Nitride- and oxide-modified electrode compositions and their methods of making

Patent metadata

Field	Value
Publication number	US-10044038-B2
Application number	US-201414473099-A
Country	US
Kind code	B2
Filing date	Aug 29, 2014
Priority date	Sep 3, 2013
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Compositions and methods of making compositions are provided for nitride- and/or oxide-modified electrode compositions. In certain embodiments, the nitride- and/or oxide-modified compositions have the general formula M1−zM′zOaF3−xNy. Such compositions may be used as bulk or surface compositions, and used in a battery as the anode or cathode. In other embodiments, the electrode includes a surface coating composition selected from metal nitrides and metal oxides, and a core composition having the formula M1−zM′zOaF3−x, or an oxide fluoride.

First claim

What is claimed is:

1. An electrode for a battery comprising:
a nitride- or oxide-modified composition having the following formula:
M 1-z M′ z O a F 3-x N y ,

wherein:
0<z<1;
−3≤x<0 or 0<x≤3;
0≤a≤1.5;
y>0;
M is selected from the group consisting of: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Bi; and
M′ is selected from the group consisting of: Na, Mg, Al, P, K, Ca, Sc, Cr, Fe, Cu, Zn, Ga, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

2. The electrode of claim 1 , wherein a>0 and x=3.

3. The electrode of claim 1 , wherein the composition has a structure selected from the group consisting of: a ReO 3 -type structure, a rutile-type structure, a bixbyite-type structure, or a combination thereof.

4. The electrode of claim 1 , wherein the composition is a bulk composition or a surface coating composition.

5. The electrode of claim 4 , wherein the electrode further comprises a metal fluoride core composition.

6. The electrode of claim 1 , wherein the composition is used as a cathode in a lithium-ion battery further comprising an anode and an electrolyte, wherein the battery has at least one of the following performance characteristics:
(a) a capacity at least 700 mAh/g at a rate of C/10, a capacity of at least 300 mAh/g at a rate of 1 C, or a capacity of at least 100 mAh/g at a rate of 10 C; and
(b) a functional discharge capacity of at least 50%, 60%, 70%, 80%, or 90% of the initial discharge capacity after 100 cycles.

7. An electrode for a battery comprising:
a surface coating composition comprising the nitride- or oxide-modified composition of claim 1 ;
a core composition having the formula
M 1-z M′ z O a F 3-x ,

wherein:
0≤a≤1.5;
0≤z≤1;
−3≤x<0 or 0<x≤3;
M is selected from the group consisting of: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Bi; and
M′ is selected from the group consisting of: Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

8. A battery comprising:
an anode;
a cathode;
an electrolyte capable of supporting reversible deposition and stripping of metal at the anode, and reversible intercalation and deintercalation of the metal at the cathode;
wherein either the anode or the cathode comprises a nitride- or oxide-modified composition,
wherein the nitride- or oxide-modified composition has the following formula,
M 1-z M′ z O a F 3-x N y ,

wherein:
0<z<1;
−3≤x<0 or 0<x≤3;
0≤a≤1.5;
y>0;
M is selected from the group consisting of: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Bi; and
M′ is selected from the group consisting of: Na, Mg, Al, P, K, Ca, Sc, Cr, Fe, Cu, Zn, Ga, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

9. The battery of claim 8 , wherein a>0 and x=3.

10. The battery of claim 8 , wherein the nitride- or oxide-modified composition comprises a surface coating composition and a core composition,
wherein the surface coating composition comprises the nitride- or oxide-modified composition of claim 8 , and the core composition is M 1-z M′ z O a F 3-x , wherein:
0≤a≤1.5;
0≤z≤1;
−3≤x<0 or 0<x≤3;
M is selected from the group consisting of: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Bi; and
M′ is selected from the group consisting of: Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

11. The battery of claim 8 , wherein the anode comprises the nitride- or oxide-modified metal composition and the cathode comprises an active material selected from the group consisting of one or more phases: LiCoO 2 , LiMn 2 O 4 , Li 2 MnO 3 , LiNiO 2 , Li(Mn 1.5 Ni 05 )O 4 , LiFePO 4 , Li 2 FePO 4 F, Li 3 CoNiMnO 6 , and Li(Li a Ni x Mn y Co z )O 2 , or wherein the cathode comprises the nitride- or oxide-modified composition and the anode comprises an active material selected from the group consisting of: lithium ion, sodium ion, carbon, and graphite.

12. The battery of claim 8 , wherein the battery is selected from the group consisting of the following battery types: lithium-ion, aluminum-ion, magnesium-ion, sodium-ion, metal-air, and metal-sulfur, wherein the metal is lithium, aluminum, magnesium, zinc, or sodium.

13. The battery of claim 8 having at a capacity at least 700 mAh/g at a rate of C/10, a capacity of at least 300 mAh/g at a rate of 1 C, or a capacity of at least 100 mAh/g at a rate of 10 C, and having a functional discharge capacity of at least 90% of the initial discharge capacity after 100 cycles.

14. An electrode for a battery comprising:
a nitride- or oxide-modified composition having the following formula:
M 1-z M′ z O a F 3-x N y ,

wherein:
0<z<1;
−3≤x<0 or 0<x≤3;
0≤a≤1.5;
y>0;
M is selected from the group consisting of: Cr, Fe, Cu, and Bi; and
M′ is selected from the group consisting of: Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, and Bi.

15. The electrode of claim 14 , wherein a>0 and x=3.

16. A battery comprising:
an anode;
a cathode;
an electrolyte capable of supporting reversible deposition and stripping of metal at the anode, and reversible intercalation and deintercalation of the metal at the cathode;
wherein either the anode or the cathode comprises a nitride- or oxide-modified composition of claim 14 .

17. An electrode for a battery comprising:
a nitride- or oxide-modified composition having a formula selected from: V 1-z Mn z O a F 3-x N y , V 1-z Ti z O a F 3-x N y , V 1-z Co z O a F 3-x N y , V 1-z Ni z O a F 3-x N y , V 1-z Si z O a F 3-x N y , V 1-z Sn z O a F 3-x N y , V 1-z Ge z O a F 3-x N y , Cr 1-z Si z O a F 3-x N y , Cr 1-z Sn z O a F 3-x N y , Cr 1-z Ge z O a F 3-x N y , Fe 1-z Si z O a F 3-x N y , Fe 1-z Sn z O a F 3-x N y , Fe 1-z Ge z O a F 3-x N y , Cu 1-z Si z O a F 3-x N y , Cu 1-z Sn z O a F 3-x N y , Cu 1-z Ge z O a F 3-x N y , Bi 1-z Si z O a F 3-x N y , Bi 1-z Sn z O a F 3-x N y , Bi 1-z Ge z O a F 3-x N y , Ti 1-z Mn z O a F 3-x N y , Ti 1-z Co z O a F 3-x N y , Ti 1-z Ni z O a F 3-x N y , Ti 1-z V z O a F 3-x N y , Mn 1-z Ti z O a F 3-x N y , Mn 1-z Co z O a F 3-x N y , Mn 1-z Ni z O a F 3-x N y , Mn 1-z V z O a F 3-x N y , Co 1-z Ti z O a F 3-x N y , Co 1-z Mn z O a F 3-x N y , Co 1-z Ni z O a F 3-x N y , Co 1-z V z O a F 3-x N y , Ni 1-z Ti z O a F 3-x N y , Ni 1-z Co z O a F 3-x N y , Ni 1-z Mn z O a F 3-x N y , and Ni 1-z V z O a F 3-x N y , wherein:
0<z<1;
−3≤x<0 or 0<x≤3;
0≤a≤1.5; and
y>0.

18. A battery comprising:
an anode;
a cathode;
an electrolyte capable of supporting reversible deposition and stripping of metal at the anode, and reversible intercalation and deintercalation of the metal at the cathode;
wherein either the anode or the cathode comprises a nitride- or oxide-modified composition of claim 17 .

Assignees

• Ut Battelle Llc

Inventors

• Bridges Craig A
• Paranthaman Mariappan Parans
• Veith Gabriel M
• Bi Zhonghe

Classifications

• H01M4/366

  as layered products · CPC title

• H01M4/58 Primary

  of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title