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

Patent metadata

Field	Value
Publication number	US-2024170228-A1
Application number	US-202218263618-A
Country	US
Kind code	A1
Filing date	Feb 4, 2022
Priority date	Feb 5, 2021
Publication date	May 23, 2024
Grant date	—

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

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 ionic plastic crystal is a multicationic ionic plastic crystal comprising at least two delocalized anions paired with at least two guanidine, amidine or phosphazene organic superbase-derived cations.

3 . The ionic plastic crystal according to claim 1 or 2 , 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.

4 . The ionic plastic crystal according to claim 3 , wherein the delocalized anion is [TFSI] − .

5 . The ionic plastic crystal according to claim 3 , wherein the delocalized anion is [FSI] − .

6 . The ionic plastic crystal according to any one of claims 1 to 5 , wherein the guanidine, amidine or phosphazene organic superbase is selected from the group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP), tert-butylimino-tri(pyrrolidino)phosphorane (BTPP), and tert-butylimino-tris(dimethylamino)phosphorane (P 1 -t-Bu).

7 . The ionic plastic crystal according to any one of claims 1 to 6 , 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 and R 1 is an optionally 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.

8 . The ionic plastic crystal according to claim 7 , wherein R 1 is a hydrogen atom, and the ionic plastic crystal is a protic ionic plastic crystal.

9 . The ionic plastic crystal according to claim 7 , wherein R 1 is 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, and a carbonylamino-C 1 -C 10 alkyl-acrylate, and the ionic plastic crystal is a crosslinked ionic plastic crystal.

10 . The ionic plastic crystal according to any one of claims 7 to 9 , 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 and R 1 is an optionally 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.

11 . The ionic plastic crystal according to claim 10 , wherein the delocalized anion is selected from the group consisting of [TFSI] − and [FSI] − anions.

12 . The ionic plastic crystal according to claim 11 , wherein the delocalized anion is [FSI] − .

13 . An ionic plastic crystal composition comprising at least one ionic plastic crystal as defined in any one of claims 1 to 12 and at least one additional component and/or at least one polymer.

14 . The ionic plastic crystal composition according to claim 13 , wherein the additional component is selected from the group consisting of solvents, ionic conductors, inorganic particles, glass particles, ceramic particles, plasticizing agents, and a combination of at least two thereof.

15 . The ionic plastic crystal composition according to claim 14 , wherein the inorganic particle comprises a compound having a garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, anti-perovskite, or argyrodite type structure, or comprises a compound of the M-P-S, M-P—S—O, M-P—S—X, M-P—S—O—X type (where M is an alkali or alkaline earth metal, and X is F, Cl, Br, I or a combination of at least two thereof) in crystalline phase, amorphous phase and/or glass-ceramic phase, or a mixture of at least two thereof.

16 . The ionic plastic crystal composition according to claim 15 , wherein the inorganic particle comprises at least one of the following compounds:
MLZO (e.g., M 7 La 3 Zr 2 O 12 , M (7-a) La 3 Zr 2 Al b O 12 , M (7-a) La 3 Zr 2 Ga b O 12 , M (7-a) La 3 Zr (2-b) Ta b O 12 and M (7-a) La 3 Zr (2-b) Nb b O 12 ); MLTaO (e.g., M 7 La 3 Ta 2 O 12 , M 5 La 3 Ta 2 O 12 and M 6 La 3 Ta 1.5 Y 0.5 O 12 ); MLSnO (e.g., M 7 La 3 Sn 2 O 12 ); MAGP (e.g., M 1+a Al a Ge 2-a (PO 4 ) 3 ); MATP (e.g., M 1+a AlaTi 2-a (PO 4 ) 3 ); MLTiO (e.g., M 3a La (2/3-a) TiO 3 ); MZP (e.g., M a Zr b (PO 4 ) c ); MCZP (e.g., M a Ca b Zr c (PO 4 ) d ) MGPS (e.g., M a Ge b P c S d such as M 10 GeP 2 S 12 ); MGPSO (e.g., M a Ge b P c S d O e ); MSiPS (e.g., M a Si b P c S d such as M 10 SiP 2 S 12 ); MSiPSO (e.g., M a Si b P c S d O e ); MSnPS (e.g., M a Sn b P c S d such as M 10 SnP 2 S 12 ); MSnPSO (e.g., M a Sn b P c S d O e ); MPS (e.g., M a P b S c such as M 7 P 3 S 11 ); MPSO (e.g., M a P b S c O d ); MZPS (e.g., M a Zn b P c S d ); MZPSO (e.g., M a Zn b P c S d O e ); xM 2 S-yP 2 S 5 ; xM 2 S-yP 2 S 5 -zMX; xM 2 S-yP 2 S 5 -zP 2 O 5 ; xM 2 S-yP 2 S 5 -zP 2 O 5 -wMX; xM 2 S-yM 2 O-zP 2 S 5 ; xM 2 S-yM 2 O-zP 2 S 5 -wMX; xM 2 S-yM 2 O-zP 2 S 5 -wP 2 O 5 ; xM 2 S-yM 2 O-zP 2 S 5 -wP 2 O 5 -vMX; xM 2 S-ySiS 2 ; MPSX (e.g., M a P b S c Xd such as M 7 P 3 S 11 X, M 7 P 2 S 8 X and M 6 PS 5 X); MPSOX (e.g., M a P b S c O d X e ); MGPSX (e.g., M a Ge b P c S d X f ); MGPSOX (e.g., M a Ge b P c S d O e X f ); MSIPSX (e.g., M a Si b P c S d X e ); MSiPSOX (e.g., M a Si b P c S d O e X f ); MSnPSX (e.g., M a Sn b P c S d X e ); MSnPSOX (e.g., M a Sn b P c S d O e X f ); MZPSX (e.g., M a Zn b P c S d X f )

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

• H01G11/56 Primary

  Solid electrolytes, e.g. gels; Additives therein · CPC title

• H01G11/24

  characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor · CPC title

• H01G11/28

  arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives · CPC title

• H01G11/46

  Metal oxides · CPC title