Methods and systems for salt-rinse surface doping of electrode materials

Patent metadata

Field	Value
Publication number	US-12009507-B2
Application number	US-202117443805-A
Country	US
Kind code	B2
Filing date	Jul 27, 2021
Priority date	Jul 30, 2020
Publication date	Jun 11, 2024
Grant date	Jun 11, 2024

Abstract

Methods and systems are provided for salt-rinse surface doping of electrode materials for lithium-ion batteries. In one example, a method may include dissolving a dopant salt in a solvent to form a dopant salt rinse solution, rinsing an electrode active material with the dopant salt rinse solution to form a coated electrode active material, and heating the coated electrode active material to form a doped electrode active material. In some examples, a surface region of the doped electrode active material may include a uniform distribution of dopants from the dopant salt rinse solution. In this way, the electrode active material may be rinsed and doped via the dopant salt rinse solution in a single-stage process.

First claim

The invention claimed is:

1. A method, comprising:
dissolving a dopant salt in a rinsing solvent to form a dopant salt rinse solution;
rinsing an electrode active material with the dopant salt rinse solution to obtain a uniformly surface-coated electrode active material, wherein rinsing the electrode active material with the dopant salt rinse solution to obtain the uniformly surface-coated electrode active material comprises:
mixing the electrode active material with the dopant salt rinse solution to form a mixture, wherein mixing the electrode active material with the dopant salt rinse solution comprises:
dissolving a residual lithium salt on a surface of the electrode active material; and
precipitating a dopant precipitate on the surface of the electrode active material while producing a product salt, where the dopant precipitate is formed from a cation of the dopant salt and an anion of the residual lithium salt, where the product salt is formed from lithium and an anion of the dopant salt is soluble in the dopant salt rinse solution, and where the dopant precipitate has a lower solubility in the dopant salt rinse solution than each of the residual lithium salt and the product salt;

filtering the mixture to isolate a filtrate; and
drying the filtrate to obtain the uniformly surface-coated electrode active material; and

heating the uniformly surface-coated electrode active material to form a uniformly surface-doped electrode active material.

2. The method of claim 1 , wherein the dopant salt comprises cations of any one of Al, Mg, Mn, Co, Ni, Ti, Zr, Sn, Cu, Ca, La, Ce, Y, Nd, W, Na, K, V, Nb, Mo, Fe, Zn, F, Cl, Br, S, Se, P, Sb, Si, Ge, Ga, and B, or a combination thereof.

3. The method of claim 1 , wherein the dopant salt comprises cations of any one of Al, Mg, Mn, Co, Ni, Ti, Zr, W, F, and B, or a combination thereof.

4. The method of claim 2 , wherein a surface region of the uniformly surface-doped electrode active material comprises a uniform distribution of the cations.

5. The method of claim 2 , wherein the cations are included in the uniformly surface-doped electrode active material at 0.1 to 2 mol %.

6. The method of claim 1 , wherein cations of Mn and/or cations of Co are included in the dopant salt, and wherein the cations are included in the uniformly surface-doped electrode active material at 0.1 to 15 mol %.

7. The method of claim 1 , wherein the dopant salt comprises one or more dopant oxides, one or more dopant acetates, one or more dopant nitrides, one or more dopant sulfates, one or more dopant fluorides, one or more dopant nitrates, one or more dopant phosphides, one or more dopant sulfides, one or more dopant iodides, one or more dopant phosphates, one or more dopant carbonates, one or more dopant oxalates, one or more dopant acetylacetones, or a combination thereof.

8. The method of claim 1 , wherein the electrode active material comprises one or more lithium insertion electrode materials.

9. The method of claim 1 , wherein the electrode active material is a cathode active material comprising stoichiometric NMC, lithium-rich NMC, NCA, NCMA, LNO, spinel LMO, spinel LNMO, LFP, or a combination thereof.

10. The method of claim 1 , wherein the uniformly surface-doped electrode active material is NMC or doped NMC.

11. The method of claim 1 , wherein the electrode active material is an anode active material comprising LTO, graphite, graphene, silicon, a silicon oxide, a tin oxide, or a combination thereof.

12. The method of claim 1 , wherein the rinsing solvent comprises water, ethanol, methanol, isopropanol, acetone, acetone nitrile, ethyl acetate, ethylene glycol, or a combination thereof.

13. A method, comprising:
dissolving a metal salt in a rinsing solvent to form an aqueous rinse solution; and thereafter,
mixing a cathode active material with the aqueous rinse solution to form a mixture, wherein mixing the cathode active material with the aqueous rinse solution comprises:
dissolving a residual lithium salt on a surface of the cathode active material; and
precipitating a dopant precipitate on the surface of the cathode active material while producing a product salt, where the dopant precipitate is formed from a cation of the metal salt and an anion of the residual lithium salt, where the product salt is formed from lithium and an anion of the metal salt is soluble in the rinsing solvent, and where the dopant precipitate has a lower solubility in the rinsing solvent than each of the residual lithium salt and the product salt; and thereafter,

without any further rinsing:
isolating a coated cathode active material from the rinsing solvent, the rinsing solvent including dissolved Lit;
heating the coated cathode active material to obtain a surface-doped cathode active material; and
forming a cathode slurry comprising the surface-doped cathode active material.

14. The method of claim 13 , wherein the metal salt is a salt of any one of Al, Mg, Mn, Co, Ni, Ti, Zr, W, F, and B, or a combination thereof.

15. The method of claim 13 , wherein the cathode active material comprises an NMC having a molar content of nickel of 60% or greater of a total molar content of nickel, manganese, and cobalt.

Assignees

• A123 Systems Llc

Inventors

• Liu Lei
• Kim Kitae
• Wang Lixin
• Parmar Anil
• Kim Bryan
• Harrison Chloe
• Millonig Andrew
• Johnson Derek
• Lee Eunsung
• Yu Taehwan

Classifications

• 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

• H01M4/505

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

• H01M4/366 Primary

  as layered products · CPC title

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title