_hO_i.

Claims

1. A battery, comprising:

a first electrode comprising a first electrode active material represented by the general formula;

A_aM_bL_cZ_d,

wherein;

A. A is selected from the group consisting of elements from Group I of the Periodic Table, and mixtures thereof, and 0≦

a≦

9;

B. M includes at least one redox active element, and 0<

b≦

4;

C. L is selected from the group consisting of X′

[O_4-x,Y′

_x], X′

[O_4-y,Y′

_2y], X″

S₄, [X_z′

″

,X′

_1-z]O₄, and mixtures thereof, wherein;

i) X′ and

X′

″

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

ii) X″

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

iii) Y′

is selected from the group consisting of halogens selected from Group 17 of the Periodic Table, S, N, and mixtures thereof;

iv) 0≦

x≦

3, 0≦

y≦

2, 0≦

z≦

1 and 0<

z≦

3; and

v) Z is selected from the group consisting of a hydroxyl (OH), a halogen selected from Group 17 of the Periodic Table, and mixtures thereof, and 0≦

e≦

4; and

vi) wherein A, M, L, Z, a, b, c and d are selected so as to maintain electroneutrality of the first electrode active material in its nascent state;

a second counter-electrode comprising a counter-electrode active material represented by the general formula;

E_fTi_gD_hO_i,

wherein;

(i) E is selected from the group consisting of elements from Group I of the Periodic Table, and mixtures thereof, and 0<

f<

12;

(ii) 0<

g≦

6;

(iii) D is selected from the group consisting of Al, Zr, Mg, Ca, Zn, Cd, Fe, Mn, Ni, Co, and mixtures thereof, and 0≦

h≦

2; and

(iv) 2≦

i≦

12; and

(v) wherein E, D, f, g, h and i are selected so as to maintain electroneutrality of the second counter-electrode active material in its nascent state; and

an electrolyte in ion-transfer communication with the first electrode and the second electrode.

2. A battery according to claim 1, wherein the electrolyte is a RTIL electrolyte selected from the group consisting of compounds represented by general formulas (A) through (K):

3. The battery according either claim 2, wherein the first electrode active material is represented by the general formula:

A_aM_bPO₄Z_d,

wherein 0.1<

a≦

4, 8≦

b≦

1.2 and 0≦

d≦

4; and

wherein A, M, Z, a, b, and d are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

4. The battery according to claim 2, wherein the first electrode active material is represented by the general formula:

AM′

_1-jM″

_jPO₄,

wherein M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table and has a +2 valence state;

M″

is at least one metallic element which is from Group 2, 12, or 14 of the Periodic Table and has a +2 valence state; and

0<

j<

1.

5. The battery according to claim 2, wherein the first electrode active material is represented by the general formula:

LiFe_1-kM″

_kPO₄,

wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof; and

0<

k<

1.

6. The battery according to claim 2, wherein the first electrode active material is represented by the general formula:

A_aCo_uFe_vM¹³_wM¹⁴_aaM¹⁵_bbL,

wherein;

(vi) composition variable A is as described herein above, 0<

a≦

2

(vii) u>

0 and v>

0;

(viii) M¹³ is one or more transition metals, wherein w≧

0;

(ix) M¹⁴ is one or more +2 oxidation state non-transition metals, wherein aa≧

0;

(x) M¹⁵ is one or more +3 oxidation state non-transition metals, wherein bb≧

0;

(xi) L is selected from the group consisting of X′

O_4-xY′

_x, X′

O_4-yY′

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

0≦

x≦

3; and

0<

y≦

2; and

wherein 0<

(u+v+w+aa+bb)<

2, and M¹³, M¹⁴, M¹⁵, L, a, u, v, w, aa, bb, x, and y are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

7. The battery according to claim 2, wherein the first electrode active material is represented by the general formula:

LiM(PO_4-xY′

_x),

wherein M is M¹⁶_ccM¹⁷_ddM¹⁸_eeM¹⁹_ff, and

(xii) M¹⁶ is one or more transition metals;

(xiii) M¹⁷ is one or more +2 oxidation state non-transition metals;

(xiv) M¹⁸ is one or more +3 oxidation state non-transition metals;

(xv) M¹⁹ is one or more +1 oxidation state non-transition metals;

(xvi) Y′

is halogen; and

wherein cc>

0, each of dd, ee, and ff≧

0, (cc+dd+ee+ff)≦

1, and 0≦

x≦

0.2 and M¹⁶, M¹⁷, M¹⁸, M¹⁹, Y, cc, dd, ee, ff, and x are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

8. The battery according to claim 2, wherein the first electrode active material is represented by the general formula:

A¹_a(MO)_ggM′

_1-ggXO₄,

wherein

(i) A¹ is independently selected from the group consisting of Li, Na, K and mixtures thereof, 0.1<

a<

2;

(ii) M comprises at least one element, having a +4 oxidation state, which is redox active;

0<

gg≦

1;

(iii) M′

is one or more metals selected from metals having a +2 and a +3 oxidation state; and

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

wherein A¹, M, M′

, X, a and gg are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

9. The battery according to claim 2, wherein the first electrode active material is represented by the general formula:

A_aM_bL₃Z_d,

wherein 2≦

a≦

8, 1≦

b≦

3, and 0≦

d≦

6; and

wherein M, L, Z, a, b, d, x and y are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

10. The battery according to claim 2, wherein the second counter-electrode active material is selected from the group consisting of Li₄Ti₅O₁₂;

Li₅Ti₄AlO₁₂;

rutile and anatase forms of TiO₂, including magneli type phases having the general formula Ti_nO_2n-1(4≦

n≦

9);

TiO;

Ti₄O₅;

Ti₃O₅;

LiTiO₂;

Ti₄O₇;

Li₂Ti₃O₇; and

LiTi₂O₄.

11. The battery according to claim 10, wherein the second counter-electrode active material is Li₄Ti₅O₁₂.

12. The battery according either claim 1, wherein the first electrode active material is represented by the general formula:

A_aM_bPO₄Z_d,

wherein 0.1<

a≦

4, 8≦

b≦

1.2 and 0≦

d≦

4; and

wherein A, M, Z, a, b, and d are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

13. The battery according to claim 1, wherein the first electrode active material is represented by the general formula:

AM′

_1-jM″

_jPO₄,

wherein M′

is at least one transition metal from Groups 4 to 11 of the Periodic Table and has a +2 valence state;

M″

is at least one metallic element which is from Group 2, 12, or 14 of the Periodic Table and has a +2 valence state; and

0<

j<

1.

14. The battery according to claim 1, wherein the first electrode active material is represented by the general formula:

LiFe_1-kM″

_kPO₄,

wherein M″

is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof; and

0<

k<

1.

15. The battery according to claim 1, wherein the first electrode active material is represented by the general formula:

A_aCo_uFe_vM¹³_wM¹⁴_aaM¹⁵_bbL,

wherein;

(xvii) composition variable A is as described herein above, 0<

a≦

2

(xviii) u>

0 and v>

0;

(xix) M¹³ is one or more transition metals, wherein w≧

0;

(xx) M¹⁴ is one or more +2 oxidation state non-transition metals, wherein aa≧

0;

(xxi) M¹⁵ is one or more +3 oxidation state non-transition metals, wherein bb≧

0;

(xxii) L is selected from the group consisting of X′

O_4-xY′

_x, X′

O_4-yY′

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

0≦

x≦

3; and

0<

y≦

2; and

wherein 0<

(u+v+w+aa+bb)<

2, and M¹³, M¹⁴, M¹⁵, L, a, u, v, w, aa, bb, x, and y are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

16. The battery according to claim 1, wherein the first electrode active material is represented by the general formula:

LiM(PO_4-xY′

_x),

wherein M is M¹⁶_ccM¹⁷_ddM¹⁸_eeM¹⁹_ff, and

(xxiii) M¹⁶ is one or more transition metals;

(xxiv) M¹⁷ is one or more +2 oxidation state non-transition metals;

(xxv) M¹⁸ is one or more +3 oxidation state non-transition metals;

(xxvi) M¹⁹ is one or more +1 oxidation state non-transition metals;

(xxvii) Y′

is halogen; and

wherein cc>

0, each of dd, ee, and ff≧

0, (cc+dd+ee+ff)≦

1, and 0≦

x≦

0.2 and M¹⁶, M¹⁷, M¹⁸, M¹⁹, Y, cc, dd, ee, if, and x are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

17. The battery according to claim 1, wherein the first electrode active material is represented by the general formula:

A¹_a(MO)_ggM′

_1-ggXO₄,

wherein

(i) A¹ is independently selected from the group consisting of Li, Na, K and mixtures thereof, 0.1<

a<

2;

(ii) M comprises at least one element, having a +4 oxidation state, which is redox active;

0<

gg≦

1;

(iii) M′

is one or more metals selected from metals having a +2 and a +3 oxidation state; and

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

wherein A¹, M, M′

, X, a and gg are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

18. The battery according to claim 1, wherein the first electrode active material is represented by the general formula:

A_aM_bL₃Z_d,

wherein 2≦

a≦

8, 1≦

b≦

3, and 0≦

d≦

6; and

wherein M, L, Z, a, b, d, x and y are selected so as to maintain electroneutrality of the electrode active material in its nascent or as-synthesized state.

19. The battery according to claim 1, wherein the second counter-electrode active material is selected from the group consisting of Li₄Ti₅O₁₂;

Li₅Ti₄AlO₁₂;

rutile and anatase forms of TiO₂, including magneli type phases having the general formula Ti_nO_2n-1(4≦

n≦

9);

TiO;

Ti₄O₅;

Ti₃O₅;

LiTiO₂;

Ti₄O₇;

Li₂Ti₃O₇; and

LiTi₂O₄.

20. The battery according to claim 19, wherein the second counter-electrode active material is Li₄Ti₅O₁₂.