Furnace atmosphere control for lithium-ion battery cathode material production

Patent metadata

Field	Value
Publication number	US-11777073-B2
Application number	US-202117314505-A
Country	US
Kind code	B2
Filing date	May 7, 2021
Priority date	May 7, 2021
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

Abstract

A method and apparatus for controlling the atmosphere of a multizone calcination (firing) furnace for production of high-quality nickel-rich cathode material for lithium-ion and solid-state batteries. A high-quality oxygen-rich atmosphere is maintained to ensure the quality of the cathode material. An atmosphere control system continuously measures and analyzes the composition of the calcination furnace atmosphere in different zones and adjusts the flowrate of oxygen-rich atmosphere into the furnace to optimize the calcination process.

First claim

The invention claimed is:

1. A method of furnace atmosphere control for a calcination furnace for the production of a lithium ion battery cathode material, the method comprising the steps of:
(a) measuring a first oxygen concentration, a first moisture concentration and a first carbon dioxide concentration of an atmosphere inside a first zone of the calcination furnace;
(b) measuring a second oxygen concentration, a second moisture concentration and a second carbon dioxide concentration of an atmosphere inside a second zone of the calcination furnace, wherein the second zone adjoins the first zone and a border between the first and second zones is located where a temperature of the atmosphere reaches a predetermined soaking temperature;
(c) supplying an oxygen process gas comprising at least 50 percent oxygen by volume, independently, to the first and second zones of the calcination furnace;
(d) controlling a flow rate of a first stream of oxygen process gas into the first zone as a function of at least one selected from the group of (i) the first oxygen concentration measured in step (a), (ii) the first moisture concentration measured in step (a), and (iii) the first carbon dioxide concentration measured in step (a);
(e) controlling a flow rate of a second stream of oxygen process gas into the second zone as a function of at least one selected from the group of (i) the second oxygen concentration measured in step (b), (ii) the second moisture concentration measured in step (b), and (iii) the second carbon dioxide concentration measured in step (b); and
(f) maintaining the flow rate of the first stream of oxygen process gas at or below the flow rate of the second stream of oxygen process gas, to prevent to prevent a gaseous flow from the first zone into the second zone.

2. The method of claim 1 , wherein step (d) further comprises increasing the flow rate of the first stream of oxygen process gas if at least one selected from the group of (i) the first oxygen concentration measured in step (a) is less than a predetermined setpoint, (ii) the first moisture concentration measured in step (a) is greater than a predetermined set point, and (iii) the first carbon dioxide concentration measured in step (a) is greater than a predetermined set point.

3. The method of claim 1 , wherein step (e) further comprises increasing the flow rate of the second stream of oxygen process gas if at least one selected from the group of (i) the second oxygen concentration measured in step (b) is less than a predetermined setpoint, (ii) the second moisture concentration measured in step (b) is greater than a predetermined setpoint, and (iii) the second carbon dioxide concentration measured in step (b) is greater than a predetermined set point.

4. The method of claim 1 , further comprising:
(h) repeating steps (a) through (f) while simultaneously heating, gradually, the first zone to a first temperature and maintaining the second zone at a second temperature, wherein the second temperature is greater than or equal to the first temperature.

5. The method of claim 2 , further comprising:
(i) repeating steps (a) through (f) while simultaneously feeding a quantity of lithium ion battery cathode precursor material into the first zone for a time period sufficient to heat the material to a predetermined material temperature, then feeding the material into the second zone.

6. The method of claim 1 , further comprising:
(j) measuring a third oxygen concentration, a third moisture concentration and a third carbon dioxide concentration of an atmosphere inside a third temperature zone of the furnace, wherein the third temperature zone adjoins the second temperature zone;
(k) controlling a flow rate of a third stream of oxygen process gas into the third zone as a function of at least one selected from the group of (i) the third oxygen concentration measured in step (j), (ii) the third moisture concentration measured in step (j), and (iii) the third carbon dioxide concentration measured in step (j); and
(l) maintaining the flow rate of the third stream of oxygen process gas at or below the flow rate of the second stream of oxygen process gas, to prevent to prevent a gaseous flow from the third zone into the second zone.

7. The method of claim 5 , wherein the lithium ion cathode precursor material is selected from the group consisting of precursors for: lithium nickel manganese cobalt (NMC); lithium nickel cobalt aluminum (NCA); lithium nickel manganese cobalt aluminum (NMCA); nickel cobalt boron (NCB) and combinations thereof.

8. The method of claim 7 , wherein the cathode precursor material comprises a mole ratio of nickel greater than 0.5.

9. The method of claim 1 , wherein the oxygen process gas comprises a purity of at least 90 percent by volume.

10. The method of claim 1 , further comprising:
(m) withdrawing a sample of furnace atmosphere from the first zone through a sample line; and
(n) delivering the sample to at least one external analyzer configured to measure a parameter selected from the group consisting of: oxygen concentration; carbon dioxide concentration, dew point, ammonia, SOx and NOx.

11. A method of furnace atmosphere control for a calcination furnace for the production of a lithium ion battery cathode material, the method comprising the steps of:
(a) measuring a first oxygen concentration of an atmosphere inside a first zone of the calcination furnace;
(b) measuring a second oxygen concentration inside a second zone of the calcination furnace, wherein the second zone adjoins the first zone and a border between the first and second zones is located where a temperature of the atmosphere reaches a predetermined soaking temperature;
(c) supplying an oxygen process gas comprising at least 50 percent oxygen by volume, independently, to the first and second zones of the calcination furnace;
(d) controlling a flow rate of a first stream of oxygen process gas into the first zone as a function of the first oxygen concentration measured in step (a);
(e) controlling a flow rate of a second stream of oxygen process gas into the second zone as a function of the second oxygen concentration measured in step (b); and
(f) maintaining the flow rate of the second stream of oxygen process gas at or below the flow rate of the first stream of oxygen process gas, to prevent to prevent a gaseous flow from the second zone into the first zone.

Assignees

• Air Prod & Chem

Inventors

• Cai Jingjing
• Kus Paulina Weronika
• He Liang
• Plicht Guido
• Millington David

Classifications

• H01M4/0471 Primary

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

• F27D7/06 Primary

  Forming or maintaining special atmospheres or vacuum within heating chambers (supplying steam, vapour, gases or liquids F27D7/02) · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · 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

• H01M10/0525

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