Lithium ion battery having improved thermal stability
Aspects of the invention are based on the discovery that cathode materials and lithium ion batteries comprising the cathode material, having improved thermal stability may be produced from a cathode material that is comprised of a mixture of a lithium metal oxide and a lithium metal phosphate wherein the lithium metal phosphate comprises a volume fraction of secondary particles having a size of 0.1 to 3 μm that is from 5 to 100%, based on the total content of lithium metal phosphate. More specifically cathodes comprising lithium metal phosphates having the recited secondary particle ranges help provide cathode materials that are capable of passing the nail penetration test without generating smoke or flames. Methods of forming the cathode and lithium ion battery comprising the cathode are also provided.
1. A method of forming a cathode comprising:
(a) mixing a lithium metal oxide and a lithium metal phosphate in a solvent, wherein the lithium metal phosphate has a D50 equal to or less than 3.5 micrometers, has a volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is from 5 to 100%, based on the total content of the lithium metal phosphate, wherein the mixture comprises 10% to 50% by weight of lithium metal phosphate, and wherein the lithium metal oxide is represented by the following formula:
Li x Ni y Mn z Co (2−x−y−z) D w O 2 or Li x Ni y Mn z Co (2−x−y−z) O 2
wherein
x is a number from 0.9 to 1.15;
y is a number from 0.05 to 0.95;
z is a number from 0.05 to 0.95;
(2−x−y−z) is from 0.5 to 0.7; and
w is 0 to 0.4, and wherein D, when present, is selected from the group consisting of B, Al, Ti, Mg, Nb, Si, Fe, V, Cr Cu, Zn, Ga and W;
(b) coating the mixture of step (a) on to a metal foil; and
(c) removing the solvent to form the cathode having a lithium metal oxide/lithium metal phosphate coating on the metal foil, wherein the lithium metal oxide/lithium metal phosphate coating has a % theoretical density that is 40-55% of theoretical density.
2. The method of claim 1 , wherein the volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is at least 20%, based on the total content of the lithium metal phosphate.
3. The method of claim 1 , wherein the volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is at least 50%, based on the total content of the lithium metal phosphate.
4. The method of claim 1 , wherein the lithium metal phosphate has the formula:
Li 1+a Mn b Fe c M 1−b−c PO 4 , Formula (I)
wherein
a is a number from 0.0 to 0.2;
b is a number from 0.05 to 0.95;
c is a number from 0.05 to 0.95; and
(1−b−c) is from 0.0 to 0.2,
wherein M is a metal ion selected from one or more of magnesium, calcium, strontium, cobalt, titanium, zirconium, molybdenum, vanadium, niobium, nickel, scandium, chromium, copper, zinc, beryllium, lanthanum and aluminum.
5. The method of claim 1 , wherein the lithium metal phosphate comprises a mixture of two different lithium metal phosphates with a first of said lithium metal phosphates having a volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is at least 20%, and the second of said lithium metal phosphates having a volume fraction of particles having a size of 0.1 to 3 micrometers that is 0%, and wherein the mixture of lithium metal phosphates has a collective volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is at least 20%, based on the total content of the lithium metal phosphate.
6. The method according to claim 1 , wherein a pouch cell comprising the cathode of claim 1 is capable of passing a nail penetration test without generating smoke or fire.
7. A cathode material comprising a mixture of lithium metal oxide and lithium metal phosphate in a solvent, wherein the lithium metal phosphate has a D50 equal to or less than 3.5 micrometers, has a volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is from 5 to 100%, based on the total content of the lithium metal phosphate, wherein the mixture comprises 10% to 50% by weight of lithium metal phosphate, and wherein the lithium metal oxide is represented by the following formula:
Li x Ni y Mn z Co (2−x−y−z) D w O 2 or Li x Ni y Mn z Co (2−x−y−z) O 2
wherein
x is a number from 0.9 to 1.15;
y is a number from 0.05 to 0.95;
z is a number from 0.05 to 0.95;
(2−x−y−z) is from 0.5 to 0.7; and
w is 0 to 0.4, and wherein D, when present, is selected from the group consisting of B, Al, Ti, Mg, Nb, Si, Fe, V, Cr Cu, Zn, Ga and W,
wherein, when coated on a metal foil, the cathode material forms a lithium metal oxide/lithium metal phosphate coating having a % theoretical density that is 40-55% of theoretical density.
8. The cathode material of claim 7 , wherein the lithium metal phosphate comprises a volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is at least 20%, based on the total content of the lithium metal phosphate.
9. The cathode material of claim 7 , wherein the lithium metal phosphate comprises a volume fraction of secondary particles having a size of 0.1 to 3 micrometers that is at least 50%, based on the total content of the lithium metal phosphate.
10. The cathode material of claim 7 , wherein the lithium metal phosphate has the formula:
Li 1+a Mn b Fe c M 1−b−c PO 4 , Formula (I)
wherein
a is a number from 0.0 to 0.2;
b is a number from 0.05 to 0.95;
c is a number from 0.05 to 0.95; and
(1−b−c) is from 0.0 to 0.2, wherein M is a metal ion selected from one or more of magnesium, calcium, strontium, cobalt, titanium, zirconium, molybdenum, vanadium, niobium, nickel, scandium, chromium, copper, zinc, beryllium, lanthanum and aluminum.
11. The cathode material of claim 7 , wherein the lithium metal phosphate comprises a mixture of two different lithium metal phosphates, wherein
a first lithium metal phosphate comprising a 20% volume fraction of secondary particles having a size of 0.1 to 3 micrometers, and
a second lithium metal phosphate comprising a 0% volume fraction of secondary particles having a size of 0.1 to 3 micrometers is 0%, and wherein said mixture of lithium metal phosphates has at least a 20% volume fraction of secondary particles having a size of 0.1 to 3 micrometers.
12. A cathode comprised of a metal foil having a first and second face and cathode material coated on at least one face of the foil, the cathode material being comprised of a mixture of lithium metal oxide and lithium metal phosphate, wherein the lithium metal phosphate has a D50 equal to or less than 3.5 micrometers, wherein the amount of lithium metal phosphate is 10% to 50% by weight of the mixture, wherein the lithium metal phosphate comprises a volume fraction of secondary particles having a size of 0.1 to 3 micrometers is at least 20%, based on the total content of the lithium metal phosphate, and wherein the lithium metal oxide is represented by the following formula:
Li x Ni y Mn z Co (2−x−y−z) D w O 2 or Li x Ni y Mn z Co (2−x−y−z) O 2
wherein
x is a number from 0.9 to 1.15;
y is a number from 0.05 to 0.95;
z is a number from 0.05 to 0.95;
(2−x−y−z) is from 0.5 to 0.7; and
w is 0 to 0.4, and wherein D, when present, is selected from the group consisting of B, Al, Ti, Mg, Nb, Si, Fe, V, Cr Cu, Zn, Ga and W,
wherein the cathode material forms a lithium metal oxide/lithium metal phosphate coating on the metal foil, wherein the lithium metal oxide/lithium metal phosphate coating has a % theoretical density that is 40-55% of theoretical density.
13. A lithium ion battery comprising the cathode material of claim 7 .