Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries

Patent metadata

Field	Value
Publication number	US-11233239-B2
Application number	US-202117213975-A
Country	US
Kind code	B2
Filing date	Mar 26, 2021
Priority date	Mar 27, 2020
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

Abstract

Described herein are low or no-cobalt materials useful as electrode active materials in a cathode for lithium or lithium-ion batteries. For example, compositions of matter are described herein, such as electrode active materials that can be incorporated into an electrode, such as a cathode. The disclosed electrode active materials exhibit high specific energy and voltage, and can also exhibit high rate capability and/or long operational lifetime.

First claim

What is claimed is:

1. An electrode active material comprising:
Li a Ni 1-b-c Co b M c O d , wherein:
a is from 0.9 to 1.1,
b is from 0 to 0.03,
c is from 0 to 0.67,
d is from 1.9 to 2.1, and
M is Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these, and wherein the electrode active material exhibits or is characterized by a dQ·dV −1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.19 V to 4.30 V vs. Li + /Li.

2. The electrode active material of claim 1 , wherein M comprises at least Al.

3. The electrode active material of claim 1 , wherein b is 0 or wherein b is less than 0.01.

4. The electrode active material of claim 1 , wherein a is from 0.9 to 1.

5. The electrode active material of claim 1 , wherein a is from 1 to 1.1.

6. The electrode active material of claim 1 , wherein b is from 0 to 0.01 and wherein c is from 0 to 0.01.

7. The electrode active material of claim 1 , wherein d is from 1.95 to 2.05.

8. The electrode active material of claim 1 , exhibiting or characterized by a tapped density of from 2.0 g·cm −3 to 3.5 g·cm −3 .

9. The electrode active material of claim 1 , exhibiting or characterized by a specific energy for a single discharge between 4.4 V and 3 V vs. Li + /Li of from 600 Wh·kg −1 to 1000 Wh·kg −1 .

10. The electrode active material of claim 1 , exhibiting or characterized by a specific energy for a single discharge between 4.4 V and 3 V vs. Li + /Li at a 1C discharge rate of from 600 Wh·kg −1 to 1000 Wh·kg −1 at 25° C.

11. The electrode active material of claim 1 , wherein the minimum is at a voltage of from 4.20 V to 4.30 V vs. Li + /Li.

12. The electrode active material of claim 1 , wherein the minimum has a magnitude of from −3000 mAh·g −1 V −1 to −300 mAh·g −1 V −1 .

13. The electrode active material of claim 1 , exhibiting or characterized by a specific energy after 500 charge-discharge cycles of more than 80% of an original specific energy of from 600 Wh·kg −1 to 1000 Wh·kg −1 .

14. The electrode active material of claim 1 , exhibiting or characterized by a specific energy after 1000 charge-discharge cycles of more than 80% of an original specific energy of from 600 Wh·kg −1 to 1000 Wh·kg −1 .

15. The electrode active material of claim 1 , wherein only a portion comprises or is characterized by a rhombohedral crystal structure or a rhombohedral R 3 m crystal structure.

16. The electrode active material of claim 1 , having or characterized by a surface region and a bulk region, wherein the surface region corresponds to a first portion of the active material or particles thereof within 20% of a cross-sectional dimension from a surface of the active material or particles thereof, and wherein the bulk region corresponds to a second portion of the active material or particles thereof deeper than the surface region.

17. The electrode active material of claim 16 , wherein the bulk region is free or substantially free of or does not exhibit a spinel, P4 3 32 or Fd 3 m crystal structure, a lithium-excess or C2/m crystal structure, a rock salt or Fm 3 m crystal structure, or LiFePO 4 (Pmnb/Pnma) or another polyanionic crystal structure.

18. The electrode active material of claim 16 , wherein at least a portion of the surface region comprises or is characterized by a spinel, P4 3 32 or Fd 3 m crystal structure, a lithium-excess or C2/m crystal structure, a rock salt or Fm 3 m crystal structure, or LiFePO 4 (Pmnb/Pnma) or another polyanionic crystal structure.

19. The electrode active material of claim 1 , comprising particles of Li a N 1-b-c Co b M c O d having cross-sectional dimensions of from 500 nm to 30 μm.

20. The electrode active material of claim 1 , comprising a plurality of particles, which are substantially monodisperse and substantially spherical in shape.

21. An electrode active material comprising:
Li a Ni 1-b-c Co b M c O d , wherein:
a is from 0.9 to 1.1,
b is from 0 to 0.03,
c is from 0 to 0.67,
d is from 1.9 to 2.1, and
M is Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these; and
wherein the electrode active material exhibits or is characterized by a specific energy for a single discharge for a current rate of C/10 between 4.4 V and 3 V vs. Li + /Li of from 850 Wh·kg −1 to 1000 Wh·kg −1 at 25° C.

22. The electrode active material of claim 21 , wherein the electrode active material further exhibits or is further characterized by a specific energy for a 1C discharge rate between 4.4 V and 3 V vs. Li + /Li at 25° C. that is from 85% to 100% of the specific energy for a C/10 discharge rate between 4.4 V and 3 V vs. Li + /Li at 25° C.

23. The electrode active material of claim 21 , wherein the electrode active material further exhibits or is further characterized by a specific energy for a 1C discharge rate between 4.4 V and 3 V vs. Li + /Li at 25° C. that is from 90% to 100% of the specific energy for a C/10 discharge rate between 4.4 V and 3 V vs. Li + /Li at 25° C.

24. The electrode active material of claim 21 , exhibiting a dQ·dV −1 curve at the second charge-discharge formation cycle, for a current rate of C/10, which has a minimum with a magnitude of from −3000 mAh·g −1 V −1 to −300 mAh·g −1 V −1 during discharge at a voltage of from 4.15 V to 4.30 V vs. Li + /Li.

25. An electrode comprising the electrode active material of claim 1 .

26. An electrochemical cell, comprising:
a cathode, the cathode comprising the electrode of claim 25 ;
an anode; and
an electrolyte between the cathode and the anode.

27. The electrochemical cell of claim 26 , wherein the anode comprises graphite, carbon, silicon, lithium titanate (Li 4 Ti 5 O 12 ), tin, antimony, zinc, phosphorous, lithium, or a combination thereof.

28. The electrochemical cell of claim 26 , wherein the electrolyte is a liquid electrolyte, a semi-solid electrolyte, or a solid electrolyte.

29. The electrode active material of claim 21 , wherein M comprises at least Al.

Assignees

• Univ Texas

Inventors

• Manthiram Arumugam
• Li Wangda
• Lee Steven

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• C01P2002/52

  containing elements as dopants · CPC title

• C01P2006/11

  Powder tap density · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• C01P2004/52

  highly monodisperse size distribution · CPC title