Method for the purification of raw carbon nanotubes

Patent metadata

Field	Value
Publication number	US-11661344-B2
Application number	US-201816498537-A
Country	US
Kind code	B2
Filing date	Mar 29, 2018
Priority date	Mar 31, 2017
Publication date	May 30, 2023
Grant date	May 30, 2023

Abstract

The present invention proposes a process for purifying raw carbon nanotubes to obtain an content in metallic impurities comprised between 5 ppm and 200 ppm. The process includes an increase in the bulk density of the raw carbon nanotubes via compacting to produce compacted carbon nanotubes. The process further includes sintering the compacted carbon nanotubes by undergoing thermal treatment under gaseous atmosphere in order to remove at least a portion of the metallic impurities contained in the raw carbon nanotubes, and consequently producing purified carbon nanotubes. These purified carbon nanotubes are directly usable as electronic conductors serving as basis additive to an electrode material without requiring any subsequent purification step. The electrode material can then be used to manufacture an electrode destined to a lithium-ion battery.

First claim

The invention claimed is:

1. A process of purification of raw carbon nanotubes comprising metallic impurities, the process comprising:
compacting the raw carbon nanotubes to produce compacted raw carbon nanotubes having a bulk density higher than that of the raw carbon nanotubes;
sintering the compacted raw carbon nanotubes including a thermal treatment under gaseous atmosphere, to remove at least a portion of the metallic impurities and produce purified carbon nanotubes; and
conditioning the purified carbon nanotubes to produce conditioned purified carbon nanotubes for a direct application, wherein the conditioning comprises dispersing the purified carbon nanotubes to reduce the bulk density thereof to between 0.21 and 0.25 g/cm 3 .

2. The process according to claim 1 , wherein the compacting of the raw carbon nanotubes comprises agglomerating the raw carbon nanotubes to produce agglomerated carbon nanotubes having a bulk density comprised between 0.1 and 0.8 g/cm 3 .

3. The process according to claim 1 , wherein the compacting of the raw carbon nanotubes comprises briquetting the raw carbon nanotubes to produce briquettes of carbon nanotubes having a bulk density comprised between 0.1 and 0.8 g/cm 3 .

4. The process according to claim 1 , wherein the compacting of the raw carbon nanotubes comprises extruding the raw carbon nanotubes to produce granules or pellets of extruded raw carbon nanotubes having a bulk density comprised between 0.2 and 0.3 g/cm 3 .

5. The process according to claim 1 , wherein the compacting comprises at least one of the following:
agglomerating;
briquetting; and
extruding.

6. The process according to claim 5 , wherein the compacting only comprises agglomerating when the bulk density of the raw CNTs is of at least 0.2 g/cm 3 .

7. The process according to claim 1 , wherein the gaseous atmosphere during thermal treatment comprises chlorine gas, and wherein the metallic impurities are removed by a pulse vacuum system after chlorination of the metals by the chlorine gas.

8. The process according to claim 1 , wherein the gaseous atmosphere during thermal treatment comprises nitrogen gas and wherein the metallic impurities are removed by vaporization.

9. The process according to claim 1 , wherein the thermal treatment is performed at a sintering temperature comprised between 1,200° C. and 3,000° C.

10. The process according to claim 1 , wherein the thermal treatment is performed in a pusher continuous kiln or in a batch kiln.

11. The process according to claim 1 , comprising adding an inorganic base in aqueous solution or adding water before, during or after the compacting of raw carbon nanotubes.

12. The process according to claim 11 , wherein the aqueous solution of inorganic base or the water is added at a temperature between 20 and 80° C.

13. The process according to claim 11 , comprising drying the compacted raw carbon nanotubes in order to remove moisture therefrom.

14. The process according to claim 1 , wherein the conditioning further comprises packaging the purified carbon nanotubes.

15. The process according to claim 1 wherein the raw carbon nanotubes are of multi-walled type presenting a length/diameter ratio superior to 10, a specific surface area comprised between 100 and 300 m 2 /g, and a bulk density comprised between 0.02 and 0.5 g/cm 3 .

16. The process according to claim 15 , wherein the purified carbon nanotubes have a metallic impurities content between 5 ppm and 200 ppm.

17. The process according to claim 1 , wherein the metallic impurities comprise iron.

Assignees

• Hydro Quebec
• Arkema France

Inventors

• Darwiche Ali
• Dontigny Martin
• Kondo Naoyuki
• Guerfi Abdelbast
• Zaghib Karim
• Beausoleil Julien
• Korzhenko Alexander

Classifications

• C01B2202/26

  Mechanical properties · CPC title

• C01P2006/11

  Powder tap density · CPC title

• H01M10/0525

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

• C01B32/17 Primary

  Purification · CPC title

• C01B2202/06

  Multi-walled nanotubes · CPC title