Ionic plastic crystals, compositions comprising same, methods for manufacturing same and uses thereof

Patent metadata

Field	Value
Publication number	US-12469650-B2
Application number	US-202218263618-A
Country	US
Kind code	B2
Filing date	Feb 4, 2022
Priority date	Feb 5, 2021
Publication date	Nov 11, 2025
Grant date	Nov 11, 2025

Abstract

The present technology relates to an ionic plastic crystal comprising at least one delocalized anion paired with at least one an organic guanidine, amidine or phosphazene organic superbase-derived cation for use in electrochemical applications, particularly in electrochemical accumulators such as batteries, electrochromic devices, and supercapacitors. The present technology also relates to an ionic plastic crystal composition, an ionic plastic crystal-based solid electrolyte composition, an ionic plastic crystal-based solid electrolyte, an electrode material comprising the ionic plastic crystal or the ionic plastic crystal composition. Their uses in electrochemical cells and electrochemical accumulators as well as their processes of manufacturing and an NHO-stabilized intermediary ion-neutral complex are also described.

First claim

What is claimed is:

1 . An ionic plastic crystal comprising at least one delocalized anion paired with at least one guanidine, amidine or phosphazene organic superbase-derived cation.

2 . The ionic plastic crystal according to claim 1 , wherein the delocalized anion is selected from the group consisting of trifluoromethanesulfonate (or triflate) [TfO] − , bis(trifluoromethanesulfonyl)imide [TFSI] − , bis(fluorosulfonyl)imide [FSI] − , 2-trifluoromethyl-4,5-dicyanoimidazolate [TDI] − , hexafluorophosphate [PF 6 ] − , and tetrafluoroborate [BF 4 ] − anions.

3 . The ionic plastic crystal according to claim 1 , wherein the cation is selected from the group consisting of guanidine, amidine or phosphazene organic superbase-derived cations of Formulae 2 to 8:

wherein,
the ionic plastic crystal is a monocationic ionic plastic crystal and R 1 is a hydrogen atom or a linear or branched substituent selected from a C 1 -C 10 alkyl-acrylate, a C 1 -C 10 alkyl-methacrylate, a carbonylamino-C 1 -C 10 alkyl-methacrylate, a carbonylamino-C 1 -C 10 alkyl-acrylate, a carbonyloxy-C 1 -C 10 alkyl-methacrylate, and a carbonyloxy-C 1 -C 10 alkyl-acrylate; or
the ionic plastic crystal is a multicationic ionic plastic crystal comprising at least two delocalized anions paired with at last two quanidine, amidine or phosphazene organic superbase-derived cations and R 1 is an unsubstituted or substituted organic bridging group separating at least two of the cations and is selected from a linear or branched C 1 -C 10 alkylene, a linear or branched C 1 -C 10 alkyleneoxyC 1 -C 10 alkylene, a linear or branched poly(C 1 -C 10 alkyleneoxy) C 1 -C 10 alkylene, a linear or branched polyether, a linear or branched polyester, a C 6 -C 12 arylene, a C 5 -C 12 heteroarylene, a C 3 -C 12 cycloalkylene, and a C 3 -C 12 heterocycloalkylene.

4 . The ionic plastic crystal according to claim 3 , wherein the ionic plastic crystal is selected from ionic plastic crystals of Formulae 10 to 16:

wherein,
X— is a delocalized anion selected from the group consisting of [TfO] − , [TFSI] − , [FSI] − , [TDI] − , [PF 6 ] − , and [BF 4 ] − ; and
the ionic plastic crystal is a monocationic ionic plastic crystal and R 1 a hydrogen atom or a linear or branched substituent selected from a C 1 -C 10 alkyl-acrylate, a C 1 -C 10 alkyl-methacrylate, a carbonylamino-C 1 -C 10 alkyl-methacrylate, a carbonylamino-C 1 -C 10 alkyl-acrylate, a carbonyloxy-C 1 -C 10 alkyl-methacrylate, and a carbonyloxy-C 1 -C 10 alkyl-acrylate; or
the ionic plastic crystal is a multicationic ionic plastic crystal comprising at least two delocalized anions paired with at least to quanidine, amidine or phosphazene organic superbase-derived cations and R 1 is an unsubstituted or substituted organic bridging group separating at least two of the cations and is selected from a linear or branched C 1 -C 10 alkylene, a linear or branched C 1 -C 10 alkyleneoxyC 1 -C 10 alkylene, a linear or branched poly(C 1 -C 10 alkyleneoxy) C 1 -C 10 alkylene, a linear or branched polyether, a linear or branched polyester, a C 6 -C 12 arylene, a C 5 -C 12 heteroarylene, a C 3 -C 12 cycloalkylene, and a C 3 -C 12 heterocycloalkylene.

5 . An ionic plastic crystal composition comprising at least one ionic plastic crystal as defined in claim 1 and at least one additional component, at least one polymer, or a combination of at least one additional component and at least one polymer.

6 . The ionic plastic crystal composition according to claim 5 , wherein the additional component is an inorganic particle.

7 . The ionic plastic crystal composition according to claim 5 , wherein the polymer is:
linear or branched; crosslinked; a polyether-type polymer; or a block copolymer composed of at least one lithium-ion solvating segment and at least one cross-linkable segment, the lithium-ion solvating segment being selected from homo- or copolymers having repeating units of Formula 32:

wherein,
R 3 is selected from a hydrogen atom, a C 1 -C 10 alkyl group, and a —(CH 2 —O—R 4 R 5 ) group;
R 4 is (CH 2 —CH 2 —O) m ;
R 5 is selected from a hydrogen atom and a C 1 -C 10 alkyl group;
y is an integer selected from the range of 10 to 200,000; and
m is an integer selected from the range of 0 to 10.

8 . The ionic plastic crystal composition according to claim 5 , wherein the ionic plastic crystal composition is
(i) an ionic plastic crystal-based electrolyte composition, (ii) comprised in a binder; (iii) comprised in an electrochemical cell; (iv) comprised in a supercapacitor; or (v) comprised in an electrochromic material.

9 . A solid electrolyte composition comprising an ionic plastic crystal as defined in claim 1 and at least one salt or at least one additional component.

10 . The solid electrolyte composition according to claim 9 , wherein:
the salt is an ionic salt selected from the group consisting of a lithium salt, a sodium salt, a potassium salt, a calcium salt, and a magnesium salt; or the additional component is selected from the group consisting of ionically conductive materials, inorganic particles, glass particles, ceramic particles, plasticizing agents, and a combination of at least two thereof or is selected from NASICON, LISICON, thio-LISICON type compounds, garnets, in crystalline and/or amorphous form, and a combination of at least two thereof.

11 . A solid electrolyte comprising a solid electrolyte composition as defined in claim 9 .

12 . An electrode material comprising an electrochemically active material and an ionic plastic crystal as defined in claim 1 .

13 . The electrode material according to claim 12 , wherein the electrochemically active material is in the form of particles or is selected from the group consisting of metal oxides, lithium metal oxides, metal phosphates, lithium metal phosphates, titanates, lithium titanates, metal fluorophosphates, lithium metal fluorophosphates, metal oxyfluorophosphates, lithium metal oxyfluorophosphates, metal sulfates, lithium metal sulfates, metal halides, lithium metal halides, sulfur, selenium, and a combination of at least two thereof.

14 . The electrode material according to claim 12 , wherein the electrode material further comprises at least one electronically conductive material.

15 . An electrode comprising an electrode material as defined in claim 12 on a current collector.

16 . 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 at least one ionic plastic crystal as defined in claim 1 .

17 . 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 the ionic plastic crystal composition as defined in claim 5 .

18 . An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the negative electrode and the positive electrode is as defined in claim 15 .

19 . An electrochemical cell comprising a negative electrode, a positive electrode, and a solid electroly

Assignees

• Hydro Quebec

Inventors

• Daigle Jean-Christophe
• Barray Francis
• Guerfi Abdelbast
• Fleutot Benoit
• Garitte Emmanuelle
• Krachkovskiy Sergey
• Koh Ki Seok

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M10/056

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M10/0525

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

• H01M4/625

  Carbon or graphite · CPC title

• H01M4/623

  fluorinated polymers · CPC title