Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries
View Patent ↗Lithium ion battery positive electrode material are described that comprise an active composition comprising lithium metal oxide coated with an inorganic coating composition wherein the coating composition comprises a metal chloride, metal bromide, metal iodide, or combinations thereof. Desirable performance is observed for these coated materials. In particular, the non-fluoride metal halide coatings are useful for stabilizing lithium rich metal oxides.
1. A lithium ion battery positive electrode material comprising an active composition comprising lithium metal oxide coated with an inorganic coating composition wherein the coating composition comprises a metal chloride, metal bromide, metal iodide, or combinations thereof and having an average voltage of at least about 3.5 volts when discharged from 4.6 volts to 2.0 volts at room temperature at a rate of C/3, wherein the lithium metal oxide is a layered-layered crystalline composition represented by a formula Li 1+b Ni α Mn β Co γ A δ O 2 , where b ranges from about 0.05 to about 0.3, α ranges from 0 to about 0.4, β range from about 0.2 to about 0.65, γ ranges from 0 to about 0.46, and δ ranges from about 0 to about 0.15, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li, or combinations thereof.
2. The positive electrode material of claim 1 wherein the coating composition comprises mono-(non-fluoride) halide of Li, Na, or other monovalent metal cations, di-(non-fluoride)halides of Mg, Zn, Ba, Sr, Ca, or other divalent metal cations, tri-(non-fluoride)halides of Al, Ga, In, or other trivalent metal cations, tetra-(non-fluoride)halides of Zr, Ti, V, or other tetravalent metal cations, penta-(non-fluoride)halides of Ta, Nb, or other pentavalent metal cations, hexa-(non-fluoride)halides of Mo, W, Ru, or other hexa-valent metal cations, or combinations thereof, wherein the non-fluoride halide includes chloride, bromide, iodide, or combinations thereof.
3. The positive electrode material of claim 1 wherein the coating composition comprises AlCl 3 , AlBr 3 , AlI 3 , or combinations thereof.
4. The positive electrode material of claim 1 wherein the coating composition is substantially free of oxygen anions.
5. The positive electrode material of claim 1 wherein the coating composition has an average coating amount from about 0.05 mole percent to about 1 mole percent.
6. The positive electrode material of claim 1 wherein the lithium metal oxide is represented by a formula Li 1+b Ni α Mn β Co γ O 2 , where b ranges from about 0.05 to about 0.3, α ranges from about 0.1 to about 0.4, β range from about 0.3 to about 0.65, γ ranges from 0.05 to about 0.4, and b+α+β+γ≈1.
7. The positive electrode material of claim 1 wherein the lithium metal oxide is represented by a formula of xLi 2 MnO 3 .(1−x)LiMO 2 , where M represents one or more metal ions having an average valance of +3, and 0<x<1.
8. The positive electrode material of claim 1 having a specific discharge capacity of at least about 260 mAh/g with a discharge rate of C/3 when discharged from 4.6V to 2.0 V at room temperature.
9. The positive electrode material of claim 1 having a specific discharge capacity of at least about 245 mAh/g when discharged from 4.6 volts to 2.0 volts at room temperature at a rate of C/3.
10. The positive electrode material of claim 1 wherein the coating composition further comprises metal fluoride.
11. A lithium ion battery comprising
a positive electrode,
a negative electrode comprising a lithium incorporation composition,
a separator between the positive electrode and the negative electrode, and
an electrolyte comprising lithium ions,
wherein the positive electrode comprises an active material, distinct electrically conductive powders, and a polymer binder,
wherein the positive electrode active material comprises an active composition comprising lithium metal oxide coated with a coating composition comprising a metal chloride, metal bromide, metal iodide, or combinations thereof, the lithium metal oxide is a layered-layered crystalline composition represented by a formula Li 1+b Ni α Mn β Co γ A δ O 2 , where b ranges from about 0.05 to about 0.3, α ranges from 0 to about 0.4, β range from about 0.2 to about 0.65, γ ranges from 0 to about 0.46, and δ ranges from about 0 to about 0.15, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li, or combinations thereof, and the positive electrode active material having an average voltage of at least about 3.5 volts over a discharge from 4.5 to 2 volts at a rate of C/10 and a specific discharge specific capacity of at least about 160 mAh/g at cycle 500 at room temperature at a discharge rate of C/3 from 4.5 volts to 2 volts.
12. The lithium ion battery of claim 11 wherein the coating composition comprises AlCl 3 , AlBr 3 , AlI 3 , or combinations thereof.
13. The lithium ion battery of claim 11 wherein the positive electrode active composition comprises from about 0.025 mole percent to about 5 mole percent the metal chloride, metal bromide, metal iodide, or combinations thereof.
14. The lithium ion battery of claim 11 wherein the lithium metal oxide is represented by a formula of xLi2MnO3.LiMnO 2 , where M represents one or more metal ions having an average valance of +3, and 0<x<1.
15. The lithium ion battery of claim 14 wherein 0.1≦x≦0.45.
16. The lithium ion battery of claim 11 wherein the lithium ion battery has a first cycle irreversible capacity loss that is reduced by at least about 25% relative to the irreversible capacity loss of a battery formed with an uncoated lithium metal oxide.
17. The lithium ion battery of claim 11 wherein the positive electrode active material having a discharge specific capacity of at least about 170 mAh/g at cycle 500 at a discharge rate of C/3 from 4.5 volts to 2 volts.
18. The lithium ion battery of claim 11 wherein the coating composition is substantially free of oxygen anions.
19. The lithium ion battery of claim 11 wherein the coating composition has an average coating amount from about 0.05 mole percent to about 1 mole percent.
20. The lithium ion battery of claim 11 wherein the lithium metal oxide is represented by a formula Li 1+b Ni α Mn β Co δ O 2 , where b ranges from about 0.05 to about 0.3, α ranges from about 0.1 to about 0.4, β range from about 0.3 to about 0.65, γ ranges from 0.05 to about 0.4, and b+α+β+γ≈1.
21. The lithium ion battery of claim 11 wherein the positive electrode active material has a specific discharge capacity of at least about 245 mAh/g when discharged from 4.6 volts to 2.0 volts at room temperature at a rate of C/3.
22. The lithium ion battery of claim 11 wherein the positive electrode active material has an average voltage of at least about 3.65 at room temperature at a discharge rate of C/3 from 4.5 volts to 2 volts.
23. A method for making a positive electrode material coated with a metal/metalloid halide, the method comprising:
milling a powder of the positive electrode material with a selected amount of a powder of the metal/metalloid halide to coat the positive electrode material with the metal/metalloid halide to form the positive electrode active material of claim 1 .