Early transition metal stabilized high capacity cobalt free cathodes for lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-2020403216-A1
Application number	US-201916448169-A
Country	US
Kind code	A1
Filing date	Jun 21, 2019
Priority date	Jun 21, 2019
Publication date	Dec 24, 2020
Grant date	—

Abstract

A cathode for a lithium battery includes LiNi0.5-x/2Mn0.5-x/2MxO2 where M is at least one selected from the group consisting of Mo, Ti, Cr, Zr and V, and x is between 0.005-0.02. The LiNi0.5-x/2Mn0.5-x/2MxO2 can be coated with Mn2P2O7. The Mn2P2O7 can be 1-3 wt. %, based on the total weight of the LiNi0.5-x/2Mn0.5-x/2 MxO2 and Mn2P2O7. A cathode composition, a lithium battery, and a method of making a lithium battery are also disclosed.

First claim

We claim:

1 . A cathode for a lithium battery, comprising LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 where M is at least one selected from the group consisting of Mo, Ti, Cr, Zr and V, and x is between 0.005-0.02.

2 . The cathode of claim 1 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is coated with Mn 2 P 2 O 7 .

3 . The cathode of claim 2 , wherein the Mn 2 P 2 O 7 is 1-3 wt. %, based on the total weight of the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 and Mn 2 P 2 O 7 .

4 . The cathode of claim 1 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is provided as particles having a diameter of from 50 to 500 nm.

5 . The cathode of claim 4 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is coated with Mn 2 P 2 O 7 , and the coating is between 1 and 5 nm thick.

6 . The cathode of claim 1 , wherein M is Mo.

7 . The cathode of claim 1 , wherein the cathode is cobalt free.

8 . The cathode of claim 1 , wherein M is substituted at cation sites.

9 . The cathode of claim 1 , further comprising a conductive carbon and a binder.

10 . The cathode of claim 1 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is a solid solution wherein the lithium concentration is in excess between 15 to 30 at % to form a lithium excess composition.

11 . The cathode of claim 1 , wherein with usable capacity of the cathode attains 180 mAh/g when cycled to 4.5 V vs. Li/Li + .

12 . A cathode composition for a lithium battery, comprising LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 , where M is at least one selected from the group consisting of M=Mo, Ti, Cr, Zr and V, and x is 0.005-0.02.

13 . The cathode composition of claim 12 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 , is provided as particles, and the particles are coated with Mn 2 P 2 O 7 .

14 . The cathode composition of claim 13 , wherein the Mn 2 P 2 O 7 coating is 1-3 wt %, based on the total weight of the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 and Mn 2 P 2 O 7 .

15 . The cathode composition of claim 13 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is provided as particles having a diameter of from 50 to 500 nm.

16 . The cathode composition of claim 15 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is coated with Mn 2 P 2 O 7 , and the coating is between 1 and 5 nm thick.

17 . The cathode of claim 1 , further comprising conductive carbon and a binder.

18 . A lithium battery, comprising:
a cathode comprising LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 , where M is at least one selected from the group consisting of Mo, Ti, Cr, Zr and V, and x is 0.005 to 0.02; an anode; a separator; and an electrolyte.

19 . The battery of claim 18 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 , is provided as particles, and the particles are coated with Mn 2 P 2 O 7 .

20 . The battery of claim 19 , wherein the Mn 2 P 2 O 7 coating is 1-3 wt %, based on the total weight of the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 and Mn 2 P 2 O 7 .

21 . The battery of claim 18 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is provided as particles having a diameter of from 50 to 500 nm.

22 . The battery of claim 21 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is coated with Mn 2 P 2 O 7 , and the coating is between 1 and 5 nm thick.

23 . The battery of claim 18 , wherein the cathode is cobalt free.

24 . The battery of claim 18 , wherein M is substituted at cation sites.

25 . The battery of claim 18 , wherein with usable capacity of the cathode attains 180 mAh/g when cycled between 2.0-4.5 V vs. Li/Li + .

26 . A method of making a lithium battery, comprising the steps of:
providing LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 , where M is at least one selected from the group consisting of Mo, Ti, Cr, Zr and V, and x is 0.005 to 0.02; mixing the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 with conductive carbon, a binder and a solvent to form a slurry, and casting the slurry onto a current collector and drying the slurry to form a cathode; combining the cathode with an anode, a separator and an electrolyte to form a battery.

27 . The method of claim 26 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 is provided as particles having a diameter of from 50 to 500 nm.

28 . The method of claim 27 , wherein the LiNi 0.5-x/2 Mn 0.5-x/2 M x O 2 particles are coated with Mn 2 P 2 O 7 .

29 . The method of claim 28 , wherein the coating is between 1 and 5 nm thick.

30 . The method of claim 26 , wherein the binder is PVDF.

31 . The method of claim 26 , wherein the solvent is N-Methyl-2-Pyrrolidone (NMP).

32 . The method in claim 26 , wherein the electrolyte is 1.2 M LiPF 6 in EC-EMC in 3:7 weight ratio.

33 . The method in claim 26 , wherein the anode composition is a mixture of graphite and a binder.

Assignees

• Ut Battelle Llc

Inventors

• Nanda Jagjit
• Belharouak Ilias
• Self Ethan C
• Darbar Devendrasinh Udaisinh

Classifications

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M10/0568

  characterised by the solutes · CPC title