Copolymers of ester and ether units, processes for producing same and uses thereof

Patent metadata

Field	Value
Publication number	US-11999811-B2
Application number	US-201916963383-A
Country	US
Kind code	B2
Filing date	Feb 5, 2019
Priority date	Feb 5, 2018
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

Abstract

The present technology relates to a polymer comprising at least one ester repeating unit and one ether repeating unit for use in an electrochemical cell, particularly in electrochemical accumulators such as lithium batteries, sodium batteries, potassium batteries and lithium-ion batteries. More specifically, the use of this polymer as a solid polymer electrolyte (SPE), as a matrix for forming gel electrolytes, or as a binder in an electrode material are also contemplated.

First claim

The invention claimed is:

1. A polymer comprising at least one ester repeating unit and one ether repeating unit, the polymer being of Formula II:

wherein x, y and z are integers each independently selected such that the average molecular weight of the polymer is between 200 g/mol and 5,000,000 g/mol, or between 200 g/mol and 1,000,000 g/mol, or between 200 g/mol and 500,000 g/mol, or between 400 g/mol and 100,000 g/mol, or between 400 g/mol and 20,000 g/mol, and wherein x≥1 and y+z≥1.

2. The polymer of claim 1 , wherein said polymer is polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone diacrylate.

3. A polymer being polycaprolactone-block-polytetrahydrofuran-block-polycaprolactone di-2-(2-methoxyethoxy) ester.

4. The polymer of claim 1 , said polymer being crosslinked and wherein the crosslinking of said polymer is carried out by UV irradiation, by heat treatment, by microwave, under an electron beam, by gamma irradiation, or by X-ray irradiation.

5. An electrolyte comprising a polymer and an ionic salt, wherein:
the polymer comprises at least one ester repeating unit and one ether repeating unit, the polymer being of Formula I:

wherein:
x, y, and z are integers each independently selected such that the average molecular weight of the polymer is between 200 g/mol and 5,000,000 g/mol, or between 200 g/mol and 1,000,000 g/mol, or between 200 g/mol and 500,000 g/mol, or between 400 g/mol and 100,000 g/mol, or between 400 g/mol and 20,000 g/mol, where x≥1 and y+z≥1;
R 1 and R 2 are linear or branched substituents each independently selected from hydrogen, C 1-21 alkyl, C 2-22 alkenyl, C 1-10 alkoxyalkyl, C 1-10 alkyl-(acrylate), and C 1-10 alkyl-(methacrylate);
n, m, o, and p are integers, where o is between 1 and 10 and n, m, and p are between 0 and 10; and
A and B are substituted or unsubstituted groups each independently selected from alkyls, alkenyls, alkynyls, acetyls, alkoxyls, epoxy-comprising groups, furan-comprising groups, primary amine-comprising groups, maleimide-comprising groups, acrylate-comprising groups, and acid groups; and
the ionic salt is a lithium salt selected from lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO 3 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 ) (LiTf), lithium fluoroalkylphosphate Li[PF 3 (CF 2 CF 3 ) 3 ](LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF 3 ) 4 ](LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O′)borate Li[B(C 6 O 2 ) 2 ](LBBB), and their combinations.

6. An electrolyte comprising a polymer and a polar aprotic solvent, wherein:
the polymer comprises at least one ester repeating unit and one ether repeating unit, the polymer being of Formula I:

wherein:
x, y, and z are integers each independently selected such that the average molecular weight of the polymer is between 200 g/mol and 5,000,000 g/mol, or between 200 g/mol and 1,000,000 g/mol, or between 200 g/mol and 500,000 g/mol, or between 400 g/mol and 100,000 g/mol, or between 400 g/mol and 20,000 g/mol, where x≥1 and y+z≥1;
R 1 and R 2 are linear or branched substituents each independently selected from hydrogen, C 1-21 alkyl, C 2-22 alkenyl, C 1-10 alkoxyalkyl, C 1-10 alkyl-(acrylate), and C 1-10 alkyl-(methacrylate);
n, m, o, and p are integers, where o is between 1 and 10 and n, m, and p are between 0 and 10; and
A and B are substituted or unsubstituted groups each independently selected from alkyls, alkenyls, alkynyls, acetyls, alkoxyls, epoxy-comprising groups, furan-comprising groups, primary amine-comprising groups, maleimide-comprising groups, acrylate-comprising groups, and acid groups; and

the polar aprotic solvent is selected from ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), vinylene carbonate (VC), methyl butyrate (MB), γ-butyrolactone (γ-BL), γ-valerolactone (γ-VL), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 2-methyltetrahydrofuran, dimethylsulfoxide, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethylmonoglyme, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, propylene carbonate derivatives, tetrahydrofuran, and their mixtures.

7. An electrode material comprising an electrochemically active material and a polymer comprising at least one ester repeating unit and one ether repeating unit, the polymer being of Formula I:

wherein:
x, y, and z are integers each independently selected such that the average molecular weight of the polymer is between 200 g/mol and 5,000,000 g/mol, or between 200 g/mol and 1,000,000 g/mol, or between 200 g/mol and 500,000 g/mol, or between 400 g/mol and 100,000 g/mol, or between 400 g/mol and 20,000 g/mol, where x≥1 and y+z≥1;
R 1 and R 2 are linear or branched substituents each independently selected from hydrogen, C 1-21 alkyl, C 2-22 alkenyl, C 1-10 alkoxyalkyl, C 1-10 alkyl-(acrylate), and C 1-10 alkyl-(methacrylate);
n, m, o, and p are integers, where o is between 1 and 10 and n, m, and p are between 0 and 10; and
A and B are substituted or unsubstituted groups each independently selected from alkyls, alkenyls, alkynyls, acetyls, alkoxyls, epoxy-comprising groups, furan-comprising groups, primary amine-comprising groups, maleimide-comprising groups, acrylate-comprising groups, and acid groups.

8. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode, the positive electrode, and the electrolyte comprises a polymer comprising at least one ester repeating unit and one ether repeating unit, the polymer being of Formula I:

wherein:
x, y, and z are integers each independently selected such that the average molecular weight of the polymer is between 200 g/mol and 5,000,000 g/mol, or between 200 g/mol and 1,000,000 g/mol, or between 200 g/mol and 500,000 g/mol, or between 400 g/mol and 100,000 g/mol, or between 400 g/mol and 20,000 g/mol, where x≥1 and y+z≥1;
R 1 and R 2 are linear or branched substituents each independently selected from hydrogen, C 1-21 alkyl, C 2-22 alkenyl, C 1-10 alkoxyalkyl, C 1-10 alkyl-(acrylate), and C 1-10 alkyl-(methacrylate);
n, m, o, and p are integers, where o is between 1 and 10 and n, m, and p are between 0 and 10; and
A and B are substituted or unsubstituted groups each independently selected from alkyls, alkenyls, alkynyls, acetyls, alkoxyls, epoxy-comprising groups, furan-comprising groups, primary amine-comprising groups, maleimide-comprising groups, acrylate-comprising groups, and acid groups.

Assignees

• Hydro Quebec

Inventors

• Commarieu Basile
• Daigle Jean-Christophe
• Jalbert Pierre-Michel
• Lajoie Gilles
• Gagnon Catherine
• Guerfi Abdelbast
• Armand Michel
• Zaghib Karim

Classifications

• C08F290/061 Primary

  Polyesters; Polycarbonates · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08G63/08

  Lactones or lactides · CPC title

• C08G63/66

  Polyesters containing oxygen in the form of ether groups (C08G63/42, C08G63/58 take precedence) · CPC title

• C08G65/2603

  the other compounds containing oxygen · CPC title