Method and systems for metal doping on battery cathode materials

Patent metadata

Field	Value
Publication number	US-12476239-B2
Application number	US-201816765842-A
Country	US
Kind code	B2
Filing date	Nov 20, 2018
Priority date	Nov 22, 2017
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

Methods and systems are provided for a battery cathode material comprising greater than or equal to 60% nickel content, the cathode material having at least one metal doped therein. In one example, a method comprises doping the at least one metal into the cathode material using water as a solvent, wherein the at least one metal has an ionic radii greater than 60 picometers. The at least one metal may be selected from strontium (Sr), barium (Ba), rubidium (Rb), cesium (Cs), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), tungsten (W), platinum (Pt), neodymium (Nd), yttrium (Y), and cerium (Ce).

First claim

The invention claimed is:

1 . A method, comprising:
dissolving a dopant salt in water, the dopant salt comprising one or more metals having ionic radii greater than 60 picometers; forming a nickel, manganese, and cobalt oxide (NMC) cathode material by mixing an NMC precursor with a lithium salt and sintering; after sintering to form the NMC cathode material, forming a mixture of the NMC cathode material with the dissolved dopant salt in the water; and heating the mixture to form a doped cathode material, wherein heating the mixture occurs immediately after forming the mixture and gradually evaporates the water, and wherein the dopant salt is uniformly deposited at a surface of the NMC cathode material as an amount of water decreases and lithium re-enters the NMC cathode material.

2 . The method of claim 1 , wherein the one or more metals are selected from one or more of strontium (Sr), barium (Ba), rubidium (Rb), cesium (Cs), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), tungsten (W), platinum (Pt), neodymium (Nd), samarium (Sm), cerium (Ce), yttrium (Y), praseodymium (Pr), and lanthanum (La).

3 . The method of claim 1 , wherein the ionic radius of each of the one or more metals is 1.5 times greater than an ionic radius of nickel.

4 . The method of claim 3 , wherein the doped cathode material comprises greater than or equal to 60% nickel by weight.

5 . The method of claim 1 , wherein the dopant salt is NdI 3 .

6 . The method of claim 1 , wherein the dopant salt is Nd(NO 3 ) 3 .

7 . The method of claim 1 , wherein the dopant salt is Y(NO 3 ) 3 .

8 . The method of claim 1 , wherein the dopant salt is Y(CH 2 COOH) 3 .

9 . The method of claim 1 , wherein the dopant salt is dissolved into the water at an amount between 0.01 to 15 wt. % of the NMC cathode material.

10 . The method of claim 1 , wherein the dopant salt is dissolved into the water at an amount equal to 3 wt. % of the NMC cathode material.

11 . The method of claim 1 , wherein the heating the mixture includes heating the mixture to a pre-sinter temperature and a sinter temperature, where the pre-sinter temperature is less than the sinter temperature, where the pre-sinter temperature is between 150 to 900° C., and where the sinter temperature is between 300 to 950° C.

12 . The method of claim 1 , wherein the heating the mixture includes heating the mixture to a temperature between 100 to 950° C.

13 . A method for forming a doped cathode material comprising greater than or equal to 60% nickel by weight, the method comprising:
dissolving a dopant salt in water, where the dopant salt comprises a metal having an atomic radius greater than 60 picometers; forming a nickel, manganese, and cobalt oxide (NMC) cathode material by mixing an NMC precursor with a lithium salt and sintering; after sintering to form the NMC cathode material, forming a mixture comprising the NMC cathode material and the dopant salt in the water; heating a suspension of the mixture until dry, wherein heating the suspension occurs immediately after forming the mixture and gradually evaporates the water, and wherein the dopant salt is uniformly deposited at a surface of the NMC cathode material as an amount of water decreases; grinding the dry suspension; and sintering the ground, dry suspension, wherein lithium re-enters the NMC cathode material.

14 . The method of claim 13 , wherein the dissolving the dopant salt includes dissolving the dopant salt in only the water.

15 . The method of claim 13 , wherein the dissolving the dopant salt includes dissolving the dopant salt into the water at 3 wt. % of the NMC cathode material, where the dopant salt is water-soluble.

16 . The method of claim 13 , wherein the dopant salt is dissolved in the water, an organic solvent, or a combination thereof.

17 . The method of claim 13 , wherein the sintering includes heating the NMC cathode material and the dopant salt to a temperature between 100 to 950° C.

18 . A doped cathode material for a lithium ion battery, the doped cathode material comprising:
a nickel, cobalt, and manganese powder, where nickel forms greater than or equal to 60% of the powder by weight; and a dopant comprising an atomic radius greater than 60 picometers, where the dopant is doped into the powder via water, wherein lithium re-enters the powder when the doped cathode material is heated; and wherein a secondary phase of the dopant is arranged uniformly on surfaces of the doped cathode material, the secondary phase causing an x-ray diffraction peak between a 2θ of 20° and 40° that is missing from an x-ray diffraction plot of a corresponding undoped cathode material, and the dopant enlarges the crystal structure of the powder along a c-axis.

19 . The doped cathode material of claim 18 , wherein the dopant is selected from Sr, Ba, Rb, Cs, Zr, Nb, Mo, Tc, Ru, W, Pt, Nd, Ce, Y, and combinations thereof.

Assignees

• A123 Systems Llc

Inventors

• Wang Lixin
• Zhou Weidong
• Parmar Anil
• Zhou Fu
• Johnson Derek C

Classifications

• H01M10/0525

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

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• C01P2006/40

  Electric properties · CPC title