Titration-gas chromatography method and system for anode detection and quantification in energy storage devices

Patent metadata

Field	Value
Publication number	US-2023251236-A1
Application number	US-202318167026-A
Country	US
Kind code	A1
Filing date	Feb 9, 2023
Priority date	Feb 9, 2022
Publication date	Aug 10, 2023
Grant date	—

Abstract

Disclosed are methods and systems for the use of titration-gas chromatography (TGC) to differentiate and quantify metallic substances (M 0 ) and ionic metal (Mn + ) in an anode material, such as in rechargeable-battery anodes of metal type (e.g., Li, Na, K, Mg, Ca, Fe, Zn, Al, etc.) or compound type (e.g., Li x C6, Li x Si, LixSn, etc) by using the proper titrant.

First claim

What is claimed is:

1 . A method for quantifying an amount of metallic substance (M 0 ) in an anode material, comprising:
sealing a sample in a container, the sample comprising the anode material; injecting an amount of a protic titrant into the container to react with the sample; agitating the container; implementing a titration-gas chromatography (TGC) on the sample to detect an amount of hydrogen gas (H 2 ) released from a reaction between the titrant and the sample, wherein:
a reduced M 0 reacts with the titrant to produce the H 2 ; and
converting the detected amount of H 2 to the amount of M 0 .

2 . The method of claim 1 , wherein the container is located within an Argon gas-filled glovebox or a dry room.

3 . The method of claim 1 , wherein the agitating includes shaking the container.

4 . The method of claim 1 further comprising:
connecting the container to a sample injector equipped with a flow controller.

5 . The method of claim 1 , wherein the implementing the TGC includes using a H 2 detector for detection of the released hydrogen gas.

6 . The method of claim 1 , wherein the converting the detected H 2 amount to the M 0 amount includes using a calibration curve.

7 . The method of claim 1 , wherein the anode material is usable in rechargeable batteries, and the sample includes an alkaline metal anode material, an alloy type anode material, a carbon-based anode material, a composite anode material, or a multivalent anode material.

8 . The method of claim 1 , wherein the anode material is usable in lithium-ion batteries, and the sample includes Li x C 6 , Li x Si, or Li x Sn.

9 . The method of claim 1 , wherein the sample includes organic or inorganic M n+ compositions and the method is configured to differentiate an amount of M 0 from the organic or inorganic M n+ compositions based on the released H 2 gas.

10 . The method of claim 1 , wherein the titrant is selected from water, methanol, ethanol, and an acid.

11 . The method of claim 1 , wherein the M 0 includes Li, Na, K, Mg, Ca, Fe, Zn, or Al.

12 . The method of claim 1 , wherein the amount of M 0 quantified from the sample is less than 5 micrograms.

13 . The method of claim 12 , wherein the amount of M 0 quantified from the sample is less than 1 microgram.

14 . The method of claim 1 , wherein the M 0 is Li 0 and the titrant is water.

15 . The method of claim 1 , wherein the M 0 is Si in a Li—Si alloy and the titrant is ethanol.

16 . The method of claim 1 , wherein the M 0 is Li in a Li x C 6 composition and the titrant is ethanol, water or sulfuric acid.

17 . A system for quantifying an amount of metallic substance (M 0 ) in an anode material based on titration-gas chromatography (TGC), the system comprising:
a sealable sample container configured to hold a sample comprising the anode material and an amount of a protic titrant, the sample container is configured to receive the amount of the protic titrant by injection, and to allow production of hydrogen gas (H 2 ) upon reaction of a reduced M 0 in the anode material with the protic titrant; and a gas chromatography (GC) device fluidically coupled with the sample container, wherein:
the GC device is configured to detect the H 2 released from the reaction between the protic titrant and the reduced M 0 in the sample container, and to enable the detected amount of H 2 to be converted to the amount of M 0 .

18 . The system of claim 17 , further comprising an argon gas-filled glovebox, wherein the sample container and the GC device are positioned within the Argon gas-filled glovebox.

19 . The system of claim 17 , further containing a sample injector equipped with a flow controller for injecting the released hydrogen into the GC device.

20 . The system of claim 17 , wherein the sample container is configured to receive the amount of the titrant by injection by a titration pipette or burette.

Assignees

• Univ California

Inventors

• Meng Ying Shirley
• Fang Chengcheng
• Bao Wurigumula
• Wang Xuefeng

Classifications

• G01N31/16 Primary

  using titration · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M10/4285

  Testing apparatus · CPC title

• G01N30/16

  Injection (G01N30/24 takes precedence) · CPC title

• G01N2030/025

  Gas chromatography · CPC title