Lithium-containing silicon/phosphates, method of preparation, and uses thereof including as electrodes for a battery

• US 6,136,472 A
• Filed: 06/26/1998
• Issued: 10/24/2000
• Est. Priority Date: 06/26/1998
• Status: Expired due to Term

• Current Assignee: Lithium Werks Technology BV
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Saidi, M. Yazid
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): Ruthkosky, Mark
• Application Number:
  US09/105,748
• Time in Patent Office: 851 Days
• Field of Search: 429/218, 429/231.1, 429/218.2, 429/231.95
• US Class Current: 429/218.1
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• 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 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 50/409 Separators, membranes or diaphragms characterised by the material
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The invention provides a new electrode active material and cells and batteries which utilize such active material. The active material is represented by the nominal general formula Li_a M'"'"'.sub.(2-b) M"_b Si_c P.sub.(3-c) O₁₂, 0≦b≦2, 0<c<3. M'"'"' and M" are each elements selected from the group consisting of metal and metalloid elements. The value of the variable a depends upon the selection of M'"'"' and M" and on the relative proportions designated as b and c.

Claims

1. A lithium ion battery which comprises a positive electrode and a negative electrode;

said negative electrode comprising an active material consisting of an insertion material in a pre-charge state;

said positive electrode having an active material comprising a silicophosphate compound of the nominal general formula Li_a M'"'"'.sub.(2-b) M"_b Si_c P_3-c O₁₂, 0≦

b≦

2, 0<

c<

3, a is greater than zero and selected to represent the number of Li atoms to balance said formula;

where M'"'"' and M" are the same or different from one another and are each elements selected from the group consisting of metal and metalloid elements; and

wherein said compound is characterized by extraction of lithium ions therefrom during charging cycle of said battery;

said negative electrode active material characterized by inserting said extracted lithium ions during said charging cycle, and by subsequent extraction of lithium ions therefrom during discharge cycle; and

said compound further characterized by reinserting said discharge cycle lithium ions.

2. The battery according to claim 1 wherein M'"'"' and M" are the same transition metal or are different transition metals.

3. The battery according to claim 1 wherein at least one of M'"'"' and M" is selected from the group of transition metals.

4. The battery according to claim 1 wherein M'"'"' and M" are independently selected from the group consisting of:

V, Fe, Ni, Co, Cr, Mn, Ti, Al, Mo, Zr, W, Al, In, Sn, Pb, Tl, Os, Ir and Pt.

5. The battery according to claim 1 wherein said positive electrode active material is represented by the formula Li₃ M'"'"'.sub.(2-b) M"_b SiP₂ O₁₂ ;

M'"'"' has a +3 valence state; and

M" has a +4 valence state.

6. The battery according to claim 1 wherein said active material is represented by the formula Li₃ M'"'"'.sub.(2-b) M"_b SiP₂ O₁₂ ;

M'"'"' is selected from the group consisting of;

V, Zr, Mn, Ti, Mo and W; and

M" is selected from the group consisting of;

V, Fe, Ni, Co, Cr, Mn, Zr, Ti, Mo and W.

7. The battery according to claim 1 wherein said active material is represented by the formula Li₃.5 M'"'"'.sub.(2-b) M"_b Si₀.5 P₂.5 O₁₂ ;

and M'"'"' and M" each have a +3 valence state.

8. The battery according to claim 1 wherein said active material is represented by the formula Li₃.5 M'"'"'.sub.(2-b) M"_b Si₀.5 P₂.5 O₁₂ ;

and M'"'"' and M" are independently selected from the group consisting of;

Al, V, Fe, Ni, Co, Cr, Mn, Ti, Mo and W.

9. The battery according to claim 1 wherein said active material is selected from the group consisting of:

Li₃ VVSiP₂ O₁₂ ;

Li₃ MnVSiP₂ O₁₂ ;

Li₃ TiVSiP₂ O₁₂ ;

Li₃ TiCrSiP₂ O₁₂ ;

Li₃.5 AlVSi₀.5 P₂.5 O₁₂ ;

Li₃.5 VVSi₀.5 P₂.5 O₁₂ ; and

Li₃.5 AlCrSi₀.5 P₂.5 O₁₂.

10. An electrochemical cell having an electrode which comprises an active material, said active material represented by the following formula:

space="preserve" listing-type="equation">Li.sup.+1.sub.(a-y) MI.sup.d.sub.(2-b) MII.sup.e.sub.b Si.sup.+4.sub.c P.sup.+5.sub.(3-c) O.sup.-2.sub.12'"'"' ;

(A) where each superscript value represents the oxidation states of respective elements in a first condition, y=0;

Superscript +1 is the oxidation state of one atom of Li (lithium),

Superscript d is the oxidation state of one atom of MI,

Superscript e is the oxidation state of one atom of MII,

Superscript +4 is the oxidation state of one atom of Si (silicon),

Superscript +5 is the oxidation state of one atom of P (phosphorous),

Superscript -2 is the oxidation state of one atom of O (oxygen) and in the case of O₁₂, constitutes a total of -24;

(B) MI and MII are the same or different and are each elements independently selected from the group of metal and metalloid elements;

(C) a, c, d and e are each greater than zero;

d and e are each at least one;

0≦

b≦

2;

c is less than 3; and

where a, b, c, d and e fulfill the requirement;

(a×

1)+((2-b)×

d)+(b×

e)+(5×

(3-c))+(4×

c)=24; and

(D) in a second condition represented by said formula with 0<

y≦

a, and in said second condition, said oxidation state of MI is represented by d'"'"' and said oxidation state of MII is represented by e'"'"', said amount y of Li is removed from said compound, accompanied by a change in oxidation state of at least one of said MI and MII, according to ((2-b)×

(d'"'"'-d))+(b(e'"'"'-e))=y;

where d'"'"'≧

d and e'"'"'≧

e; and

where d, d'"'"', e, and e'"'"' are each less than or equal to 8.

11. The cell according to claim 10 wherein d and e are each at least 2, 0<

b≦

2, and d, d'"'"', e, and e'"'"' are each less than or equal to 6.

12. The cell according to claim 10 wherein d, d'"'"', e and e'"'"' are each less than or equal to 7;

and at least one of the following two conditions are met;

(1) d'"'"'>

d and (2) e'"'"'>

e.

13. The cell according to claim 10 wherein MI and MII are each independently selected from the group consisting of:

V, Fe, Ni, Co, Cr, Mn, Ti, Al, Mo and Zr.

14. An electrode having an active material comprising a silicophosphate in a first condition represented by the nominal general formula Li_3-x E'"'"'.sub.(2-b) E"_b Si_c P.sub.(3-c) O₁₂, x=0, 0≦

b≦

2, 0<

c<

3;

where at least one of E'"'"' and E" is an element selected from the group consisting of metals and metalloids; and

E'"'"' and E" are the same or different from one another; and

in a second condition by the nominal general formula Li_3-x E'"'"'.sub.(2-b) E"_b Si_c P.sub.(3-c) O₁₂, 0<

x≦

3;

where at least one of E'"'"' and E" has an oxidation state higher than its oxidation state in said first condition.

15. An electrode which comprises an active material, represented by the nominal general formula Li_a M'"'"'.sub.(2-b) M"_b Si_c P.sub.(3-c) O₁₂, 0≦

b≦

2, 0<

c<

3, a is greater than zero and selected to represent the number of Li atoms to balance said formula; and

where M'"'"' and M" are each elements selected from the group consisting of metal and metalloid elements, and said M'"'"' and M" are the same or different from one another.

16. The electrode according to claim 15 wherein M'"'"' and M" are each independently selected from the group consisting of transition metals.

17. The electrode according to claim 15 wherein at least one of M'"'"' and M" is selected from the group of transition metals.

18. The electrode according to claim 15 wherein M'"'"' is a transition metal and M" is a metalloid or non-transition-metal metal.