Cellulose-based self-standing films for use in Li-ion batteries

Patent metadata

Field	Value
Publication number	US-11811068-B2
Application number	US-201917048717-A
Country	US
Kind code	B2
Filing date	May 15, 2019
Priority date	May 15, 2018
Publication date	Nov 7, 2023
Grant date	Nov 7, 2023

Abstract

The present technology relates to self-standing electrodes, their use in electrochemical cells, and their production processes using a water-based filtration process. For example, the self-standing electrodes may be used in lithium-ion batteries (LIBs). Particularly, the self-standing electrodes comprise a first electronically conductive material serving as a current collector, the surface of the first electronically conductive material being grafted with a hydrophilic group, a binder comprising cellulose fibres, an electrochemically active material, and optionally a second electronically conductive material. A process for the preparation of the self-standing electrodes is also described.

First claim

The invention claimed is:

1. A self-standing electrode comprising:
a first electronically conductive material serving as a current collector, the surface of said first electronically conductive material being grafted with at least one aryl group of Formula I:

wherein:
FG is a hydrophilic functional group; and n is an integer in the range of 1 to 5;
a binder comprising cellulose fibers;
an electrochemically active material; and
optionally a second electronically conductive material;
wherein,
the self-standing electrode is made of a solid film having a first and a second surfaces;
the concentration of the first electronically conductive material increases from the second surface to the first surface of the solid film; and
the concentration of the electrochemically active material and, if present, of the second electronically conductive material increase from the first surface to the second surface of the solid film.

2. The self-standing electrode according to claim 1 , wherein the first electronically conductive material comprises carbon fibers.

3. The self-standing electrode according to claim 1 , wherein the cellulose fibers are unmodified cellulose fibers, or wherein the cellulose fibers are free of aluminum cations, or wherein the average length of the cellulose fibers is between 5 nm and 5 mm, or between 250 nm and 3 mm, or between 500 nm and 3 mm, or between 1 μm and 3 mm, or between 100 μm and 3 mm, or between 250 μm and 3 mm, or between 500 μm and 3 mm, or between 750 μm and 2.5 mm, or between 1 mm and 2.5 mm.

4. The self-standing electrode according to claim 1 , wherein the electrochemically active material is in the form of particles coated with a carbon layer in a core-shell configuration and/or wherein the electrochemically active material is selected from metal oxide particles, lithiated metal oxide particles, metal phosphate particles, lithiated metal phosphate particles, carbon-based materials, and active organic materials.

5. The self-standing electrode according to claim 1 , wherein the self-standing electrode is:
a positive electrode, and the electrochemically active material comprises lithiated iron phosphate particles (LiFePO 4 ), pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA), or 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA); or
a negative electrode, and the electrochemically active material comprises lithium titanate (Li 4 Ti 5 O 12 ) particles or a carbon-based material.

6. The self-standing electrode according to claim 1 , wherein the second electronically conductive material is selected from carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination of at least two thereof.

7. The self-standing electrode according to claim 1 , wherein the hydrophilic functional group is a carboxylic acid or a sulfonic acid functional group.

8. A process for the manufacturing of a self-standing electrode as defined in claim 1 , the process comprising the following steps:
(a) grafting at least one aryl group of Formula I on a first electronically conductive material;
(b) dispersing the first modified electronically conductive material obtained in step (a) in an aqueous mixture comprising cellulose fibers to obtain a first aqueous dispersion;
(c) filtering the first aqueous dispersion on a filter membrane to obtain a film;
(d) dispersing an electrochemically active material and optionally a second electronically conductive material in an aqueous medium to obtain a second aqueous dispersion;
(e) filtering the second aqueous dispersion on the film obtained in step (c) to produce a self-standing electrode on the filter membrane; and
(f) peeling off the self-standing electrode from the filter membrane.

9. The process according to claim 8 , further comprising at least one of:
a step of drying the film obtained in step (c);
a step of grafting at least one aryl group of Formula I on the second electronically conductive material prior to step (d);
a step of calendering the self-standing electrode; and
a step of producing a separator by filtering an aqueous mixture comprising cellulose fibers directly on the self-standing electrode obtained in step (e) prior to step (f).

10. The process according to claim 8 , wherein the electrochemically active material is in the form of particles coated with a carbon layer, the process further comprising a step of grafting at least one aryl group of Formula Ion said carbon layer prior to step (d).

11. The process according to claim 8 , wherein the grafting steps of the process comprise:
(i) generating an aryl diazonium ion by contacting an aniline of Formula II:

wherein:
FG and n are as defined in claim 1 , with a diazotizing agent; and
(ii) reacting the aryl diazonium ion generated in step (i) with the carbon of a carbon layer on the surface of the electrochemically active material, or with the first or second electronically conductive material.

12. The process according to claim 11 , wherein the diazotizing agent is present in a range of from 0.01 to 0.04 equivalent with respect to the carbon, or of about 0.03 equivalent with respect to the carbon.

13. The process according to claim 11 , wherein the diazotizing agent is present in a range of from 1 to 4 equivalents with respect to the aniline of Formula II, or of about 3 equivalents with respect to the aniline of Formula II.

14. The process according to claim 11 , wherein the diazotizing agent is a nitrite salt or an alkyl nitrite.

15. The process according to claim 8 , wherein the grafting step is carried out in an acidic aqueous medium or in a polar aprotic solvent.

16. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative and positive electrodes is a self-standing electrode as defined in claim 1 .

17. The electrochemical cell according to claim 16 , further comprising a separator.

18. The electrochemical cell according to claim 16 , wherein the electrolyte is a liquid electrolyte comprising a lithium salt in a solvent, a gel electrolyte comprising a lithium salt in a solvent and/or a solvating polymer, or a solid polymer electrolyte comprising a lithium salt in a solvating polymer.

19. A battery comprising at least one electrochemical cell as defined in claim 16 .

20. The self-standing electrode according to claim 1 , wherein the first surface mainly comprises the first electronically conductive material.

21. The self-standing electrode according to claim 1 , wherein the second surface mainly comprises the electrochemically active material and, if present, the second electronically conductive material.

22. The self-standing electrode according to claim 1 , wherein the second electronically conductive material is grafted with at least one aryl group of Formula I as defined in claim 1 .

23. The self-standing electrode according to claim 4 , wherein the carbon layer is grafted with at least one aryl group of Formula I as defined in claim 1 .

24. The process according to claim 11 , wherein the aryl diazonium ion is generated in situ su

Assignees

• Hydro Quebec

Inventors

• Delaporte Nicolas
• Guerfi Abdelbast
• Zaghib Karim

Classifications

• H01M4/806 Primary

  Nonwoven fibrous fabric containing only fibres · CPC title

• H01M4/131 Primary

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• H01M4/1391

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

• H01M4/1397

  of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title