CN116806221A - Ionic plastic crystals, compositions comprising the same, methods of manufacture and uses thereof - Google Patents

Ionic plastic crystals, compositions comprising the same, methods of manufacture and uses thereof Download PDF

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CN116806221A
CN116806221A CN202280013197.5A CN202280013197A CN116806221A CN 116806221 A CN116806221 A CN 116806221A CN 202280013197 A CN202280013197 A CN 202280013197A CN 116806221 A CN116806221 A CN 116806221A
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ion
plastic crystal
ionic
lithium
branched
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J-C·戴格尔
F·巴雷
A·盖尔斐
B·弗勒托
E·加里特
S·克拉奇科夫斯基
K·S·高
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Hydro Quebec
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Hydro Quebec
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Priority claimed from PCT/CA2022/050159 external-priority patent/WO2022165598A1/en
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Abstract

The present technology relates to an ionic plastic crystal comprising at least one delocalized anion paired with at least one cation derived from guanidine, amidine or phosphazene organic superbase for electrochemical applications, in particular for electrochemical energy storage devices such as batteries, electrochromic devices and supercapacitors. The present technology also relates to ion plastic crystal compositions, ion plastic crystal-based solid electrolyte compositions, ion plastic crystal-based solid electrolytes, electrode materials comprising the ion plastic crystals or the ion plastic crystal compositions. Their use in electrochemical cells and electrochemical accumulators is also described, as well as their method of manufacture and NHO-stabilised intermediate ion neutral complexes.

Description

Ionic plastic crystals, compositions comprising the same, methods of manufacture and uses thereof
RELATED APPLICATIONS
The present application is based on the priority of U.S. provisional patent application Ser. No.63/146,356, filed on 5/2/2021, and U.S. provisional patent application Ser. No.63/260,710, filed on 8/2021, which are incorporated herein by reference in their entireties for all purposes, as if set forth in applicable legal requirements.
Technical Field
The present application relates to the field of ion plastic crystals and their use in electrochemical applications. More particularly, the present application relates to the field of ion plastic crystals, compositions comprising them, methods of their manufacture and their use as solid state electrolytes in electrochemical cells, electrochromic devices, supercapacitors, electrochemical accumulators, in particular in all-solid state batteries.
Background
Ionic plastic crystals are considered as promising materials for solid state electrolytes. While this technology is still in the initiation phase, ion conductors based on plastic crystals exhibit significant advantages over conventional solid state electrolyte materials, including high flexibility and plasticity, nonflammability, excellent ionic conductivity, and good thermal and electrochemical properties.
Despite their significant advantages, the mechanism of conduction and the relationship between cations or anions and the physical properties of these materials are not well understood. Thus, it is not easy to predict whether a combination of cations and anions may form an ionic melt or ionic liquid or form plastic crystals at a particular temperature.
Accordingly, there is a need to develop new solid state electrolytes based on ionic plastic crystals that do not include one or more of the disadvantages of conventional solid state electrolytes or that provide one or more advantages over them.
SUMMARY
According to a first aspect, the present technology relates to an ionic plastic crystal comprising at least one delocalized anion paired with at least one cation derived from a guanidine, amidine or phosphazene organic superbase.
According to one embodiment, the ionic plastic crystal is a polycationic ionic plastic crystal comprising at least two delocalized anions paired with at least two cations derived from guanidine, amidine or phosphazene organic superbase.
According to another embodiment, the delocalized anion is selected from the group consisting of triflate (or triflate) [ TfO ]] - Bis (trifluoromethanesulfonyl) imide [ TFSI] - Bis (fluorosulfonyl) imide [ FSI ]] - 2-trifluoromethyl-4, 5-dicyanoimidazo [ TDI ]] - Hexafluorophosphate [ PF ] 6 ] - And tetrafluoroborate [ BF ] 4 ] - An anion. According to one example, the delocalized anion is [ TFSI ]] - . According to another example, the delocalized anion is [ FSI ]] - 。
According to another embodiment, the guanidine, amidine or phosphazene organic super-base is selected from 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-dimethylperfhydro-1, 3, 2-diazaphosphorine (BEMP), tert-butylimino-tris (pyrrolidine) phosphine (BTPP), and tert-butylidene Amino-tris (dimethylamino) phosphane (P) 1 -t-Bu)。
According to another embodiment, the cation is selected from cations derived from guanidine, amidine or phosphazene organic superbases of formulae 2 to 8:
wherein, the liquid crystal display device comprises a liquid crystal display device,
the ion plastic crystal is a single cation ion plastic crystal, and R 1 Is a hydrogen atom or is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-acrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates and carbonyloxy-C 1 -C 10 Linear or branched substituents of alkyl-acrylates; or (b)
The ion plastic crystal is a multi-cation ion plastic crystal, and R 1 Is an optionally substituted organic bridging group separating at least two cations and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
In some embodiments, R 1 Is a hydrogen atom, and the ion plastic crystal is a proton ion plastic crystal.
In other embodiments, R 1 Is selected fromC 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates and carbonylamino-C 1 -C 10 A linear or branched substituent of an alkyl-acrylate, and the ionic plastic crystal is a cross-linked ionic plastic crystal.
According to some preferred embodiments, the ionic plastic crystal is selected from ionic plastic crystals of formulae 10 to 16:
wherein, the liquid crystal display device comprises a liquid crystal display device,
X - is selected from [ TfO ]] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Is a delocalized anion of (a); and
the ion plastic crystal is a single cation ion plastic crystal, and R 1 Is a hydrogen atom or is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-acrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates and carbonyloxy-C 1 -C 10 Linear or branched substituents of alkyl-acrylates; or (b)
The ion plastic crystal is a multi-cation ion plastic crystal, and R 1 Is an optionally substituted organic bridging group separating at least two cations and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene radicals And C 3 -C 12 Heterocycloalkylene group.
According to some preferred embodiments, the delocalized anion is selected from [ TFSI] - And [ FSI ]] - Anions, preferably [ FSI ]] - 。
According to another aspect, the present technology relates to an ionic plastic crystal composition comprising at least one ionic plastic crystal as defined herein and at least one additional component and/or at least one polymer.
According to one embodiment, the additional component is selected from the group consisting of solvents, ionic conductors, inorganic particles, glass particles, ceramic particles, plasticizers, and combinations of at least two thereof.
In some embodiments, the inorganic particles comprise a compound having a garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, anti-perovskite, or thiosilver-germanium ore (argyrodite) type structure, or comprise a compound of the M-P-S, M-P-S-O, M-P-S-X, M-P-S-O-X type (wherein M is an alkali metal or alkaline earth metal, and X is F, cl, br, I or a combination of at least two thereof), be a crystalline phase, an amorphous phase, and/or a glass ceramic phase, or a mixture of at least two thereof.
In some preferred embodiments, the inorganic particles comprise 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 ) The method comprises the steps of carrying out a first treatment on the surface of the 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 ) The method comprises the steps of carrying out a first treatment on the surface of the MLSnO (e.g. M 7 La 3 Sn 2 O 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MAGP (e.g. M 1+a Al a Ge 2-a (PO 4 ) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the MATP (e.g. M 1+a Al a Ti 2-a (PO 4 ) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the MLTiO (e.g. M 3a La (2/3-a) TiO 3 ) The method comprises the steps of carrying out a first treatment on the surface of the MZP (e.g. M a Zr b (PO 4 ) c ) The method comprises the steps of carrying out a first treatment on the surface of the MCZP (e.g. M a Ca b Zr c (PO 4 ) d ) The method comprises the steps of carrying out a first treatment on the surface of the MGPS (e.g. M a Ge b P c S d For example M 10 GeP 2 S 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MGPSO (e.g. M a Ge b P c S d O e ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPS (e.g. M a Si b P c S d For example M 10 SiP 2 S 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPSO (e.g. M a Si b P c S d O e ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPS (e.g. M a Sn b P c S d For example M 10 SnP 2 S 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPSO (e.g. M a Sn b P c S d O e ) The method comprises the steps of carrying out a first treatment on the surface of the MPS (e.g. M a P b S c For example M 7 P 3 S 11 ) The method comprises the steps of carrying out a first treatment on the surface of the MPSO (e.g. M a P b S c O d ) The method comprises the steps of carrying out a first treatment on the surface of the MZPS (e.g. M a Zn b P c S d ) The method comprises the steps of carrying out a first treatment on the surface of the MZISO (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 The method comprises the steps of carrying out a first treatment on the surface of the MPSX (e.g. M a P b S c X d For example 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 ) The method comprises the steps of carrying out a first treatment on the surface of the MGPSX (e.g. M a Ge b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MGPSOX (e.g. M a Ge b P c S d O e X f ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPSX (e.g. M a Si b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPSox (e.g. M a Si b P c S d O e X f ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPSX (e.g. M a Sn b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPSOX (e.g. M a Sn b P c S d O e X f ) The method comprises the steps of carrying out a first treatment on the surface of the MZPSX (e.g. M a Zn b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MZIPSOX (e.g. M a Zn b P c S d O e X f )；M 3 OX；M 2 HOX；M 3 PO 4 ；M 3 PS 4 The method comprises the steps of carrying out a first treatment on the surface of the And M a PO b N c (wherein a=2b+3c-5); a crystalline phase, an amorphous phase, a glass ceramic phase, or a combination thereof;
wherein the method comprises the steps of
M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, the amount of M is adjusted to achieve electroneutrality;
x is selected from F, cl, br, I or a combination thereof;
a. b, c, d, e and f are non-0 values and are independently selected among the formulae to achieve electroneutrality; and
v, w, x, y and z are non-0 values and are independently selected in the formulae to obtain stable compounds.
In other embodiments, the inorganic particles are ceramic or glass-ceramic. According to one example, the ceramic or glass-ceramic is an oxide-type ceramic, a sulfide-type ceramic, an oxysulfide-type ceramic, or a combination of at least two thereof. For example, sulfide type ceramics are selected from Li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 2 S-P 2 S 5 、Li 7 P 3 S 11 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 9.6 P 3 S 12 And Li (lithium) 3.25 P 0.95 S 4 . According to a related variant, the sulfide ceramic is Li 6 PS 5 Cl。
In other embodiments, the ceramic or glass-ceramic is present in the ion plastic crystal composition at a concentration of at least 50% by weight. For example, the ceramic or glass-ceramic is present in the ion plastic crystal composition at a concentration of about 50 wt% to about 95 wt%, or about 55 wt% to about 95 wt%, or about 60 wt% and about 95 wt%, or about 65 wt% to about 95 wt%, or about 70 wt% to about 95 wt%, or about 75 wt% to about 95 wt%, or about 80 wt% to about 95 wt%, or about 85 wt% to about 95 wt%, or about 90 wt% to about 95 wt%, inclusive. According to a related variant, the ceramic or glass-ceramic is present in the ion plastic crystal composition in a concentration of about 90% by weight. According to another related variant, the plastic crystals are present in the ionic plastic crystal composition at a concentration of about 10% by weight.
In other preferred embodiments, the inorganic particles are selected from titanium dioxide (TiO 2 ) Alumina (Al) 2 O 3 ) And silicon dioxide (SiO) 2 ) Filler additives for particles or nanoparticles.
In some embodiments, the polymer is linear or branched.
In some embodiments, the polymer is crosslinked.
In some embodiments, the polymer is present in the ionic plastic crystalline composition at a concentration of at least 10% by weight. For example, the polymer is present in the ion plastic crystal composition at a concentration of about 5 wt% to about 45 wt%, or about 10 wt% to about 45 wt%, or about 15 wt% to about 45 wt%, or about 20 wt% to about 45 wt%, or about 25 wt% to about 45 wt%, or about 30 wt% to about 45 wt%, or about 35 wt% to about 45 wt%, or about 40 wt% to about 45 wt%, including upper and lower limits.
In some preferred embodiments, the polymer is a polyether polymer. For example, the polyether polymer is a polyethylene oxide (PEO) based polymer.
In other preferred embodiments, the polymer is a block copolymer consisting of at least one lithium ion solvating segment and optionally at least one crosslinkable segment, the lithium ion solvating segment being selected from the group consisting of homopolymers or copolymers having repeating units of formula 32:
Wherein, the liquid crystal display device comprises a liquid crystal display device,
R 3 selected from hydrogen atoms, C 1 -C 10 Alkyl or- (CH) 2 -O-R 4 R 5 ) A group;
R 4 is (CH) 2 -CH 2 -O) m ；
R 5 Selected from hydrogen atoms and C 1 -C 10 An alkyl group;
y is an integer selected from 10 to 200,000; and
m is an integer selected from 0 to 10.
In some preferred embodiments, the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group that is multi-dimensionally crosslinkable by irradiation or heat treatment.
According to another embodiment, the ionic plastic crystal composition is an electrolyte composition based on ionic plastic crystals.
According to another aspect, the present technology relates to an adhesive comprising an ion plastic crystal composition as defined herein.
According to another aspect, the present technology relates to an electrochemical cell comprising an ion plastic crystal composition as defined herein.
According to another aspect, the present technology relates to a supercapacitor comprising an ion plastic crystalline composition as defined herein.
According to one embodiment, the supercapacitor is a carbon-carbon supercapacitor.
According to another aspect, the present technology relates to an electrochromic material comprising an ion plastic crystal composition as defined herein.
According to another aspect, the present technology relates to a solid electrolyte composition comprising an ionic plastic crystal as defined herein or an ionic plastic crystal composition as defined herein and at least one salt or at least one additional component.
In some embodiments, the salt is an ionic salt. For example, the ionic salt is selected from lithium, sodium, potassium, calcium and magnesium salts, preferably the ionic salt is a lithium salt. According to a related variant, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiFeSI), (fluorosulfonyl) (trifluoromethanesulfonyl) imide) lithium (Li (FSI) (TFSI)), lithium 2-trifluoromethyl-4, 5-dicyanoimidazole (LiTDI), lithium 4, 5-dicyano-1, 2, 3-triazole (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), lithium difluorophosphate (LiDFP), 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 triflate (LiSO) 3 CF 3 ) (LiOTf), lithium fluoroalkyl phosphate Li [ PF ] 3 (CF 2 CF 3 ) 3 ]Lithium tetrakis (trifluoroacetoxy) borate Li [ B (OCOCF) 3 ) 4 ]Lithium (LiTFAB), bis (1, 2-benzenediol (2-) -O, O') borate Li [ B (C) 6 O 2 ) 2 ](LiBBB), lithium difluoro (oxalate) borate (LiBF 2 (C 2 O 4 ) (LiFeB), liBF 2 O 4 R x (wherein R is x ＝C 2-4 Alkyl) and combinations of at least two thereof.
In some embodiments, the additional component is selected from the group consisting of ion conductive materials, inorganic particles, glass particles, ceramic particles, plasticizers, other similar components, and combinations of at least two thereof. For example, the ceramic particles are nanoceramics. According to a related variant, the additional component is selected from NASICON, LISICON, thio-LISICON type compounds, garnet, in crystalline and/or amorphous form, and combinations of at least two thereof.
According to another aspect, the present technology relates to a solid electrolyte comprising a solid electrolyte composition as defined herein, wherein the solid electrolyte is optionally crosslinked.
According to another aspect, the present technology relates to a solid electrolyte comprising an ionic plastic crystal as defined herein, wherein the solid electrolyte is optionally crosslinked.
According to another aspect, the present technology relates to an electrode material comprising an electrochemically active material and an ion plastic crystal composition as defined herein, wherein the ion plastic crystal composition is optionally crosslinked.
According to another aspect, the present technology relates to an electrode material comprising an electrochemically active material and an ion plastic crystal as defined herein, wherein the ion plastic crystal is optionally crosslinked.
According to one embodiment, the ionic plastic crystal or ionic plastic crystal composition is a binder.
In some embodiments, the electrochemically active material is in the form of particles.
In some embodiments, the electrochemically active material 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 oxofluorophosphates, lithium metal oxofluorophosphates, metal sulfates, lithium metal sulfates, metal halides (e.g., metal fluorides), lithium metal halides (e.g., lithium metal fluorides), sulfur, selenium, and combinations of at least two thereof. For example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), and combinations of at least two thereof.
In some embodiments, the electrode material further comprises at least one electronically conductive material. For example, the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and combinations of at least two thereof. According to a related variant, the electronically conductive material is acetylene black.
In some embodiments, the electrode material has an ion plastic crystal ratio of electrochemically active material to ion plastic of less than about 6, or less than about 5, or less than about 4, or less than about 3, preferably less than about 4.
In some embodiments, the electrode material has a porosity of less than about 8%, or less than about 7%, or less than about 6%, or less than about 5%, or less than about 4%, or less than about 3%, or less than about 2%, or less than about 1%, preferably less than about 5%.
According to another aspect, the present technology relates to an electrode comprising an electrode material as defined herein on a current collector.
According to another aspect, the present technology relates to 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 ion plastic crystal as defined herein, wherein the ion plastic crystal is optionally crosslinked.
According to another aspect, the present technology relates to 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 an ionic plastic crystal composition as defined herein, wherein the ionic plastic crystal composition is optionally crosslinked.
According to another aspect, the present technology relates to 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 herein.
According to another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode, and a solid electrolyte as defined herein.
According to another aspect, the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein.
According to one embodiment, the electrochemical accumulator is a battery selected from the group consisting of a lithium battery, a lithium ion battery, a sodium ion battery, a magnesium battery, and a magnesium ion battery. According to a related variant, the battery is a lithium battery or a lithium ion battery.
According to another aspect, the present technology relates to a method of preparing an ion plastic crystal as defined herein or an ion plastic crystal composition as defined herein, the method comprising the steps of:
(i) Reacting at least one guanidine, amidine, or phosphazene organic superbase with at least one proton source to form at least one complex comprising a protonated guanidine, amidine, or phosphazene organic superbase-derived cation and a counter ion; and
(ii) A complex comprising a protonated guanidine, amidine, or phosphazene organic superbase derived cation and a counterion is reacted with at least one ionic salt.
According to one embodiment, the guanidine, amidine or phosphazene organic super-base is selected from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu. According to a related variant, the guanidine, amidine or phosphazene organic super-base is BEMP. According to another related variant, the guanidine, amidine or phosphazene organic super base is DBU.
According to another embodiment, the ionic salt comprises a salt selected from [ TfO ]] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Delocalized anions of anions. According to a related variant, the delocalized anion is [ TFSI] - . According to another related variant, the delocalized anion is [ FSI] - 。
According to another embodiment, the ionic salt is an alkali metal or alkaline earth metal salt. For example, the alkali metal or alkaline earth metal salt is a lithium salt, sodium salt, potassium salt, calcium salt or magnesium salt, preferably a lithium salt.
According to another embodiment, steps (i) and (ii) are carried out sequentially, simultaneously or partially overlapping each other in time. For example, steps (i) and (ii) are performed sequentially and the step of reacting the guanidine, amidine, or phosphazene organic superbase with a proton source is performed prior to the step of reacting a complex comprising a protonated guanidine, amidine, or phosphazene organic superbase derived cation and a counter ion with an ionic salt.
In another embodiment, guanidine, amidine, or phosphazene organic superbase, proton source, and ionic salt are mixed together and reacted.
According to another embodiment, steps (i) and (ii) are carried out in the presence of a solvent. For example, the solvent is selected from the group consisting of methylene chloride, dimethyl carbonate, acetonitrile, ethanol, and miscible combinations of at least two thereof. According to another related variant, the solvent is acetonitrile.
In some embodiments, the solvent is the proton source of step (i).
According to another embodiment, the proton source of step (i) is a first proton source and steps (i) and (ii) are performed in the presence of a second proton source. For example, the second proton source is an acid selected from carboxylic acids (e.g., formic acid, acetic acid, propionic acid, lactic acid, and trifluoroacetic acid), p-toluenesulfonic acid, sulfuric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, nitric acid, and hydrofluoric acid.
According to another embodiment, steps (i) and (ii) are performed in the presence of an activator and/or a stabilizer, and the method further comprises forming a stabilized intermediate ion neutral complex.
In some embodiments, the activator and/or stabilizer is a bis-silylated compound of formula 17:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z is a substituted or unsubstituted organic group selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, linear or branched polyether, linear or branched polycarbonate, linear or branched polythiocarbonate, linear or branched polyamide, linear or branched polyimide, linear or branched polyurethane, linear or branched polysiloxane, linear or branched thioether, linear or branched polyphosphazene, linear or branched polyester, and linear or branched polythioester; and
R 2 independently and at each occurrence is selected from alkyl, aryl, and arylalkyl.
According to another embodiment, the method further comprises the step of preparing the bis-silylated compound of formula 17.
In some embodiments, the step of preparing the bis-silylated compound of formula 17 is performed by a silylation reaction of a compound comprising at least two hydroxyl groups with a silylating agent. For example, the compound comprising at least two hydroxyl groups is selected from the group consisting of glycerol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-propanediol, 1, 2-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 2-ethyl-1, 3-hexanediol, p-menthyl-3, 8-diol, 2-methyl-2, 4-pentanediol, polycaprolactone diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentylene glycol, polyethylene glycol, 2,3, 4, 5-octafluoro-1, 6-hexanediol, and combinations of at least two thereof. According to a related variant, the bis-silylated compound of formula 17 is bis-silylated diethylene glycol. According to another related variant, the bis-silylated compound of formula 17 is bis-silylated glycerol.
In some embodiments, the silylation reaction is carried out by a base-catalyzed silylation reaction and involves the use of (R 2 ) 3 The Si-group replaces the acidic or active hydrogen on the hydroxyl group.
In some embodiments, the silylation reaction is carried out in the presence of a base. According to a related variant, the base is 4-dimethylaminopyridine. According to another related variant, the base is imidazole.
In some embodiments, the silylation reaction is carried out in the presence of an aprotic solvent. According to a related variant, the aprotic solvent is dichloromethane. According to another related variant, the aprotic solvent is tetrahydrofuran.
In some embodiments, the silylating agent is selected from the group consisting of trialkylsilyl chloride, trimethylsilyl chloride (TMS-Cl), triethylsilyl chloride (TES-Cl), isopropyldimethylsilyl chloride (IPMS-Cl), diethylisopropylsilyl chloride (DEIPS-Cl), tert-butyldimethylsilyl chloride (TBDMS-Cl or TBS-Cl), tert-butyldiphenylsilyl chloride (TBDPS-Cl or TPS-Cl) and triisopropylsilyl chloride (TIPS-Cl), nitrogen-containing silyl ethers, N, O-bis (tert-butyldimethylsilyl) acetamide (BSA), N-methyl-N- (trimethylsilyl) trifluoroacetamide (MSTFA), N- (trimethylsilyl) dimethylamine (TMSPDEA), N- (trimethylsilyl) imidazole (TMSI or TSIM), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), and N-methyl-N- (trimethylsilyl) acetamide (MSA). According to a related variant, the silylating agent is trimethylsilyl chloride (TMS-Cl). According to another related variant, the silylating agent is t-butyldimethylsilyl chloride (TBDMS-Cl or TBS-Cl).
In some embodiments, the silylating agent is added at a molar ratio of "silyl groups to be derivatized" of about 1:0.9.
In other embodiments, the silylating agent is added at a molar ratio of "OH groups to be derivatized: silyl" of about 1:1.
In other embodiments, the silylating agent is added in excess relative to the number of hydroxyl groups on the compound comprising at least two hydroxyl groups. According to one example, the amount of silylating agent is in the range of about 2 equivalents to about 5 equivalents per equivalent of compound containing at least two hydroxyl groups, including upper and lower limits. For example, the amount of silylating agent is in the range of about 2 equivalents to about 4.5 equivalents, or about 2 equivalents to about 4 equivalents, or about 2 equivalents to about 3.75 equivalents, or about 2 equivalents to about 3.5 equivalents, including upper and lower limits, per equivalent of compound containing at least two hydroxyl groups.
In some embodiments, the silylation reaction is performed at room temperature.
In some embodiments, steps (i) and (ii) are performed at a temperature of about 20 ℃ to about 200 ℃, including upper and lower limits. For example, steps (i) and (ii) are performed at a temperature of about 40 ℃ to about 80 ℃, or about 45 ℃ to about 75 ℃, or about 50 ℃ to about 70 ℃, or about 55 ℃ to about 65 ℃, including upper and lower limits.
In some embodiments, steps (i) and (ii) are performed for at least 4 days.
According to another embodiment, the method further comprises a purification step. For example, the purification step is carried out by extraction, distillation or evaporation.
According to another embodiment, the method further comprises a functionalization step. According to one example, the functionalization step is carried out by reaction between the-NH functional group of the protonated guanidine, amidine or phosphazene organic super-base derived cation and at least one crosslinkable functional group precursor. For example, the crosslinkable functional group is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-acrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates and carbonylamino-C 1 -C 10 Alkyl-acrylate groups.
According to another embodiment, the method further comprises the step of coating the ion plastic crystal composition or suspension comprising ion plastic crystals on the substrate. For example, the coating step is performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method. According to a related variant, the coating step is performed by at least one of a blade coating method or a slot die coating method.
According to another embodiment, the method further comprises drying the composition or suspension. According to one example, the drying and coating steps are performed simultaneously.
According to another embodiment, the method further comprises a crosslinking step. According to one example, the crosslinking step is carried out by ultraviolet radiation, by heat treatment, by microwave radiation, under an electron beam, by gamma irradiation or by X-ray irradiation. According to a related variant, the crosslinking step is carried out by ultraviolet radiation, heat treatment or under an electron beam. In some embodiments, the crosslinkingThe step is performed in the presence of a crosslinking agent, a thermal initiator, a photoinitiator, a catalyst, a plasticizer, or a combination of at least two thereof. According to a related variant, the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone (Irgacure) TM 651)。
According to another aspect, the present technology relates to a stabilized intermediate ion neutral complex obtained by reacting at least one cation derived from a guanidine, amidine or phosphazene organic superbase and at least one bis-silylated compound of formula 17:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z is a substituted or unsubstituted organic group selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, linear or branched polyether, linear or branched polycarbonate, linear or branched polythiocarbonate, linear or branched polyamide, linear or branched polyimide, linear or branched polyurethane, linear or branched polysiloxane, linear or branched thioether, linear or branched polyphosphazene, linear or branched polyester, and linear or branched polythioester; and
R 2 independently and at each occurrence is selected from alkyl, aryl, and arylalkyl.
According to one embodiment, the cation derived from guanidine, amidine or phosphazene organic superbase is selected from protonated 1, 8-diazabicyclo [5.4.0]Undec-7-ene [ H-DBU ]] + Protonated 1, 5-diazabicyclo [4.3.0]Non-5-ene [ H-DBN] + Protonated 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene [ H-MTBD] + Protonated 2-t-butylimino-2-diethylamino-1, 3-dimethylperfhydro-1, 3, 2-diazaphosphole [ H-BEMP] + Protonated t-butylimino-tris (pyrrolidine) phosphane [ H-BTPP] + And protonated t-butylimino-tris (dimethylamino) phosphane [ P 1 -t-Bu] + 。
In some embodiments, the stabilized intermediate ion neutral complex has the formula 25 to 31:
/>
Wherein, the liquid crystal display device comprises a liquid crystal display device,
z and R 2 As defined herein; and
X - is selected from [ TfO ]] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Is a delocalized anion of (a).
According to another aspect, the present technology relates to a method of preparing an ion plastic crystal as defined herein or an ion plastic crystal composition as defined herein, the method comprising the steps of:
(i) Reacting a guanidine, amidine, or phosphazene organic superbase with an organic bridging compound to form a polycationic complex comprising at least two organic superbase-based cationic moieties separated by an optionally substituted organic bridging group and paired with a counter ion; and
(ii) Reacting the polycationic complex with at least one ionic salt.
According to one embodiment, the guanidine, amidine or phosphazene organic super-base is selected from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu. According to a related variant, the guanidine, amidine or phosphazene organic super-base is BEMP. According to another related variant, the guanidine, amidine or phosphazene organic super base is DBU.
According to another embodiment, the organic bridging compound comprises an optionally substituted organic bridging group and at least two anionic leaving groups. For example, the anionic leaving group is a halide. According to a correlation changeA body, a halogen ion selected from F - 、Cl - 、Br - And I - . According to another related variant, the halide ion is Br - 。
According to another embodiment, the optionally substituted organic bridging group is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
In some embodiments, the organic bridging group is 1,2,4, 5-tetrakis (bromomethyl) benzene.
According to another embodiment, the ionic salt comprises a salt selected from [ TfO ]] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Is a delocalized anion of (a). According to a related variant, the delocalized anion is [ TFSI] - . According to another related variant, the delocalized anion is [ FSI] - 。
According to another embodiment, the ionic salt is an alkali metal or alkaline earth metal salt. For example, the alkali or alkaline earth metal salt is a lithium, sodium, potassium, calcium or magnesium salt. Preferably, the alkali or alkaline earth metal salt is a lithium salt.
According to another embodiment, steps (i) and (ii) are carried out sequentially, simultaneously or partially overlapping each other in time. According to one example, steps (i) and (ii) are carried out sequentially and the step of reacting the guanidine, amidine or phosphazene organic superbase with the organic bridging compound is carried out before the step of reacting the polycationic complex with the ionic salt.
In another embodiment, guanidine, amidine, or phosphazene organic superbase, organic bridging compound, and ionic salt are mixed together and reacted.
According to another embodiment, steps (i) and (ii) are carried out in the presence of a solvent. For example, the solvent is selected from the group consisting of methylene chloride, dimethyl carbonate, acetonitrile, ethanol, and miscible combinations of at least two thereof. According to a related variant, the solvent is dichloromethane.
According to another embodiment, the step of reacting a guanidine, amidine or phosphazene organic superbase with an organic bridging compound is performed in the presence of a base. According to a related variant, the base is triethylamine (Et 3 N)。
In some embodiments, steps (i) and (ii) are performed at room temperature.
In some embodiments, the step of reacting the guanidine, amidine, or phosphazene organic superbase with the organic bridging compound is performed for about 4 days.
In some embodiments, the step of reacting the polycationic complex with the ionic salt is performed for about 3 days.
According to another embodiment, the method further comprises a purification step. For example, the purification step is carried out by extraction, distillation or evaporation.
According to another embodiment, the method further comprises the step of coating the ion plastic crystal composition or suspension comprising ion plastic crystals on the substrate. For example, the coating step is performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method. According to a related variant, the coating step is performed by at least one of a blade coating method or a slot die coating method.
According to another embodiment, the method further comprises the step of drying the composition or suspension.
In some embodiments, the drying and coating steps are performed simultaneously.
According to another aspect, the present technology relates to a method of producing an electrode material as defined herein, the method comprising the steps of:
(i) Preparing a carbon and binder slurry;
(ii) Preparing a catholyte solution based on ionic plastic crystals; and
(iii) Ion plastic crystals, carbon and binder slurries were prepared.
According to one embodiment, the step of preparing the carbon and binder slurry comprises dispersing the carbon in the binder composition.
According to another embodiment, the method further comprises preparing an adhesive composition.
In some embodiments, the carbon comprises carbon black.
In some embodiments, the carbon comprises vapor grown carbon fibers.
According to another embodiment, the adhesive composition comprises an adhesive and optionally a solvent and/or a carbon dispersant.
In some embodiments, the binder comprises a fluoropolymer. For example, the fluoropolymer is polytetrafluoroethylene, polyvinylidene fluoride, or poly (vinylidene fluoride-co-hexafluoropropylene). According to a related variant, the fluoropolymer is polyvinylidene fluoride.
In some embodiments, the solvent is N-methyl-2-pyrrolidone.
In some embodiments, the carbon dispersant is polyvinylpyrrolidone.
According to another embodiment, the step of preparing the adhesive composition is performed by mixing the adhesive with a solvent and/or a carbon dispersant. For example, the mixing step is performed by a rolling process.
According to another embodiment, the step of preparing the ion plastic crystal catholyte solution comprises diluting the ion plastic crystal and the ion salt in a solvent. For example, the solvent is N-methyl-2-pyrrolidone.
According to another embodiment, the step of preparing the ion plastic crystals, carbon and binder slurry comprises gradually adding a catholyte solution based on ion plastic crystals to the carbon and binder slurry.
According to another embodiment, the method further comprises adding an electrochemically active material to the ion plastic crystal, the carbon, and the binder slurry. For example, the electrochemically active material is lithium nickel manganese cobalt oxide (NMC).
According to another embodiment, the method further comprises coating the ion plastic crystal, carbon and binder slurry on a current collector to obtain an ion plastic crystal, carbon and binder electrode film on the current collector. For example, the coating step is performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method. According to a related variant, the coating step is carried out by a blade coating method.
According to another embodiment, the method further comprises drying the ion plastic crystal, the binder and the carbon electrode film.
According to another embodiment, the method further comprises calendering the ion plastic crystal, the binder, and the carbon electrode film. For example, the rolling step is performed by a roll method.
Brief Description of Drawings
Fig. 1 is a flow chart of a method of producing an electrode material according to one embodiment.
Fig. 2 is a flow chart of a method of producing an electrode material according to one embodiment.
FIG. 3 is a para-1, 8-diazabicyclo [5.4.0 ] as described in example 1 (b)]Proton nuclear magnetic resonance obtained from undec-7-ene (DBU) 1 H NMR) spectra.
FIG. 4 shows the nuclear magnetic resonance of carbon-13 obtained for plastic crystal 1 as described in example 1 (b) 13 CNMR) spectra.
FIG. 5 shows the fluorine-19 nuclear magnetic resonance of plastic crystal 1 obtained as described in example 1 (b) 19 FNMR) spectra.
FIG. 6 shows the lithium-7 NMR of the plastic crystal 1 obtained as described in example 1 (b) 7 Li NMR) spectra.
FIG. 7 shows the effect of the negative mode (ESI) in (A) respectively as described in example 1 (b) - ) And (B) a positive mode (ESI) + ) High performance liquid chromatography-time of flight mass spectrometry (HPLC TOF-MS) of electrospray ionization (ESI) source below was used to obtain mass spectra for plastic crystal 1.
Fig. 8 shows the results of differential scanning calorimetric analysis obtained for plastic crystal 1 as described in example 1 (b).
FIG. 9 shows the effect of the test according to example 1 (b) by having the test parameters in (A) positive mode (ESI) + ) And (B) negative mode (ESI) - ) HPLC TOF-MS of ESI ionization source under the spectrum obtained for plastic crystal 11.
Fig. 10 shows the result of differential scanning calorimetric analysis obtained for plastic crystal 11 as described in example 1 (b).
FIG. 11 is a plot of the plastic crystals 15 obtained after post-functionalization as described in example 1 (d) 1 HNMR spectra.
Fig. 12 shows the results of differential scanning calorimetric analysis obtained for plastic crystal 15 after post-functionalization as described in example 1 (d).
Fig. 13 shows the results of thermogravimetric analysis obtained on plastic crystal 15 after post-functionalization as described in example 1 (d).
Fig. 14 shows the results of differential scanning calorimetric analysis obtained for plastic crystal 16 after post-functionalization as described in example 1 (d).
FIG. 15 is a graph showing the ionic conductivity results (S.cm) of the cells as described in example 1 (e) -1 ) vs. temperature (1000/T, K) -1 ) Is a graph of (2).
Fig. 16 is a graph showing the ion conductivity result vs. temperature of the battery as described in example 1 (e).
Fig. 17 is a graph showing the ion conductivity results vs. temperature of the batteries 1 (+), 2 (■), 3 (×t), 4 (+) and 5 (+) as described in example 2.
Fig. 18 is a graph showing the ion conductivity results vs. temperature of the batteries 6 (+), 7 (+), 8 (X), 9 (■), 10 (solidline), and 11 (solidline, dashed line) as described in example 2.
FIG. 19 shows in (A) the atom numbers of protonated DBU and the bis-silylated diethylene glycol derivative prepared in example 1 (a); in (B) and (C) are obtained, respectively, as described in example 5 for the stabilized intermediate ion neutral complex 1 H NMR 13 C NMR spectrum.
FIG. 20 shows in (A) and (B), respectively, the results obtained for the stabilized intermediate ion neutral complex over a period of 3 weeks as described in example 5 1 H NMR spectra 13 C NMR spectrum. At the beginning of the experiment (blue), after 2 days (red)) Results were obtained after 3 days (green), after 9 days (purple) and after 21 days (yellow).
FIG. 21 shows the intermediate ion neutral complex stabilized over a period of 3 weeks as described in example 5 1 H NMR spectra and were recorded between 3.99ppm and 4.30ppm in (a) and between 6ppm and 10.4ppm in (B). Results were obtained at the start of the experiment (blue), after 2 days (red), after 3 days (green), after 9 days (violet) and after 21 days (yellow).
FIG. 22 shows the result of the test in example 6 (b) by having the test in (A) positive mode (ESI) + ) And (B) negative mode (ESI) - ) HPLC TOF-MS of ESI ionization source under mass spectrum obtained for plastic crystal 30.
Fig. 23 shows the results of differential scanning calorimetric analysis obtained on plastic crystal 30 as described in example 6 (b).
FIG. 24 is a graph obtained for a tetra-cationic ion plastic crystal as described in example 7 (b) 1 HNMR spectra.
FIG. 25 is a graph obtained for a tetra-cationic ion plastic crystal as described in example 7 (b) 19 FNMR spectrum.
Fig. 26 is a graph of relaxation time vs. temperature obtained for a tetra-cationic ion plastic crystal as described in example 7 (b).
Fig. 27 shows a Scanning Electron Microscope (SEM) image obtained for the counter electrode 1 as described in example 8 (a).
Fig. 28 shows photographs of (a) a surface of a positive electrode based on plastic crystals and (B) a surface of an electrode 5 obtained by a conventional mixing method as described in example 8 (B).
Fig. 29 is a graph of discharge capacity (mAh/g) vs. cycle number of the battery 12 as described in example 8 (c).
Fig. 30 is a graph of current density and potential vs. time for battery 13 as described in example 9.
Fig. 31 is a graph of current density and potential vs. time for battery 14 as described in example 9.
Fig. 32 is a graph of current density and potential vs. time for batteries 15 and 16 as described in example 9.
FIG. 33 shows the logarithm vs.1/k of the diffusion coefficient (D) as described in example 10 B Arrhenius plot of T, which shows CH 2 (. Sub.m.), NH (X), FSI (. Sub.solid.), TFSI (. Sub.t.), LATP (delta.) and Li + (■) temperature dependence of diffusion rate.
Detailed description of the preferred embodiments
The following detailed description and examples are merely illustrative and should not be construed as further limiting the scope of the invention. On the contrary, they are intended to cover all alternatives, modifications and equivalents as may be included as defined by the specification. The objects, advantages and other features of the ionic plastic crystals, the solid electrolyte composition based on ionic plastic crystals, the solid electrolyte based on ionic plastic crystals and the electrode material comprising said ionic plastic crystals, their preparation method and use will be more apparent and better understood upon reading the following non-limiting description and upon reference to the accompanying drawings.
Where applicable, although process flow diagrams may be used to describe embodiments, the invention is not limited to these diagrams or to the corresponding descriptions. Furthermore, for simplicity and clarity, not all figures contain all steps, reactants and/or products, in particular, so as not to unduly add steps, reactants and/or products to the figures. Certain steps, reactants, and/or products may be present in a single figure and steps, reactants, and/or products of the disclosure shown in other figures can be readily inferred therefrom.
All technical and scientific terms and expressions used herein have the same definition as commonly understood by one of ordinary skill in the art when referring to this technology. Nonetheless, definitions of certain terms and expressions used herein are provided below.
The term "about" when used herein refers to approximately, about, and near. When the term "about" is used with respect to a numerical value, it modifies that numerical value by 10% above and below its nominal value. This term may also take account of experimental errors or rounding of the measuring device, for example.
When numerical ranges are mentioned in the present application, the lower and upper limits of the ranges are always included in the definition unless otherwise indicated. When numerical ranges are referred to in this disclosure, all intermediate ranges and subranges are included in the definition as individual values included in the numerical ranges.
When the article "a" is used in this disclosure to describe an element, it does not have the meaning of "only one" but rather "one or more". Of course, when the specification states a particular step, component, element, or feature "may" or "may" be included, that particular step, component, element, or feature is not required to be included in the respective embodiments.
The chemical structures described herein are drawn according to convention in the art. Furthermore, when a drawn atom, such as a carbon atom, appears to include an unsatisfied valence, it is presumed that the valence is satisfied by one or more hydrogen atoms, even though they are not explicitly drawn.
The term "alkyl" as used herein refers to saturated hydrocarbons having from 1 to 10 carbon atoms, including straight or branched chain alkyl groups. Non-limiting examples of alkyl groups can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, t-butyl, sec-butyl, isobutyl, and the like. When an alkyl group is located between two functional groups, the term alkyl also includes alkylene groups such as methylene, ethylene, propylene, and the like. The term "C m -C n Alkyl "and" C m -C n Alkylene "refers to an alkyl or alkylene group having the indicated number" m "to the indicated number" n ", respectively.
The term "cycloalkyl" or "cycloalkylene" as used herein refers to a group comprising one or more 3-to 12-membered saturated or partially unsaturated (non-aromatic) carbocyclic rings in a single ring or multiple ring system, including spiro (sharing one atom) or fused (sharing at least one bond) carbocyclic rings, and may be optionally substituted. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopenten-1-yl, cyclopenten-2-yl, cyclopenten-3-yl, cyclohexyl, cyclohexen-1-yl, cyclohexen-2-yl, cyclohexen-3-yl, cycloheptyl, and the like. The term cycloalkenylene may also be used when a cycloalkyl group is located between two functional groups An alkyl group. The term "C m -C n Cycloalkyl radicals "and" C m -C n Cycloalkyl "refers to cycloalkyl or cycloalkylene, respectively, having the indicated number" m "to the indicated number" n "of carbon atoms in the ring structure.
The term "heterocycloalkyl" or "heterocycloalkylene" as used herein refers to a group comprising a 3 to 12 membered saturated or partially unsaturated (non-aromatic) carbocyclic ring in a single ring or multiple ring system, including spiro (sharing one atom) or fused (sharing at least one bond) carbocycles, and optionally substituted, wherein one or more atoms in the ring structure are substituted or unsubstituted heteroatoms (e.g., N, O, S or P) or groups containing such heteroatoms (e.g., NH, NR x (R x Is alkyl, acyl, aryl, heteroaryl or cycloalkyl), PO 2 、SO、SO 2 And other similar groups). The heterocycloalkyl group may be attached to a carbon atom or a heteroatom (e.g., via a nitrogen atom), where possible. The term heterocycloalkyl includes unsubstituted and substituted heterocycloalkyl. The term heterocycloalkylene may also be used when a heterocycloalkyl is located between two functional groups. The term "C m -C n Heterocyclylalkyl groups and C m -C n Heterocyclylene "refers to a heterocycloalkyl or heterocycloalkylene group having the indicated number" m "to the indicated number" n "of carbon atoms and heteroatoms, respectively, in the ring structure.
The term "aryl" or "aromatic" as used herein refers to an aryl group having 4n+2 pi (pi) electrons in a single ring or conjugated polycyclic ring system (fused or unfused) and having a total of 6 to 12 ring members, wherein n is an integer from 1 to 3. The polycyclic ring system comprises at least one aromatic ring. The radical may be via C 1 -C 3 The alkyl group is directly attached or attached. The term "aryl" or "aromatic" also includes substituted or unsubstituted groups. Examples of aryl groups include, but are not limited to, phenyl, benzyl, phenethyl, 1-phenylethyl, tolyl, naphthyl, biphenyl, terphenyl, indenyl, benzocyclooctenyl, benzocycloheptenyl, azulenyl, acenaphthylenyl, fluorenyl, phenanthryl, anthracenyl, perylenyl, and the like. The term arylene may also be used when an aryl group is located between two functional groups. The term "C m -C n Aryl "and" C m -C n Arylene "refers to an aryl or aromatic group and arylene group, respectively, having the indicated number" m "to the indicated number" n "of carbon atoms in the ring structure.
The term "heteroaryl", "heteroarylene" or "heteroaromatic" refers to a group having 4n+2 pi (pi) electrons (where n is an integer from 1 to 3) in a single ring or conjugated polycyclic ring system (fused or unfused) and having 5 to 12 ring members, including 1 to 6 substituted or unsubstituted heteroatoms (e.g., N, O or S) or containing such heteroatoms (e.g., NH, NR x (R x Is alkyl, acyl, aryl, heteroaryl or cycloalkyl), SO and other similar groups). The polycyclic ring system comprises at least one heteroaromatic ring. Heteroaryl groups can be substituted by C 1 -C 3 The alkyl group is directly attached or attached (also known as a heteroarylalkyl or heteroaralkyl). Heteroaryl groups may be attached to a carbon atom or a heteroatom (e.g., via a nitrogen atom), where possible. The term "C m -C n Heteroaryl "refers to heteroaryl groups having the indicated number" m "to the indicated number" n "of carbon atoms and heteroatoms in the ring structure.
The term "substituted" as used herein means that one or more hydrogen atoms on a given group are replaced with a suitable substituent. Examples of the substituent include a halogen atom (i.e., F, cl, br or I) and a cyano group, an amide group, a nitro group, a trifluoromethyl group, a lower alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, a lower alkoxy group, an aryloxy group, a benzyloxy group, a benzyl group, an alkoxycarbonyl group, a sulfonyl group, a sulfonic acid group, a silane, a siloxane, a phosphonic acid group (phosphinato) and other similar groups. Where possible, for example, if the group contains an alkyl group, an alkoxy group, an aryl group, or the like, these substituents may also be substituted.
The present technology relates to an ionic plastic crystal comprising at least one delocalized anion paired with at least one cation derived from a guanidine, amidine or phosphazene organic superbase. For example, the ion plastic crystal may be mono-cationic or multi-cationic.
According to a related variant, the ionic plastic crystal may be a single cationic ionic plastic crystal comprising a delocalized anion paired with a cation derived from a guanidine, amidine or phosphazene organic superbase. The cation derived from guanidine, amidine or phosphazene organic superbase may be a proton cation derived from guanidine, amidine or phosphazene organic superbase, and the ion plastic crystal may be a proton monocationic ion plastic crystal.
According to another related variant, the ionic plastic crystal may be a polycationic ionic plastic crystal comprising at least two delocalized anions, each paired with a cationic moiety derived from a cation of guanidine, amidine or phosphazene organic superbase. For example, the polycationic ionic plastic crystals may be biscationic, trication, tetracationic, pentacationic, or hexacationic ionic plastic crystals. It is understood that the cationic moieties are linked together by an organic bridging group that separates the cationic moieties.
According to one example, the delocalized anion may be selected from trifluoromethylsulfonate (or trifluoromethylsulfonate) [ TfO] - Bis (trifluoromethanesulfonyl) imide [ TFSI] - Bis (fluorosulfonyl) imide [ FSI ]] - 2-trifluoromethyl-4, 5-dicyanoimidazo [ TDI ]] - Hexafluorophosphate [ PF ] 6 ] - And tetrafluoroborate [ BF ] 4 ] - . According to one example, the delocalized anion may be selected from [ TFSI ]] - And [ FSI ]] - . According to a related variant, the delocalized anion is [ FSI] - 。
According to another example, guanidine, amidine or phosphazene organic superbases can be chosen for their affinity for hydrogen ions in organic solvents and for their ability to delocalize charges in their protonated cationic form. For example, guanidine, amidine, or phosphazene organic superbases can bond hydrogen cations to nitrogen lone pairs.
According to another example, the guanidine, amidine or phosphazene organic superbase may have an acyclic, monocyclic or polycyclic structure.
According to another example, the guanidine, amidine or phosphazene organic superbase may be chosen from 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-dimethylperfhydro-1, 3, 2-diazaphosphorine (BEMP), tert-butylimino-tris (pyrrolidine) phosphine (BTPP), and tert-butylimino-tris (dimethylamino) phosphine (P) 1 -t-Bu). According to a related variant, the organic superbase may be DBU or BEMP.
According to another example, the cation derived from guanidine, amidine or phosphazene organic superbase may be a proton cation.
According to another example, the cation derived from guanidine, amidine or phosphazene organic superbase may comprise at least one crosslinkable functional group. For example, the crosslinkable functional groups may be selected from cyanate, acrylate and methacrylate groups. According to a related variant, the crosslinkable functional group may be selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-acrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates and carbonylamino-C 1 -C 10 Alkyl-acrylate groups. Of course, at least partially crosslinked versions of these crosslinkable groups are also intended to be included in this definition.
According to another example, the cation derived from a guanidine, amidine or phosphazene organic superbase may be a cation derived from an amidine organic superbase of formula 1:
wherein, the liquid crystal display device comprises a liquid crystal display device,
a forms an optionally substituted saturated, unsaturated or aromatic ring comprising 4 to 8 members with the C-N group to which it is attached;
b forms with the amidino group to which it is attached an optionally substituted unsaturated non-aromatic ring comprising 4 to 8 elements; and
Wherein, the liquid crystal display device comprises a liquid crystal display device,
the ion plastic crystal is single cation ion plastic crystalAnd R is 1 Is a hydrogen atom or is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-acrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates and carbonyloxy-C 1 -C 10 Linear or branched substituents of alkyl-acrylates; or (b)
The ion plastic crystal is a multi-cation ion plastic crystal, and R 1 Is an optionally substituted organic bridging group separating two or more cations and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
According to another example, a may comprise a heteroatom or a heteroatom-containing group. A may be further fused to C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene or C 3 -C 12 Heterocycloalkylene group.
According to another example, B may be monounsaturated or polyunsaturated and may be further fused to C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene or C 3 -C 12 Heterocycloalkylene group.
According to another example, the cation derived from guanidine, amidine or phosphazene organic superbase may be one of the cations of formulae 2 to 8:
wherein, the liquid crystal display device comprises a liquid crystal display device,
the ion plastic crystal is a single cation ion plastic crystal, and R 1 Is a hydrogen atom or is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-acrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates and carbonyloxy-C 1 -C 10 Linear or branched substituents of alkyl-acrylates; or (b)
The ion plastic crystal is a multi-cation ion plastic crystal, and R 1 Is an optionally substituted organic bridging group separating at least two cations and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
According to another example, the cation derived from guanidine, amidine or phosphazene organic superbase may be selected from [ R 1 -DBU] + 、[R 1 -DBN] + 、[R 1 -MTBD] + 、[R 1 -BEMP] + 、[R 1 -BTPP] + And [ R ] 1 -P 1 -t-Bu] + . According to a related variant, the cation derived from guanidine, amidine or phosphazene organic superbase is [ R 1 -DBU] + Or [ R ] 1 -BEMP] + 。
According to another example, the cation derived from guanidine, amidine or phosphazene organic superbase may be selected from [ H-DBU ] ] + 、[H-DBN] + 、[H-MTBD] + 、[H-BEMP] + 、[H-BTPP] + And [ H-P ] 1 -t-Bu] + . According to a related variant, the cation derived from guanidine, amidine or phosphazene organic superbase is [ H-DBU ]] + Or [ H-BEMP] + 。
According to another example, the ion plastic crystal may have formula 9:
wherein, the liquid crystal display device comprises a liquid crystal display device,
A. b and R 1 As defined herein; and
X - is a delocalized anion as defined herein.
According to another example, the ion plastic crystal may be one of the ion plastic crystals of formulas 10 to 16:
/>
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 as defined herein; and
X - is a delocalized anion as defined herein.
According to another example, the ionic plastic crystal may be selected from [ R ] 1 -DBU][OTf]、[R 1 -DBU][TFSI]、[R 1 -DBU][FSI]、[R 1 -DBU][TDI]、[R 1 -DBU][PF 6 ]、[R 1 -DBU][BF 4 ]、[R 1 -DBN][OTf]、[R 1 -DBN][TFSI]、[R 1 -DBN][FSI]、[R 1 -DBN][TDI]、[R 1 -DBN][PF 6 ]、[R 1 -DBN][BF 4 ]、[R 1 -MTBD][OTf]、[R 1 -MTBD][TFSI]、[R 1 -MTBD][FSI]、[R 1 -MTBD][TDI]、[R 1 -MTBD][PF 6 ]、[R 1 -MTBD][BF 4 ]、[R 1 -BEMP][OTf]、[R 1 -BEMP][TFSI]、[R 1 -BEMP][FSI]、[R 1 -BEMP][TDI]、[R 1 -BEMP][PF 6 ]、[R 1 -BEMP][BF 4 ]、[R 1 -P 1 -t-Bu][OTf]、[R 1 -P 1 -t-Bu][TFSI]、[R 1 -P 1 -t-Bu][FSI]、[R 1 -P 1 -t-Bu][TDI]、[R 1 -P 1 -t-Bu][PF 6 ]、[R 1 -P 1 -t-Bu][BF 4 ]、[R 1 -BTPP][OTf]、[R 1 -BTPP][TFSI]、[R 1 -BTPP][FSI]、[R 1 -BTPP][TDI]、[R 1 -BTPP][PF 6 ]And [ R ] 1 -BTPP][BF 4 ]. According to a related variant, the ionoplast crystal is [ R 1 -DBU][FSI]Or [ R ] 1 -BEMP][FSI]。
According to another example, the ion plastic crystal may be selected from [ H-DBU ]][OTf]、[H-DBU][TFSI]、[H-DBU][FSI]、[H-DBU][TDI]、[H-DBU][PF 6 ]、[H-DBU][BF 4 ]、[H-DBN][OTf]、[H-DBN][TFSI]、[H-DBN][FSI]、[H-DBN][TDI]、[H-DBN][PF 6 ]、[H-DBN][BF 4 ]、[H-MTBD][OTf]、[H-MTBD][TFSI]、[H-MTBD][FSI]、[H-MTBD][TDI]、[H-MTBD][PF 6 ]、[H-MTBD][BF 4 ]、[H-BEMP][OTf]、[H-BEMP][TFSI]、[H-BEMP][FSI]、[H-BEMP][TDI]、[H-BEMP][PF 6 ]、[H-BEMP][BF 4 ]、[H-P 1 -t-Bu][OTf]、[H-P 1 -t-Bu][TFSI]、[H-P 1 -t-Bu][FSI]、[H-P 1 -t-Bu][TDI]、[H-P 1 -t-Bu][PF 6 ]、[H-P 1 -t-Bu][BF 4 ]、[H-BTPP][OTf]、[H-BTPP][TFSI]、[H-BTPP][FSI]、[H-BTPP][TDI]、[H-BTPP][PF 6 ]And [ H-BTPP][BF 4 ]. According to a related variant, the ionoplast crystal is [ H-DBU][FSI]Or [ H-BEMP][FSI]。
The present technology also relates to a stabilized intermediate ion neutral complex obtained by the reaction of a cation derived from a guanidine, amidine or phosphazene organic superbase as described herein, a proton source and a delocalized anion as described herein in the presence of a bis-silylated compound of formula 17:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z is a substituted or unsubstituted organic group selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, linear or branched polyether, linear or branched polycarbonate, linear or branched polythiocarbonate, linear or branched polyamide, linear or branched polyimide, linear or branched polyurethane, linear or branched polysiloxane, linear or branched thioether, linear or branched polyphosphazene, linear or branched polyester, and linear or branched polythioester; and
R 2 independently and at each occurrence is selected from alkyl, aryl, and arylalkyl.
According to one example, the bis-silylated compound of formula 17 is a bis-silylated derivative of a compound comprising at least two hydroxyl groups selected from the group consisting of glycerol (glycerin), 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-propanediol (or Propylene Glycol (PG)), 1, 2-butanediol, 2, 3-butanediol (or dimethylene glycol (dimethylene glycol)), 1, 3-butanediol (or butylene glycol), 1, 2-pentanediol, 2-ethyl-1, 3-hexanediol (etohexadiol), p-menthyl-3, 8-diol, 2-methyl-2, 4-pentanediol, polycaprolactone diol, ethylene glycol (1, 2-ethylene glycol), diethylene glycol (or diethylene glycol (ethylene diglycol)), triethylene glycol, tetraethylene glycol, pentylene glycol, polyethylene glycol, 2,3, 4, 5-octafluorohexane-1, 6-diol, and other diols, and combinations of at least two of these and the like. According to a related variant, the compound comprising at least two hydroxyl groups is diethylene glycol or glycerol.
According to another example, the stabilized intermediate ion neutral complex may be one of the complexes of formulae 18 to 24:
wherein, the liquid crystal display device comprises a liquid crystal display device,
Z、X - and R is 2 As defined herein.
According to one example, the silane group of the bis-silylated compound of formula 17 may be cleaved and the N-H proton derived from the cation of guanidine, amidine or phosphazene organic superbase may be added to hydrogen bond to form a NHO-stabilized intermediate ion neutral complex. For example, only about 1% of the bis-silylated compounds of formula 17 eventually have cleaved silane groups. For example, NHO-stabilized intermediate ion neutral complexes are byproducts of this reaction.
According to another example, the NHO-stabilized intermediate ion neutral complex may be one of the complexes of formulae 25 to 31:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z and R 2 As defined herein.
The present technology also relates to an ionic plastic crystal composition comprising at least one ionic plastic crystal as defined herein and at least one additional component and/or at least one polymer.
According to one example, the additional component may be selected from solvents, ionic conductors, inorganic particles, glass particles, ceramic particles (e.g., nanoceramics), plasticizers, and other similar components, or a combination of at least two thereof. For example, the additional component may be a filler additive and may include metal oxide particles or nanoparticles. For example, the filler additive may be Comprising titanium dioxide (TiO) 2 ) Alumina (Al) 2 O 3 ) And/or silicon dioxide (SiO) 2 ) Or nanoparticles of (a).
According to another example, the polymer may be a polymer such as those commonly used in Solid Polymer Electrolytes (SPE). The solid polymer electrolyte may generally include one or more optionally crosslinked solid polar polymers, and a salt (e.g., as defined above). Polyether polymers such as those based on poly (ethylene oxide) (PEO) may be used, but several other compatible polymers are also known and contemplated for use in preparing solid polymer electrolytes. The polymer may be crosslinked. Examples of such polymers include branched polymers, such as star polymers or comb polymers, such as those described in U.S. Pat. No.7,897,674B2 (Zaghib et al) (US' 674).
According to some examples, the polymer may be a block copolymer composed of at least one lithium ion solvating segment and optionally at least one crosslinkable segment. For example, the lithium ion solvating segment is selected from a homopolymer or copolymer having repeating units of formula 32:
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 3 selected from hydrogen atoms, C 1 -C 10 Alkyl or- (CH) 2 -O-R 4 R 5 ) A group;
R 4 is (CH) 2 -CH 2 -O) m ；
R 5 Selected from hydrogen atoms and C 1 -C 10 An alkyl group;
y is an integer selected from 10 to 200,000; and
m is an integer selected from 0 to 10.
According to another example, the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group that is multi-dimensionally crosslinkable by irradiation or heat treatment.
According to another example, the concentration of the polymer in the ion plastic crystal composition may be at least 10 wt%. For example, the concentration of the polymer in the ion plastic crystal composition may be in the range of about 5 wt% to about 45 wt%, or about 10 wt% to about 45 wt%, or about 15 wt% to about 45 wt%, or about 20 wt% to about 45 wt%, or about 25 wt% to about 45 wt%, or about 30 wt% to about 45 wt%, or about 35 wt% to about 45 wt%, or about 40 wt% to about 45 wt%, inclusive of upper and lower limits. According to a related variant, the ion plastic crystal composition comprises about 40% by weight of the polymer and 60% by weight of ion plastic crystals as described herein. It will be appreciated that the optimum concentration of the polymer in the ion plastic crystal composition will depend on the polymer used.
According to another example, the additional component may be inorganic particles comprising a compound having a garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, inverse perovskite or suchlike type structure, or comprising a compound of the M-P-S, M-P-S-O, M-P-S-X, M-P-S-O-X type (wherein M is an alkali metal or alkaline earth metal and X is F, cl, br, I or a combination of at least two thereof), being a crystalline phase, an amorphous phase and/or a glass ceramic phase, or a mixture of at least two thereof.
According to another example, the additional component may be an inorganic particle of a crystalline phase, an amorphous phase and/or a glass ceramic phase, or a mixture of at least two thereof, and comprises at least one of the inorganic compounds of the following formula: 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 ) The method comprises the steps of carrying out a first treatment on the surface of the 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 ) The method comprises the steps of carrying out a first treatment on the surface of the MLSnO (e.g. M 7 La 3 Sn 2 O 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MAGP (e.g. M 1+a Al a Ge 2-a (PO 4 ) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the MATP (e.g. M 1+a Al a Ti 2-a (PO 4 ) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the MLTiO (e.g. M 3a La (2/3-a) TiO 3 ) The method comprises the steps of carrying out a first treatment on the surface of the MZP (e.g. M a Zr b (PO 4 ) c ) The method comprises the steps of carrying out a first treatment on the surface of the MCZP (e.g. M a Ca b Zr c (PO 4 ) d ) The method comprises the steps of carrying out a first treatment on the surface of the MGPS (e.g. M a Ge b P c S d For example M 10 GeP 2 S 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MGPSO (e.g. M a Ge b P c S d O e ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPS (e.g. M a Si b P c S d For example M 10 SiP 2 S 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPSO (e.g. M a Si b P c S d O e ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPS (e.g. M a Sn b P c S d For example M 10 SnP 2 S 12 ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPSO (e.g. M a Sn b P c S d O e ) The method comprises the steps of carrying out a first treatment on the surface of the MPS (e.g. M a P b S c For example M 7 P 3 S 11 ) The method comprises the steps of carrying out a first treatment on the surface of the MPSO (e.g. M a P b S c O d ) The method comprises the steps of carrying out a first treatment on the surface of the MZPS (e.g. M a Zn b P c S d ) The method comprises the steps of carrying out a first treatment on the surface of the MZISO (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 The method comprises the steps of carrying out a first treatment on the surface of the MPSX (e.g. M a P b S c X d For example 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 ) The method comprises the steps of carrying out a first treatment on the surface of the MGPSX (e.g. M a Ge b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MGPSOX (e.g. M a Ge b P c S d O e X f ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPSX (e.g. M a Si b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MSiPSox (e.g. M a Si b P c S d O e X f ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPSX (e.g. M a Sn b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MSnPSOX (e.g. M a Sn b P c S d O e X f ) The method comprises the steps of carrying out a first treatment on the surface of the MZPSX (e.g. M a Zn b P c S d X e ) The method comprises the steps of carrying out a first treatment on the surface of the MZIPSOX (e.g. M a Zn b P c S d O e X f )；M 3 OX；M 2 HOX；M 3 PO 4 ；M 3 PS 4 The method comprises the steps of carrying out a first treatment on the surface of the And M a PO b N c (wherein a=2b+3c-5);
wherein the method comprises the steps of
M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, the amount of M is adjusted to achieve electroneutrality;
x is selected from F, cl, br, I or a combination thereof;
a. b, c, d, e and f are non-0 values and are independently selected among the formulae to achieve electroneutrality; and
v, w, x, y and z are non-0 values and are independently selected in the formulae to obtain stable compounds.
According to another example, the additional component may be a ceramic or a glass-ceramic. For example, the additional component may be a sulfide ceramic or a glass ceramic, such as Li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 2 S-P 2 S 5 、Li 7 P 3 S 11 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 9.6 P 3 S 12 、Li 3.25 P 0.95 S 4 And other similar ceramics and glass-ceramics. According to a related variant, the sulfide ceramic or glass ceramic is Li 6 PS 5 Cl. The concentration of the ceramic or glass-ceramic in the ion plastic crystal composition may be at least 50 wt%. For example, the concentration of the ceramic or glass-ceramic in the ion plastic crystal composition may be in the range of about 50 wt% to about 95 wt%, or about 55 wt% to about 95 wt%, or about 60 wt% to about 95 wt%, or about 65 wt% to about 95 wt%, or about 70 wt% to about 95 wt%, or about 75 wt% to about 95 wt%, or about 80 wt% to about 95 wt%, or about 85 wt% to about 95 wt%, or about 90 wt% to about 95 wt%, inclusive of the upper and lower limits. According to a related variant, the ionic plastic crystal composition comprises about 90% by weight of Li 6 PS 5 Cl and 10 wt% of an ion plastic crystal as described herein. It will be appreciated that the optimum concentration of the additional component in the ion plastic crystal composition depends on the additional component used (e.g. on the particle size, its specific surface area, etc.).
According to one example, the ion plastic crystals may be prepared by any compatible synthetic method. For example, the synthesis of the ion plastic crystals may include at least one of a proton exchange reaction, a counter ion exchange reaction, and any other suitable reaction.
According to another example, a method of synthesizing a proton-type ion plastic crystal may include at least two synthesis steps. The first step may involve reacting a neutral organic superbase of the amidine, guanidine or phosphazene type with at least one proton source to form a complex, adduct or ion pair comprising a protonated cation. For example, the organic superbase may be selected based on its ability to remove protons (or its affinity for protons). For example, the organic superbase may be a non-nucleophilic organic superbase or a weak nucleophilic organic superbase. According to a related variant, the organic superbase may be chosen from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu or its derivativesAnd (3) an object. For example, the organic superbase may be DBU or BEMP. For example, the second step may involve a counter ion exchange reaction between the complex, adduct or ion pair comprising the protonated cation formed in the first step and an ionic salt based on a delocalized anion as described above. For example, the ionic salt may be an alkali or alkaline earth metal salt, such as a lithium, sodium, potassium, calcium or magnesium salt. For example, the ionic salt may be selected from lithium triflate (LiSO 3 CF 3 ) (LiOTf), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium 2-trifluoromethyl-4, 5-dicyanoimidazole (LiTDI), lithium hexafluorophosphate (LiPF) 6 ) And lithium tetrafluoroborate (LiBF) 4 ) Is a lithium salt of (a). According to a related variant, the lithium salt is LiFSI.
According to another example, the ionic plastic crystal may be a proton-type ionic plastic crystal formed by transferring protons from a bronsted acid to a bronsted base. For example, the bronsted base may be a neutral organic super base of the amidine, guanidine or phosphazene type, and may be selected based on its ability to remove protons (or its affinity for protons). According to a related variant, the organic superbase may be chosen from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu or a derivative thereof. For example, the organic superbase may be DBU or BEMP. According to another related variant, the Bronsted acid may be selected from the group consisting of trifluoromethanesulfonic acid (TfOH), bis (trifluoromethanesulfonyl) imide acid (HTFSI), bis (fluorosulfonyl) imide acid (HFSI), 22- (trifluoromethyl) -1H-imidazole-4, 5-carbonitrile (HTDI), hexafluorophosphoric acid (HPF) 6 ) And tetrafluoroboric acid (HBF) 4 ). According to a related variant, the bronsted acid is HFSI.
The present technology thus also relates to a process for preparing an ion plastic crystal or ion plastic crystal composition as defined herein, said process comprising the steps of:
(i) At least one organic super base as described above is reacted with a bronsted acid based on a delocalized anion as defined herein to form an ionic plastic crystal.
The present technology thus also relates to a process for preparing an ion plastic crystal or ion plastic crystal composition as defined herein, said process comprising the steps of:
(i) Reacting at least one organic superbase as described above with a proton source to form at least one complex comprising a protonated cation and a counter ion; and
(ii) Reacting the complex comprising a protonated cation and a counter-ion with at least one ionic salt based on a delocalized anion as described above.
According to one example, the organic superbase is a neutral organic superbase of the amidine, guanidine or phosphazene type. According to a related variant, the organic superalkali is selected from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu or a derivative thereof. For example, the organic superbase may be DBU or BEMP.
According to another example, the method further comprises a step of preparing an organic superbase performed before step (i). In some examples, the organic superbase may be a neutral polycyclic amidine organic superbase prepared by the condensation of an aromatic dialdehyde with a 1, 2-diamine. For example, neutral polycyclic amidine organic superalkins can be prepared by the method described by Braddock et al (Braddock, D.C. et al, "The reaction of aromatic dialdehydes with enantiopure 1, 2-diamides: an expeditious route to enantiopure tricyclic amines," Tetrahedron: asymmetry 21.24 (2010): 2911-2919).
According to another example, the ionic salt based on a delocalized anion as defined herein may be an alkali metal or alkaline earth metal salt, such as a lithium, sodium, potassium, calcium or magnesium salt, based on a delocalized anion as defined herein. For example, the ionic salt may have formula M n+ [(FSI) n ] n- Wherein M is n+ Is selected from Na + 、K + 、Li + 、Ca 2+ And Mg (magnesium) 2+ Alkali metal or alkaline earth metal ions of the ions. According to a related variant, M n+ Is Li + 。
According to another example, the two reaction steps may be carried out sequentially, simultaneously or partially overlapping each other in time. According to a related variant, the two reaction steps are carried out sequentially and the step of reacting at least one organic superbase with a proton source is carried out before the step of reacting a complex comprising a protonated cation and a counter-ion with an ionic salt based on a delocalized anion. According to another related variant, all reactants may be mixed together and reacted under appropriate reaction conditions.
According to another example, the synthesis may be carried out in the presence of a solvent. For example, the solvent may act as a proton source and may be selected based on its ability to readily provide protons or its ability to stabilize base and/or solvent conjugated acid cations. For example, stabilization of base and/or solvent conjugated acid cations may be achieved by solvation, non-covalent interactions (e.g., hydrogen bonding and dipole-dipole interactions) or van der Waals interactions. Without wishing to be bound by theory, the ability to solubilize efficiently and thus improve the solvation stability of the protonated form of the organic superbase can significantly improve the reaction yield. For example, the solvent may be a polar solvent selected from the group consisting of Dichloromethane (DCM), dimethyl carbonate (DMC), acetonitrile (ACN), ethanol (EtOH), and miscible combinations of at least two thereof. According to a related variant, the solvent may be ACN.
According to a related example, the synthesis of the ionic plastic crystals can be carried out by the method as shown in scheme 1 (where no by-products of the reaction are shown):
wherein, the liquid crystal display device comprises a liquid crystal display device,
M n+ is selected from Na + 、K + 、Li + 、Ca 2+ And Mg (magnesium) 2+ Alkali metal or alkaline earth metal ions of the ions.
According to a related variant, M n+ Is Li + 。
According to another example, the synthesis may be carried out in the presence of a second proton source, such as a suitable acid. The second proton source may be selected, for example, based on its ability to readily provide protons or its ability to stabilize base and/or solvent conjugated acid cations. For example, the second proton source may also act as an activator and/or catalyst to obtain ionic plastic crystals, and may significantly improve reaction yields. Examples of the second proton source include, but are not limited to, carboxylic acids (e.g., formic acid, acetic acid, propionic acid, lactic acid, and trifluoroacetic acid), p-toluenesulfonic acid (or benzenesulfonic acid), sulfuric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, nitric acid, hydrofluoric acid, and other similar acids. According to a related variant, the acid is formic acid.
According to a related example, the synthesis of the ionic plastic crystals can be carried out by the method as shown in scheme 2 (where no by-products of the reaction are shown):
Wherein, the liquid crystal display device comprises a liquid crystal display device,
M n+ is selected from Na + 、K + 、Li + 、Ca 2+ And Mg (magnesium) 2+ Alkali metal or alkaline earth metal ions of the ions.
According to another example, the synthesis may be performed in the presence of an activator, which may also act as a stabilizer and/or proton source. The activator may react with the organic super base to form a stable intermediate non-covalent complex. For example, the activator may form the stable intermediate non-covalent complex by electrophilic nucleophilic activation to significantly promote the formation of ionic plastic crystals. For example, the stable intermediate non-covalent complex may be a NHO-stable intermediate ion neutral complex. For example, the activator may be a bis-silylated compound as described above.
According to a related example, the synthesis of the ionic plastic crystals can be carried out by the method as shown in scheme 3 (where no by-products of the reaction are shown):
wherein, the liquid crystal display device comprises a liquid crystal display device,
M n+ is selected from Na + 、K + 、Li + 、Ca 2+ And Mg (magnesium) 2+ Alkali metal or alkaline earth metal ions of the ions; and R is 2 As defined herein.
According to another example, the method further comprises the step of preparing a bis-silylated compound. The preparation of the bis-silylated compounds may be carried out by silylation of compounds comprising at least two hydroxyl groups, which may be derivatized by a silylating agent, e.g., compounds comprising at least two hydroxyl groups may be as described above. For example, the silylation reaction may be carried out by a base-catalyzed silylation reaction, and may involve replacement of acidic (or active) hydrogen with a silyl (e.g., alkylsilyl) group, such as a trialkylsilyl group. For example, a compound comprising at least two hydroxyl groups may be deprotonated with a base and then treated with at least one silylating agent. The base-catalyzed silylation reaction may be carried out in the presence of any known compatible base. For example, the base may be a nucleophilic lewis base such as imidazole, 4-Dimethylaminopyridine (DMAP), other similar nucleophilic lewis bases, and combinations thereof. According to a related variant, the base is imidazole. For example, the silylation reaction may be carried out in a polar aprotic solvent such as Tetrahydrofuran (THF), N-Dimethylformamide (DMF), dichloromethane (DCM), dimethylsulfoxide (DMSO) or a miscible combination of at least two thereof. According to a related variant, the aprotic solvent is THF, DCM or a combination of DCM and DMF, with DCM being clearly predominant.
For example, the silylating agent may be selected based on its reactivity and selectivity to compounds comprising at least two hydroxyl groups, stability of the silylated derivative, and reaction by-products. For example, universal silylating agents may be used to derivatize hydroxyl groups of a compound comprising at least two hydroxyl groups. Non-limiting examples of silylating agents include trialkylsilyl chloride, trimethylsilyl chloride (TMS-Cl), triethylsilyl chloride (TES-Cl), isopropyldimethylsilyl chloride (IPMS-Cl), diethylisopropylsilyl chloride (DEIPS-Cl), tert-butyldimethylsilyl chloride (TBDMS-Cl or TBS-Cl), tert-butyldiphenylsilyl chloride (TBDPS-Cl or TPS-Cl), triisopropylsilyl chloride (TIPS-Cl), nitrogen-containing silyl ethers, N, O-bis (tert-butyldimethylsilyl) acetamide (BSA), N-methyl-N- (trimethylsilyl) trifluoroacetamide (MSTFA), N- (trimethylsilyl) dimethylamine (TMSOA), N- (trimethylsilyl) imidazole (TMSI or TSIM), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), and N-methyl-N- (trimethylsilyl) acetamide (MSA). According to a related variant, the silylating agent comprises trialkylsilyl chloride, such as TMS-Cl or TBDMS-Cl.
For example, TBDMS-Cl can be used to replace active hydrogen on hydroxyl groups, and synthesis of bis-silylated compounds can be performed by silylation reactions as shown in schemes 4 (a) or 4 (b):
wherein, the liquid crystal display device comprises a liquid crystal display device,
z is a substituted or unsubstituted organic group selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, linear or branched polyether, linear or branched polycarbonate, linear or branched polythiocarbonate, linear or branched polyamide, linear or branched polyimide, linear or branched polyurethane, linear or branched polysiloxane, linear or branched thioether, linear or branched polyphosphazene, linear or branched polyester, and linear or branched polythioester.
A general example of a silylation reaction is shown in scheme 4 (a), which uses TBDMS-Cl as the silylating agent and involves nucleophilic attack on silicon. For example, 1 equivalent of a compound comprising at least two hydroxyl groups may be reacted with 2 equivalents of TBDMS-Cl to form a bis-silylated compound and hydrochloric acid (HCl) as a by-product of the reaction. It is understood that the reaction involves one silyl group per hydroxyl group to be derivatized.
Another example of a silylation reaction is described by Sharpless et al (Sharpless, K.B. et al, "SuFEx-Based Synthesis of Polysulfates" Angewandte Chemie International Edition 53.36 (2014): 9466-9470 (Supplementary Materials)). An example of such a silylation reaction is shown in scheme 4 (b). For example, the silylating agent may be added at a molar ratio of (to be derivatized-OH groups) to (silyl groups) of about 1:1 or about 1:0.9. Alternatively, the silylating agent may be added in excess. For example, the amount of silylating agent may be in the range of about 2 equivalents to about 5 equivalents, including upper and lower limits, per equivalent of compound comprising at least two hydroxyl groups. For example, the amount of silylating agent may be in the range of about 2 equivalents to about 4.5 equivalents, or about 2 equivalents to about 4 equivalents, or about 2 equivalents to about 3.75 equivalents, or about 2 equivalents to about 3.5 equivalents, including upper and lower limits, per equivalent of compound comprising at least two hydroxyl groups. According to a related variant, when the compound comprises two and three hydroxyl groups, respectively, the amount of silylating agent may be in the range of about 2.2 equivalents to about 3.3 equivalents per equivalent of compound comprising at least two hydroxyl groups.
According to another example, the silylation reaction may be conducted at room temperature for a sufficient time to achieve a substantially complete reaction. For example, when the silylation reaction is performed by the reaction shown in scheme 4 (a), it may be performed for at least 15 hours. For example, the silylation reaction may be conducted for a period of time ranging from about 15 hours to about 24 hours, including upper and lower limits. Alternatively, when the silylation reaction is performed by the reaction shown in scheme 4 (b), it may be performed for about 3 hours.
It is understood that the use of DCM as a solvent has a significant impact on the reaction rate. Thus, DCM can be used for larger scale synthesis of bis-silylated compounds compared to other solvents such as THF or DMF.
According to another example, the preparation of an ion plastic crystal or ion plastic crystal composition as defined herein may thus involve a protonation reaction and an anion exchange reaction.
A general example of this mechanism is shown in scheme 3 and involves the reaction of DBU with a metal bis (fluorosulfonyl) imide in the presence of the bis-silylated compound obtained in scheme 4 (a) or 4 (b) to obtain ionic plastic crystals and byproducts (not shown in scheme 3).
According to another example, the activator (i.e., the bis-silylated compound) may be reacted with about an equimolar amount of the organic super-base. Alternatively, the organic superbase may be added in excess, for example, the excess may be in the range of about 0.01 mole% to about 10 mole%, including upper and lower limits. According to a related variant, the activator may be reacted with an approximately equimolar amount of the organic super base.
According to another example, the two reaction steps may be conducted at a sufficiently high temperature and for a sufficient time to achieve a substantially complete reaction. For example, the two reaction steps may be carried out at a temperature of about 20 ℃ to about 200 ℃, including an upper limit and a lower limit. For example, the two reaction steps may be carried out at a temperature of about 40 ℃ to about 80 ℃, or about 45 ℃ to about 75 ℃, or about 50 ℃ to about 70 ℃, or about 55 ℃ to about 65 ℃, including upper and lower limits. For example, both reaction steps may be performed for at least 4 days.
According to another example, the method further comprises the step of removing at least one by-product generated during any process step. For example, the removal step may be performed by distillation or evaporation. For example, depending on the boiling point of the by-product to be removed, the by-product may be removed at ambient atmospheric pressure or under vacuum. The by-product may be removed by washing with any suitable solvent that dissolves the by-product but does not dissolve the ionic plastic crystals. For example, byproducts may also be removed by more than one process, if necessary. According to a related variant, the by-product may be removed by extraction, for example by dissolving the by-product in DCM and extracting with water and brine.
According to another example, the method further comprises a functionalization step, for example functionalizing the ion plastic crystals with respect to their cross-linking. For example, functionalization of the ion plastic crystal may optionally be performed to functionalize the ion plastic crystal, for example by introducing at least one functional group as defined above, e.g. a crosslinkable functional group. The crosslinkable functional groups may be present on cations or on side chains of the cationic backbone of the ionic plastic crystal.
According to another example, the reaction step and the functionalization step may be carried out sequentially, simultaneously or partially overlapping each other in time. According to a related variant, the reaction step and the functionalization step are carried out sequentially, wherein the reaction step is carried out before the functionalization step. For example, the functionalization step is a post-functionalization step.
According to another example, the functionalization step can be carried out by a reaction between a protonated cation and at least one crosslinkable functional group. For example, the functionalization step can be carried out by protonating the cation and selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-acrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates and carbonylamino-C 1 -C 10 The reaction between at least one crosslinkable functional group of the alkyl-acrylate group proceeds.
According to another example, the post-functionalization step can be carried out by a reaction as shown in scheme 5 (wherein no reaction by-products are shown):
according to another example, the method further comprises the step of coating the ion plastic crystal composition or the suspension comprising ion plastic crystals as described above. For example, the coating step may be performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method. According to a related variant, the coating step is carried out by a blade coating method or a slot die coating method. According to one example, the ion plastic crystal composition or suspension comprising ion plastic crystals may be coated on a substrate or carrier film (e.g., a substrate made of silicone, polypropylene, or siliconized polypropylene). For example, the substrate or carrier film may be subsequently removed. According to another example, the ion plastic crystal composition or suspension comprising ion plastic crystals may be coated directly on the electrode.
According to another example, the method further comprises the step of drying the ion plastic crystal composition or ion plastic crystal as defined above. According to one example, a drying step may be performed to remove any residual solvent. According to another example, the drying step and the coating step may be performed simultaneously and/or separately.
According to another example, the method further comprises the step of crosslinking the ion plastic crystal composition or ion plastic crystal as defined above. For example, the cation contains at least one functional group capable of cross-linking the ionoplast crystal. According to another example, the crosslinking step may be carried out by ultraviolet radiation, by heat treatment, by microwave radiation, under an electron beam, by gamma irradiation or by X-ray irradiation. According to a related variant, the crosslinking step is carried out by ultraviolet radiation. According to another related variant, the crosslinking step is carried out by heat treatment. According to another related variant, the crosslinking step is carried out under an electron beam. According to another example, the crosslinking step may be performed in the presence of a crosslinking agent, a thermal initiator, a photoinitiator, a catalyst, a plasticizer, or a combination of at least two thereof. For example, the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone (Irgacure) TM 651). For example, the ion plastic crystal composition or ion plastic crystal may be cured after crosslinking.
The present technology also relates to a process for preparing a polycationic ionic plastic crystal or a composition of polycationic ionic plastic crystals as defined in the present application, comprising the steps of:
(i) Reacting an organic superbase as described above with an organic bridging compound to form a polycationic complex comprising at least two organic superbase-based cationic moieties separated (or linked) by an organic bridging group as described above and paired with a counter ion; and
(ii) Reacting the polycationic complex with at least one ionic salt based on a delocalized anion as defined herein.
According to one example, the organic superbase is a neutral amidine, guanidine or phosphazene type organic superbase. According to a related variant the organic super-base is selected from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu or a derivative thereof. For example, the organic superbase may be DBU or BEMP.
According to another example, the organic bridging compound includes an organic bridging group as described above and at least two anionic leaving groups. The anionic leaving group of the organic bridging compound may be selected based on its leaving group capacity. Any compatible anionic leaving group is contemplated. Non-limiting examples of anionic leaving groups include halide ions, e.g., F - 、Cl - 、Br - And I - . According to a related variant, the anionic leaving group is Br - 。
According to another example, the organic bridging group is an optionally substituted organic bridging group and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group. According to a related variant, the organic bridging group is C 6 -C 12 Arylene groups. In some examples, the organic bridging group is 1,2,4, 5-tetrakis (bromomethyl) benzene.
According to another example, the two reaction steps may be carried out sequentially, simultaneously or partially overlapping each other in time. According to a related variant, the two reaction steps are carried out sequentially and the step of reacting the organic super base with the organic bridging compound is carried out before the step of reacting the polycationic complex with the ionic salt. According to another related variant, all reactants may be mixed together and reacted under appropriate reaction conditions.
According to another example, the step of reacting the organic superbase with the organic bridging compound may be performed in the presence of a solvent. For example, the solvent may be a polar solvent selected from DCM, DMC, ACN, etOH and miscible combinations of at least two thereof. According to a related variant, the solvent may be DCM.
According to another example, the step of reacting the organic superbase with the organic bridging compound may be carried out in a base such as triethylamine (Et) 3 N), N-diisopropylethylamine (iPr) 2 NEt), pyridine and pyridine derivatives. According to a related variant, the base is Et 3 N。
According to a related example, the synthesis of a polycationic ionic plastic crystal can be performed by the method as shown in scheme 6 (where no by-products of the reaction are shown):
wherein, the liquid crystal display device comprises a liquid crystal display device,
M n+ is selected from Na + 、K + 、Li + 、Ca 2+ And Mg (magnesium) 2+ Alkali metal or alkaline earth metal ions of the ions.
According to another example, the step of reacting the organic superbase with the organic bridging compound may further comprise recovering the polycationic complex. For example, the step of recovering the polycationic complex may be performed by centrifugation. Centrifugation may be carried out at a number of revolutions per minute sufficient to recover the polycationic complex for a sufficient period of time. For example, centrifugation may be performed at about 5000rpm for about 10 minutes.
According to another example, the two reaction steps may be conducted at a sufficiently high temperature and for a sufficient time to achieve a substantially complete reaction. For example, the step of reacting the organic superbase with the organic bridging compound may be performed at room temperature for about 4 days. For example, the step of reacting the polycationic complex with the ionic salt may be performed at room temperature for about 3 days.
According to another example, the method further comprises recovering the polycationic ionic plastic crystals, e.g., by centrifugation. Centrifugation may be carried out for a sufficient time at a number of revolutions per minute sufficient to recover the polycationic ion plastic crystals.
According to another example, the method further comprises drying the polycationic ionoplastic crystals. The drying step may be carried out at a sufficiently high temperature and for a sufficient time to substantially dry the polycationic ionic plastic crystals. For example, the drying step may be performed under vacuum at a temperature of about 45 ℃ for about 48 hours.
According to another example, the method further comprises removing at least one by-product generated during any process step. For example, the removal step may be performed by distillation or evaporation. For example, depending on the boiling point of the by-product to be removed, the by-product may be removed at ambient atmospheric pressure or under vacuum. The by-product may be removed by washing with any suitable solvent that dissolves the by-product but does not dissolve the polycationic ionic plastic crystals. For example, byproducts may also be removed by more than one process, if necessary. According to a related variant, the by-product may be removed by extraction, for example by dissolving the product in DCM.
The present technology also relates to the use of an ion plastic crystal composition or ion plastic crystal as defined above in electrochemical applications.
According to one example, the ion plastic crystal composition or ion plastic crystal can be used in electrochemical cells, batteries, supercapacitors (e.g., carbon-carbon supercapacitors, hybrid supercapacitors, etc.). According to another example, the ion plastic crystal composition or ion plastic crystal may be used in electrochromic materials, electrochromic cells, electrochromic devices (ECDs), and electrochromic sensors, such as those described in U.S. patent No.5,356,553, U.S. patent No.8,482,839, and U.S. patent No.9,249,353.
According to another example, the ion plastic crystal composition as defined herein may be a solid electrolyte composition based on ion plastic crystals. According to another example, the ion plastic crystal composition as defined herein may be used as a component of an electrode material, for example as a binder in an electrode material.
The invention thus also relates to a solid electrolyte based on ionic plastic crystals comprising ionic plastic crystals as defined above or an ionic plastic crystal composition as defined above (i.e. comprising ionic plastic crystals as defined above), wherein the ionic plastic crystals may be optionally crosslinked if crosslinkable functional groups are present therein.
According to one example, the ion plastic crystal solid electrolyte composition or ion plastic crystal solid electrolyte as defined above may further comprise at least one salt. For example, the salt may be dissolved in the ion plastic crystal solid electrolyte composition or ion plastic crystal solid electrolyte.
According to another example, the salt may be an ionic salt, such as a lithium, sodium, potassium, calcium or magnesium salt. According to a related variant, the ionic salt is a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF 6 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiFeSI), (fluorosulfonyl) (trifluoromethanesulfonyl) imide) lithium (Li (FSI) (TFSI)), lithium 2-trifluoromethyl-4, 5-dicyanoimidazole (LiTDI), lithium 4, 5-dicyano-1, 2, 3-triazole (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), lithium difluorophosphate (LiDFP), 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 triflate (LiSO) 3 CF 3 ) (LiOTf), lithium fluoroalkyl phosphate Li [ PF ] 3 (CF 2 CF 3 ) 3 ]Lithium tetrakis (trifluoroacetoxy) borate Li [ B (OCOCF) 3 ) 4 ](LiTFAB), lithium bis (1, 2-benzenediol (2-) -O, O') borate [ B (C) 6 O 2 ) 2 ](LiBBB), lithium difluoro (oxalate) borate (LiBF 2 (C 2 O 4 ) (LiFeB), liBF 2 O 4 R x (wherein R is x ＝C 2-4 Alkyl) and combinations of at least two thereof. According to a related variant, the lithium salt may be LiPF 6 . According to another related variant, the lithium salt may be LiFSI. According to another related variant, the lithium salt may be LiTFSI. Non-limiting examples of sodium salts include the above salts in which lithium ions are replaced with sodium ions. Non-limiting examples of potassium salts include the above salts in which lithium ions are replaced by potassium ions. Non-limiting examples of calcium salts include the above salts in which lithium ions are replaced with calcium ions and in which the number of anions present in the salt is adjusted according to the charge of the calcium ions. Non-limiting examples of magnesium salts include the above salts in which lithium ions are replaced with magnesium ions and in which the number of anions present in the salt is adjusted according to the charge of the magnesium ions.
According to another example, the ion plastic crystal-based solid electrolyte composition or ion plastic crystal-based solid electrolyte as defined above may further comprise additional components such as ion conductive materials, inorganic particles, glass particles, ceramic particles (e.g. nanoceramics), plasticizers and other similar components or a combination of at least two thereof. For example, the additional components may be selected based on their mechanical, physical, and/or chemical properties. For example, the additional component may be selected on the basis of its high ionic conductivity and may be added in particular in order to improve the conduction of lithium ions. According to a related variant, the additional component may be selected from NASICON, LISICON, thio-LISICON type compounds, garnet, in crystalline and/or amorphous form, and combinations of at least two thereof.
According to another example, the ionic plastic crystal-based solid electrolyte may be in the form of a thin film. For example, the membrane may comprise at least one electrolyte layer comprising a solid electrolyte based on ionic plastic crystals. For example, the additional component may comprise and/or be substantially dispersed in the electrolyte layer or be separate from the ion-conducting layer, such as being deposited on the electrolyte layer.
The present technology also relates to an adhesive composition comprising an ion plastic crystal as defined herein or an ion plastic crystal composition as defined herein, and an adhesive.
According to another example, the binder may be a polymeric binder and may be selected, for example, based on its ability to dissolve in a solvent that also dissolves the plastic crystals as defined herein and to mix effectively with the plastic crystals. For example, the solvent may be an organic solvent (e.g., N-methyl-2-pyrrolidone (NMP)). The solvent may also comprise, for example, a polar protic solvent (e.g., isopropanol) to dissolve the polymer.
Non-limiting examples of polymeric binders include fluoropolymers (e.g., polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP)), synthetic or natural rubber (e.g., ethylene-propylene-diene monomer (EPDM) rubber), and ion-conductive polymeric binders such as copolymers composed of at least one lithium ion solvating segment, such as polyether, and optionally at least one crosslinkable segment (e.g., PEO-based polymers comprising methyl methacrylate repeat units). According to a related variant, the polymeric binder is a fluoropolymer binder. For example, the fluoropolymer binder is PTFE. Alternatively, the fluoropolymer binder is PVDF or PVDF-HFP, preferably PVDF. According to another related variant, the polymeric binder is a fluorine-free polymeric binder. For example, the polymeric binder is EPDM.
According to another example, the binder may be a polymeric binder and may be, for example, a polymer as described above with respect to Solid Polymer Electrolytes (SPEs).
The present technology also relates to the use of the binder composition as defined herein in an electrode material.
The present technology also relates to an electrode material comprising at least one electrochemically active material and an ion plastic crystal or ion plastic crystal composition as defined herein. According to one example, the ion plastic crystal or ion plastic crystal composition is a binder in an electrode material. In one example, the electrode material is a positive electrode material. In another example, the electrode material is a negative electrode material.
According to one example, the electrochemically active material may be in the form of particles. Non-limiting examples of electrochemically active materials include metal oxides, lithium metal oxides, metal phosphates, lithium metal phosphates, titanates, lithium titanates, metal fluorophosphates, lithium metal fluorophosphates, metal oxofluorophosphates, lithium metal oxofluorophosphates, metal sulfates, lithium metal sulfates, metal halides (e.g., metal fluorides), lithium metal halides (e.g., lithium metal fluorides), sulfur, selenium, and combinations of at least two thereof. According to a related variant, the electrochemically active material is selected from the group consisting of metal oxides, lithium metal oxides, metal phosphates, lithium metal phosphates, titanates, lithium metal fluorides, lithium metal fluorophosphates, lithium metal oxyfluorophosphates, metal sulfates, metal halides, sulfur, selenium and combinations of at least two thereof.
For example, the metal of the electrochemically active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), antimony (Sb), zirconium (Zr), zinc (Zn), niobium (Nb), and combinations of at least two thereof when compatible. According to a related example, the metal of the electrochemically active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), and, when compatible, a combination of at least two thereof. According to another related example, the metal of the electrochemically active material may be selected from titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), and combinations of at least two thereof when compatible.
Non-limiting examples of electrochemically active materials also include titanates and lithium titanates (e.g., tiO 2 、Li 2 TiO 3 、Li 4 Ti 5 O 12 、H 2 Ti 5 O 11 、H 2 Ti 4 O 9 Or combinations thereof), metal phosphates, and lithium metal phosphates (e.g., liM' PO 4 And M' PO 4 Wherein M' may be Fe, ni, mn, mg, co or a combination of at least two thereof), vanadium oxide and vanadium metal oxideObjects (e.g. LiV 3 O 8 、V 2 O 5 、LiV 2 O 5 And other similar oxides) and other limns 2 O 4 、LiM”O 2 (wherein M 'is selected from Mn, co, ni, and combinations thereof) or Li (NiM') O 2 (wherein M' "is selected from Mn, co, al, fe, cr, ti, zr, another similar metal, and combinations thereof) and, when compatible, combinations of at least two thereof.
According to another example, the electrochemically active material may optionally be doped with other elements in lower amounts, for example to adjust or optimize its electrochemical properties. For example, an electrochemically active material may be doped by replacing its metal with other ionic moieties. For example, the electrochemically active material may be doped with a transition metal (e.g., ti, V, cr, mn, fe, co, ni, cu, zn or Y) and/or an element other than a transition metal (e.g., mg, al, or Sb).
According to another example, the electrochemically active material may be in the form of particles (e.g., microparticles and/or nanoparticles), which may be newly formed or from commercial sources. For example, the electrochemically active material may be in the form of particles coated with a layer of the coating material. The coating material may be an electronically conductive material, for example, a conductive carbon coating.
According to another example, the electrode material is a negative electrode material comprising, for example, carbon-coated lithium titanate (C-LTO) as an electrochemically active material.
According to another example, the electrode material as defined herein further comprises an additive. For example, the additive may be selected from inorganic ion conductor materials, inorganic materials, glass ceramics, including nanoceramics (e.g., al 2 O 3 、TiO 2 、SiO 2 And other similar compounds), salts (e.g., lithium salts), and other similar additives or combinations of at least two thereof. For example, the additive may be an inorganic ion conductor selected from NASICON, LISICON, thio-LISICON type compounds, garnet, sulfide, thiohalide, phosphate and thiophosphate compounds (in crystalline and/or amorphous form) and combinations of at least two thereof.
According to another oneAs an example, the electrode material as defined herein further comprises an electronically conductive material. Non-limiting examples of electronically conductive materials include carbon sources such as carbon black (e.g., ketjen TM Carbon and Super P TM Carbon), acetylene black (e.g. Shawinigan carbon and Denka TM Carbon black), graphite, graphene, carbon fibers (e.g., vapor Grown Carbon Fibers (VGCFs)), carbon nanofibers, carbon Nanotubes (CNTs), and combinations of at least two thereof.
According to another example, an electrode material as defined herein may have an ion-plastic crystal ratio of electrochemically active material to ion-plastic of less than about 6, or less than about 5, or less than about 4, or less than about 3, preferably less than about 4.
According to another example, the electrode material as defined herein may have a porosity of less than about 8%, or less than about 7%, or less than about 6%, or less than about 5%, or less than about 4%, or less than about 3%, or less than about 2%, or less than about 1%, preferably less than about 5%. For example, excessive porosity may limit electrode performance, as the porosity of a plastic crystal-based electrode may act as a resistance to lithium ion transport.
According to another example, the ratio of electrochemically active material to ionic plastic crystals may substantially affect the porosity of the electrode material. In some examples, less than about 4 of electrochemically active material, ion plastic crystals are used to obtain electrodes having less than about 5% porosity to obtain very high electrochemical performance.
The present technology also relates to an electrode comprising an electrode material as defined herein and applied on a current collector (e.g. aluminum or copper foil). Alternatively, the electrode may be a self-supporting electrode. According to a related variant, the electrode as defined herein is a positive electrode. According to another related variant, the electrode as defined herein is a negative electrode.
The present technology thus also relates to a method of producing an electrode material as defined herein and an electrode as defined herein. For a more detailed understanding of the present description, reference is now made to fig. 1, which shows a flow chart of a method of producing an electrode material as defined herein, according to one possible embodiment.
As shown in fig. 1, the method may include a step of preparing a Carbon Binder Slurry (CBS). The CBS preparation step comprises dispersing the electronically conductive material as described above in the adhesive composition. For example, the adhesive composition may comprise an adhesive (e.g., an adhesive as described above), a solvent as described above, and/or a carbon dispersant. For example, the electronically conductive material may be a combination of carbon black and VGCF, and the binder composition may include PVDF and polyvinylpyrrolidone (PVP) as binders in combination with NMP as a solvent. It should be noted that PVP may also be used as a carbon dispersant. The step of dispersing the electronically conductive material in the adhesive composition may be performed by any compatible method. For example, the step of dispersing the electron conductive material in the binder composition may be performed by a milling method, such as a ball milling method. The step of dispersing the electronically conductive material in the binder composition may be performed for a time sufficient to obtain a substantially uniform CBS.
According to one example, the step of preparing the CBS may further comprise the step of preparing the binder composition, for example by mixing a binder, a solvent and/or a carbon dispersant. The step of preparing the adhesive composition may be performed by any compatible method. For example, the step of preparing the adhesive composition may be performed by a milling process, such as a roll milling process. The step of preparing the adhesive composition may be performed for a time sufficient to substantially dissolve the adhesive and/or the carbon dispersant in the solvent. For example, the step of preparing the adhesive composition may be performed for more than 10 hours.
Still referring to fig. 1, the method may further include the step of preparing a catholyte solution based on ion plastic crystals (PCr). For example, the PCr catholyte solution may be a dilute PCr catholyte solution. Illustratively, the step of preparing a diluted PCr catholyte solution may include diluting PCr as described herein and an ionic salt (e.g., a lithium salt, such as LiFSI) as described above by adding an additional solvent to the solution. For example, the additional solvent may be NMP.
Still referring to fig. 1, the method may further comprise preparing a PCr-CBS slurry. For example, the step of preparing the PCr-CBS slurry may be performed by adding a diluted PCr catholyte solution to the CBS. For example, a dilute PCr catholyte solution may be gradually added to the CBS to prevent too abrupt an increase in the polarity of the slurry.
Still referring to fig. 1, the method may further include adding an electrochemically active material as described above to the PCr-CBS slurry. For example, the electrochemically active material may be lithium nickel manganese cobalt oxide (NMC).
Fig. 2 shows a flow chart of a method of producing an electrode as defined herein according to one possible embodiment.
As shown in fig. 2, the method may further comprise the step of coating the PCr-CBS slurry as described above on a current collector or on a substrate or carrier film (e.g. a substrate made of silicone, polypropylene or siliconized polypropylene) to obtain a PCr-based positive electrode film on the current collector or carrier. For example, the substrate or carrier film may be subsequently removed. According to a related variant, the PCr-CBS slurry is coated on the current collector. For example, the coating step may be performed by any compatible coating method. For example, the coating step may be performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method. According to a related variant, the coating step is carried out by a blade coating method.
According to another example, the method may further comprise the step of drying the PCr-based cathode film. For example, the drying step may be conducted at a temperature and for a time sufficient to substantially remove any residual solvent. For example, the drying step may be performed in a vacuum oven at a temperature of about 120 ℃ for more than 10 hours to substantially remove any residual solvent.
Still referring to fig. 2, the method may further include the step of calendaring or pressing the positive electrode film to substantially reduce its thickness. For example, the calendering or pressing step may be performed by any compatible calendering or pressing method. For example, the calendaring or pressing step may be performed by a roll-in (or between) process.
According to another example, an electrode material obtained by a method as defined herein may be substantially or completely free of carbonaceous agglomerates compared to an electrode material obtained by a conventional mixing method. In practice, the electrode material obtained by conventional mixing methods generally comprises carbon agglomerates. This may be due to the fact that carbon is easily agglomerated in highly polar solvents due to its hydrophobic surface properties.
The present technology also relates to 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 an ion plastic crystal as defined herein or an ion plastic crystal composition as defined herein.
The present technology also relates to 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 is as defined herein. According to a related variant, the electrolyte is an ionic plastic crystalline solid electrolyte as defined herein. According to another related variant, the negative electrode is as defined herein. According to another related variant, the positive electrode is as defined herein. According to another related variant, the electrolyte is a solid electrolyte based on ionic plastic crystals as defined herein, and the positive electrode is as defined herein.
In some cases, the negative electrode (counter electrode) comprises an electrochemically active material, which may be any known electrochemically active material, and which may be selected based on its electrochemical compatibility with the various elements of the electrochemical cell as defined herein. For example, the electrochemically active material of the negative electrode is selected based on its electrochemical compatibility with the material of the positive electrode as defined herein. Non-limiting examples of electrochemically active anode materials include alkali metals, alkali metal alloys, graphite, silicon (Si), tin (Sn), and pre-lithiated electrochemically active materials. In some examples, the electrochemically active material of the negative electrode includes lithium titanate, carbon-coated lithium titanate, an alkali metal, or an alkali metal alloy. In a related variant, the electrochemically active material of the negative electrode is lithium metal.
The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery pack may be selected from the group consisting of a lithium battery pack, a lithium ion battery pack, a lithium-sulfur battery pack, a sodium ion battery pack, a magnesium battery pack, and a magnesium ion battery pack. According to a related variant, the battery is a lithium battery or a lithium ion battery. For example, the battery pack may be an all-solid-state battery pack (e.g., an all-solid-state lithium battery pack).
Examples
The following examples are for illustration only and should not be construed as further limiting the scope of the invention as contemplated. These embodiments are better understood with reference to the drawings.
Unless otherwise indicated, all numbers expressing quantities of ingredients, manufacturing conditions, concentrations, properties, and so forth used herein are to be understood as being modified in all instances by the term "about". At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Thus, unless otherwise indicated, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties. Notwithstanding that the numerical ranges and parameters setting forth the ranges of the embodiments are, in fact, approximations, the numerical values set forth in the following examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors resulting from variation in experimentation, experimental measurements, statistical analysis, and the like.
EXAMPLE 1 Synthesis and characterization of Mono-cationic ion Plastic Crystal
Two methods have been developed to produce substantially pure (about 99% pure) proton-type ion plastic crystals. The proton ion plastic crystal has a glass transition temperature (T) between about-70 ℃ and about-60 DEG C g ) And a melting point between about 10 ℃ and about 45 ℃. It is noted that with the insertion of methacrylate functionality, the melting point decreases. The reaction yield is improved in the presence of silylated derivatives of formic acid, diethylene glycol (SiDEG) and/or silylated derivatives of glycerol (SiGLY).
(a) Synthesis of silylated derivatives of diethylene glycol and glycerol
The synthesis of silylated derivatives of diethylene glycol (SiDEG) and of glycerol (SiGLY) was carried out by silylation of diethylene glycol or glycerol with tert-butyldimethylsilyl chloride (TBDMS-Cl) in DCM as solvent and imidazole as base and catalyst.
The silylation reaction was carried out in a glove box by adding all reagents to a pre-cleaned and dried round bottom flask equipped with a magnetic stirrer. The round bottom flask was dried at a temperature of 120 ℃ for at least 3 hours to remove any residual water before adding the reagents.
All reagents were also pre-dried and then weighed. Diethylene glycol and glycerol are dried by azeotropic distillation with toluene and added at the end, i.e. after all other reactants.
The round bottom flask was then fitted with a stopper and stirred at 1,000rpm at room temperature for at least 15 to 24 hours. The mixture thus obtained is then filtered, the filtrate is dissolved in another 50 ml of DCM, washed three times with 10% (v/v) aqueous hydrochloric acid, washed three times with saturated aqueous sodium carbonate (Na 2 CO 3 ) Three washes, three washes with water and finally three washes with brine. The organic phase was stirred over magnesium sulfate (MgSO) 4 ) Drying for 12 hours. The solution thus obtained is then filtered. The filtrate was evaporated to dryness and dried under vacuum for 12 hours. In the case of an impure solution, the solution is distilled under vacuum at a temperature of 130 ℃ for 30 minutes and volatile contaminants are removed.
The amounts, moles and equivalents of reagents used for small scale silylation of diethylene glycol and glycerol are presented in tables 1 and 2, respectively.
TABLE 1 reagents for silylation of diethylene glycol
Reagent(s) Quantity (g) n(mmol) Equivalent weight
Imidazole 10.5 154 2.7
Diethylene glycol 6.0 56.6 1.0
DCM, anhydrous 120 -- --
TBDMS-Cl 20.5 135.84 2.4
TABLE 2 reagents for silylation of glycerol
Reagent(s) Quantity (g) n(mmol) Equivalent weight
Imidazole 15.4 226.4 4.0
Glycerol 5.2 56.6 1.0
THF, anhydrous 120 -- --
TBDMS-Cl 28.2 186.8 3.3
Silylated derivatives of diethylene glycol (SiDEG) and glycerin (SiGLY) prepared in this example were prepared by Fourier transform Infrared Spectroscopy (FTIR) and proton Nuclear magnetic resonance 1 H NMR).
(b) Preparation of ion plastic crystal
The synthesis was performed in a glove box by adding all reagents to a pre-cleaned and dried round bottom flask equipped with a magnetic stirrer. All reagents were also pre-dried under vacuum at a temperature below 60 ℃ for about 48 hours and then weighed. The round bottom flask was dried at a temperature of 120 ℃ for at least 3 hours to remove any residual water before adding the reagents.
The round bottom flask was equipped with a reflux condenser, heated to a preselected temperature and stirred at 500rpm under an inert atmosphere of nitrogen for at least 4 days. The mixture thus obtained was then cooled and the pH measured to ensure that the mixture was under alkaline (alkaline (basic)) conditions. The mixture was then evaporated to dryness in vacuo at a temperature below 50 ℃. The residue was then dissolved in 45 ml DCM, washed four times with water and then twice with brine. The solution thus obtained is then filtered and the filtrate is evaporated to dryness. The two phases thus formed were separated using a separating funnel. The lower phase (pale yellow phase) was recovered and concentrated. The viscous solid was then vacuum distilled at 160 ℃ for about 12 hours to remove volatile contaminants. The viscous solid became a solid at room temperature.
Ionic plastic crystals (plastic crystals 1 to 14) were obtained by the method of the present example. The equivalent numbers and synthesis conditions of the respective reagents are presented in table 3, and the reaction yields and melting points of the respective ion plastic crystals are presented in table 4.
TABLE 3 Synthesis of Plastic Crystal 1 to 14
Table 4 reaction yields (%) and melting points (. Degree. C.) obtained for the plastic crystals 1 to 14
Plastic crystal Yield (%) Melting point (. Degree. C.)
1 72 12 and 41
2 82 11 and 38
3 74 21
4 56 12 and 32
5 66 5 and 32
6 48 14 and 41
7 45 N/A
8 84 13 and 42
9 58 N/A
10 62 N/A
11 56 45
12 60 14 and 44
13 62 12 and 39
14 52 12 and 34
BEMP was used as a 1M solution of BEMP in hexane. The solvents in table 3 were anhydrous Acetonitrile (ACN), dichloromethane (DCM), dimethyl carbonate (DMC) and ethanol (EtOH).
Using the method of this example, ion plastic crystals (plastic crystals 15 and 16) were obtained, and the amounts, moles and equivalents of reagents used in the synthesis are shown in tables 5 and 6, respectively.
TABLE 5 reagents used in the Synthesis of Plastic Crystal 15
TABLE 6 reagents used in the Synthesis of Plastic Crystal 16
Reagent(s) Amount, weight percent
LiFSI 32.9
SiGLY prepared in example 1 (a) 57
SiDEG prepared in example 1 (a) 0.87
ACN, anhydrous --
DBU 9.2
FIG. 3 shows the formation of a complex between deuterated dimethyl sulfoxide (DMSO-d 6 ) Proton NMR spectra obtained for commercial sources of DBU. The proton NMR spectrum was obtained for comparison purposes.
FIGS. 4, 5 and 6 show the formation of a mixture of deuterium and chloroform (CDCl) 3 ) Nuclear magnetic resonance of carbon-13, fluorine-19 and lithium-7 obtained from plastic crystal 1 13 C NMR、 19 F NMR 7 Li NMR) spectra.
As shown in FIG. 6, no observation was made in the region of 21ppm to-19 ppm 7 Li NMR peaks.
Fig. 7 shows a mass spectrum obtained for plastic crystal 1 by a high performance liquid chromatography-time of flight mass spectrometer (HPLC TOF ESI-MS) with electrospray ionization source. Is given in negative mode (ESI) - ) And positive mode (ESI) + ) The following results.
Fig. 8 shows the results of Differential Scanning Calorimetric (DSC) analysis obtained for plastic crystal 1. Isothermal measurements (at 150.00 ℃ and-90.00 ℃) and non-isothermal measurements (3.00 ℃/min ramp) were performed. Repeated DSC heat-cool cycle measurements were performed according to the thermal program: 3.00 ℃/min ramp from-90.00 ℃ to 150.00 ℃ (1), isothermal 3min at 150.00 ℃,3.00 ℃/min ramp from 150.00 ℃ to-90.00 ℃ (2), isothermal 3min at-90.00 ℃, and 3.00 ℃/min ramp from-90.00 ℃ to 150.00 ℃ (3).
FIG. 9 showsMass spectra obtained by HPLC TOF ESI-MS on plastic crystal 11 are shown. Displayed in ESI - And ESI (electronic service interface) + The following results.
Fig. 10 shows the DSC results obtained for plastic crystal 11. Isothermal measurements (at 150.00 ℃ and-90.00 ℃) and non-isothermal measurements (3.00 ℃/min ramp) were performed. Repeated DSC heat-cool cycle measurements were performed using the following thermal procedure: 3.00 ℃/min ramp from-90.00 ℃ to 150.00 ℃ (1), isothermal 3min at 150.00 ℃,3.00 ℃/min ramp from 150.00 ℃ to-90.00 ℃ (2), isothermal 3min at-90.00 ℃, and 3.00 ℃/min ramp from-90.00 ℃ to 150.00 ℃ (3).
(c) Preparation of ion plastic crystal
Ion plastic crystals are also synthesized by the following method. The synthesis was carried out in a glove box in a previously cleaned and dried round-bottomed flask equipped with a magnetic stirrer. All reagents were also pre-dried under vacuum at a temperature below 60 ℃ for about 48 hours and then weighed. The round bottom flask was dried at a temperature of 120 ℃ for at least 3 hours to remove any residual water before adding the reagents.
Using the method of this example, ion plastic crystals (plastic crystals 17 and 18) were obtained, and the amounts, moles and equivalents of reagents used in the synthesis are shown in tables 7 and 8, respectively.
TABLE 7 reagents used in the Synthesis of Plastic Crystal 17
Reagent(s) Quantity (g) n(mmol) Equivalent weight
LiFSI, anhydrous 1.0 5.35 1.0
Formic acid 0.246 5.35 1.0
SiDEG prepared in example 1 (a) 1.6 5.35 1.0
ACN, anhydrous 15 -- --
DBU 0.75 5.35 0.35
TABLE 8 reagents used in the Synthesis of Plastic Crystal 18
Reagent(s) Quantity (g) n(mmol) Equivalent weight
LiFSI, anhydrous 1.0 5.35 1.0
Formic acid 0.246 5.35 1.0
ACN, anhydrous 15 -- --
DBU 0.75 5.35 0.35
Solvent and DBU were added to a round bottom flask. The round bottom flask was then equipped with a septum, taken out of the glove box and cooled to a temperature of about 4 ℃. Formic acid was then added drop wise to the round bottom flask with stirring. The mixture was then heated to a temperature of about 21 ℃ and stirred under an inert argon atmosphere for about 1 hour. The round bottom flask was equipped with a reflux condenser and stirred at 500rpm for at least 4 days at a temperature of 21 ℃ under an inert atmosphere of nitrogen. The mixture thus obtained was then cooled and the pH measured to ensure that the mixture was under alkaline (alkaline (basic)) conditions. The mixture was then filtered and the filtrate evaporated to dryness in vacuo at a temperature below 50 ℃. Evaporated to dryness in vacuo at a temperature below 50 ℃. The residue was dissolved in 45 ml DCM, washed four times with water and twice with brine. The two phases thus formed were separated using a separating funnel. The lower phase (pale yellow phase) was recovered and concentrated. The viscous solid was then vacuum distilled at 160 ℃ for about 12 hours to remove volatile contaminants. The viscous solid became a solid at room temperature.
(d) Post-functionalization of Ionic Plastic Crystal prepared in examples 1 (b) and 1 (c)
Post-functionalization of the ionoplast crystals prepared in examples 1 (b) and 1 (c) was performed to introduce crosslinkable functional groups.
1.50 g of the ionic plastic crystals prepared in examples 1 (b) and 1 (c) were dissolved in 25 ml of anhydrous THF. 0.70 ml of 2-isocyanatoethyl methacrylate was added to the solution. The mixture thus obtained was stirred under an inert atmosphere of nitrogen at a temperature of about 60 ℃ for about 5 hours. At the end of the reaction 5 ml of methanol are added and the mixture is cooled. The solid thus obtained is then evaporated to dryness and dried under vacuum at a temperature of about 60 ℃.
Fig. 11 shows the proton NMR spectrum obtained for the plastic crystal 15 after post-functionalization as described in this example. In DMSO-d 6 Is performed in the middle of 1 H NMR measurement.
Fig. 12 shows the DSC results obtained for plastic crystal 15 after post-functionalization as described in this example. Isothermal measurements (at 150.00 ℃ and-90.00 ℃) and non-isothermal measurements (10.00 ℃/min ramp) were performed. Repeated DSC heat-cool cycle measurements were performed using the following thermal procedure: 10.00 ℃/min ramp from-90.00 ℃ to 150.00 ℃ (dashed line, 1), isothermal 3min at 150.00 ℃ (dashed line-dot line, 2), 10.00 ℃/min ramp from 150.00 ℃ to-90.00 ℃ (solid line, 3), isothermal 3min at-90.00 ℃ (dashed line-dot line, 4), and 10.00 ℃/min ramp from-90.00 ℃ to 150.00 ℃ (dot line, 5).
Fig. 13 shows the thermogravimetric analysis (TGA) results obtained for the plastic crystal 15 after post-functionalization as described in this example. Thermal degradation of the ion plastic crystal occurs in a programmed temperature range from room temperature to 800 ℃. The ion plastic crystal was heated in an oven from room temperature to 800 ℃ under an oxidizing environment (air) at a heating ramp rate of 10 ℃/min.
Fig. 14 shows the DSC results obtained for plastic crystals 16 after post-functionalization as described in this example. Isothermal measurements (at 150.00 ℃ and-20.00 ℃) and non-isothermal measurements (2.00 ℃/min ramp) were performed. Repeated DSC heat-cool cycle measurements were performed using the following thermal procedure: 2.00 ℃/min ramp from-20.00 ℃ to 150.00 ℃ (dashed line, 1), isothermal 3min at 150.00 ℃ (solid line, 2), 2.00 ℃/min ramp from 150.00 ℃ to-20.00 ℃ (dashed line-point-dotted line, 3), isothermal 3min at-20.00 ℃ (solid line, 4), and 2.00 ℃/min ramp from-20.00 ℃ to 150.00 ℃ (dotted line, 5).
(e) Ion conductivity of Ionic Plastic Crystal given in example 1 (d)
Ion conductivity measurements were made by alternating current electrochemical impedance spectroscopy recorded with a VPM3 multichannel potentiostat. The electrochemical impedance spectroscopy is performed at a temperature range of 20 ℃ to 80 ℃ (increasing and decreasing, 10 ℃ each) between 200mHz to 1 mHz.
Each electrochemical impedance measurement was obtained after the oven temperature was stabilized at temperature (T).
The ion plastic crystal film is placed at two active surface areas of 2.01cm 2 Is between the electrodes.
The ionic conductivity of lithium ions was calculated from electrochemical impedance spectroscopy measurements using equation 1:
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wherein, the liquid crystal display device comprises a liquid crystal display device,
sigma is the ionic conductivity (S.cm) -1 ) L is the thickness of the ion plastic crystal film between the two blocking electrodes, A is the contact surface area between the ion plastic crystal film and the two blocking electrodes, and R t Is the total resistance measured by electrochemical impedance spectroscopy.
Fig. 15 shows the temperature (K) versus time for the assembled symmetrical cell in this embodiment -1 ) Measured ionic conductivity (S.cm) -1 ) As a result. FIG. 15 shows that 1.52X10 of plastic crystal 15 after post-functionalization as described in example 1 (d) is obtained at a temperature of 50 ℃ -5 S.cm -1 Ion conductivity values of (2).
FIG. 16 presents the temperature (K) versus time for a symmetrical cell assembled with plastic crystal 16 after post-functionalization as described in example 1 (d) -1 ) Measured ionic conductivity (S.cm) -1 ) As a result.
Example 2 preparation of ceramic-ion Plastic Crystal composite Membrane
For a composition containing 90 wt% Li 6 PS 5 The ceramic-ion plastic crystal composite film of Cl and 10 wt% of plastic crystal 1 or 13 achieves ion conductivity results.
For a composition containing 90 wt% Li 6 PS 5 The ion conductivity results were obtained with Cl and 10 wt% of an ion plastic crystal mixture comprising a polymer as described in the US '674 patent (hereinafter referred to as US'674 polymer) and the ceramic-ion plastic crystal composite films of ion plastic crystals prepared in examples 1 (b) to 1 (d).
Finally, for a composition containing 90 wt% Li 6 PS 5 Ceramic-polymer composite film of Cl and 10 wt% of US'674 polymer and Li for comparison purposes 6 PS 5 The Cl film gave the ion conductivity results.
DCM or ACN was added to the mixture as necessary to obtain the appropriate viscosity. The mixture was then cast onto a pre-degreased aluminum foil. Pellets of 10mm diameter were placed in a mold and compressed using a press at a pressure of 2.8 tons and then transferred to a conductive cell at a pressure of 5 MPa. The temperature was allowed to stabilize for about 1 hour. The ceramic-ion plastic crystal composite film has a conductivity resulting in a range of about 3.0 to about 7.0x10 at a temperature of 20 DEG C -4 Within S/cm, this is similar to the case of this ceramic (Li 6 PS 5 Cl) the conductivity results obtained. The conductivity result of the ceramic-ion plastic crystal composite membrane is also obviously better than that of the ceramic-polymer composite membrane. Impedance measurements were recorded twice at each temperature for 15 minutes between each measurement. The conductivity cell was assembled according to the configuration shown in table 9.
TABLE 9 conductivity cell configuration
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In table 9, the expression "not dried" means that the film was dried under vacuum at 25 ℃ for 12 hours to remove ACN only. In table 9, the expression "dry" means that the film was dried under vacuum at 80 ℃ for 12 hours to ensure proper drying. Thus, the plastic crystals melt and may slightly diffuse into the polymer.
Fig. 17 shows the temperature (K) for the assembled conductivity cell in this embodiment -1 ) Measured ionic conductivity (S.cm) -1 ) As a result. The results of battery 1 (+), battery 2 (■), battery 3 (×x), battery 4 (+) and battery 5 (+) as described in the present embodiment are presented.
Fig. 18 shows the temperature (K) for the assembled conductivity cell in this embodiment -1 ) Measured ionic conductivity (S.cm) -1 ) As a result. The results of the batteries 6 (+), 7 (+), 8 (X), 9 (■), 10 (solid, solid line) and 11 (solid, broken line) as described in the present embodiment are presented.
Example 4 anion and cation pairs
The effect of ion pairing on reaction yield was also determined. Ionic plastic crystals (plastic crystals 19 to 28) comprising different combinations of cations and delocalized anions derived from guanidine, amidine or phosphazene organic superbases were obtained by the method described in example 1 (b). The reaction was carried out at a temperature of about 21 ℃ for about 4 days.
The amounts of reagents used in the synthesis are shown in table 10. The reaction yields and the masses of the obtained ion plastic crystals are shown in table 11.
TABLE 10 Synthesis of Plastic crystals 19 to 28
Table 11 reaction yields (%) and quality of Plastic crystals 19 to 28
Plastic crystal Mass (g) of ion plastic crystal Yield (%)
19 3.49 80
20 N/A N/A
21 0.25 10
22 1.26 59
23 1.89 57
24 21.6 84
25 2.27 60
26 N/A N/A
27 0.92 83
28 2.6 84
29 1.1 82
Although not providing all results, all combinations of delocalized anions and cations derived from guanidine, amidine and phosphazene organic superbases produce ionic plastic crystals. However, it should be understood that the pairing of anions and cations has a significant impact on the quality of the product obtained by the reaction and thus on the yield of the reaction.
EXAMPLE 5 characterization of stabilized intermediate ion neutral Complex
As described above, the reaction yield may be improved by forming a stabilized intermediate ion neutral complex obtained from the reaction of a cation derived from a guanidine, amidine or phosphazene organic super base and a bis-silylated compound of formula 17 as described herein.
The stabilized intermediate ion neutral complex formed by the reaction of the bis-silylated derivative of diethylene glycol (SiDEG) prepared in example 1 (a) with protonated DBU was characterized.
Pass over a period of about 3 weeks 1 H NMR 13 C NMR characterizes the stabilized intermediate ion neutral complex to assess its ability to stabilize the protonated base.
Fig. 19 (a) shows the atom numbers of protonated DBU and the bis-silylated derivative (side) of diethylene glycol prepared in example 1 (a).
Fig. 19 (B) shows a proton NMR spectrum obtained for the stabilized intermediate ion neutral complex as described in this example. In acetonitrile-d 3 (CD 3 CN) in a single reactor 1 H NMR measurements and peak assignments are indicated on the spectra.
FIG. 19 (C) shows that the neutral complex of the stabilized intermediate ion is obtained as described in this example 13 C NMR spectrum. In CD 3 In CN 13 C NMR measurements and peak assignments are indicated on the spectra.
Fig. 20 (a) shows proton NMR spectra obtained over a period of 3 weeks for the stabilized intermediate ion neutral complex as described in this example. Is shown at the beginning of the experiment (blue) 1 H NMR spectrum), after 2 days (red 1 H NMR spectrum), after 3 days (green 1 H NMR spectrum), after 9 days (purple) 1 H NMR spectrum) and after 21 days (yellow 1 H NMR spectrum). In CD 3 In CN 1 HNMR measurements and peak assignments are indicated on the spectra.
FIG. 20 (B) shows that the stabilized intermediate ion neutral complex as described in this example was obtained over a period of 3 weeks 13 C NMR spectrum. Is shown at the beginning of the experiment (blue) 13 C NMR spectrum), after 2 days (Red 13 C NMR spectrum), after 3 days (green 13 C NMR spectrum), after 9 days (purple) 13 C NMR spectrum) and after 21 days (yellow 13 C NMR spectrum). In CD 3 In CN 13 C NMR measurements and peak assignments are indicated on the spectra.
As can be seen in fig. 20 (a) and 20 (B), no significant change was detected in the spectra after 3 weeks, which means that there was no significant product conversion accompanied by structural change during this period.
FIG. 21 (A) shows at 3 weeksProton NMR spectra obtained from the stabilized intermediate ion neutral complex as described in this example. At the beginning of the experiment (blue) 1 H NMR spectrum), after 2 days (red 1 H NMR spectrum), after 3 days (green 1 H NMR spectrum), after 9 days (purple) 1 H NMR spectrum) and after 21 days (yellow 1 H NMR spectrum) between 3.99ppm and 4.30 ppm. In CD 3 In CN 1 H NMR measurements and peak assignments are indicated on the spectra.
Fig. 21 (B) shows proton NMR spectra obtained over a period of 3 weeks for the stabilized intermediate ion neutral complex as described in this example. At the beginning of the experiment (blue) 1 H NMR spectrum), after 2 days (red 1 H NMR spectrum), after 3 days (green 1 H NMR spectrum), after 9 days (purple) 1 H NMR spectrum) and after 21 days (yellow 1 H NMR spectrum) between 6ppm and 10.4 ppm. In CD 3 In CN 1 H NMR measurements and peak assignments are indicated on the spectra.
The appearance of an additional secondary peak (1% of the primary compound after 21 days of reaction) was observed at 4.16ppm in FIG. 21 (A). The position of this peak and its multiplicity may indicate that it corresponds to the CH of diethylene glycol without a silane group at the end 2 Protons.
As can be seen in fig. 21 (B), the peak corresponding to N-H becomes significantly narrower and moves to higher frequencies, a common behavior associated with the formation of hydrogen bonds.
EXAMPLE 6 Synthesis and characterization of polycyclic ion Plastic Crystal
(a) Synthesis of tetracyclic ion Plastic Crystal (Plastic Crystal 30)
The synthesis of polycyclic amidines was carried out by a method analogous to that described by Braddock et al (Braddock, D.C. et al, "The reaction of aromatic dialdehydes with enantiopure 1, 2-diamides: an expeditious route to enantiopure tricyclic amines." Tetrahedron: asymmetry 21.24 (2010): 2911-2919).
Tetracyclic ion plastic crystals (plastic crystals 30) were prepared by the method as shown in scheme 7:
0.8947 g of 2, 3-naphthalenedialdehyde and 60.0 ml of DCM were added to a pre-cleaned and dried round-bottomed flask equipped with a magnetic stirrer. The solution was then stirred until dissolved. Then 3.30 ml of ethylenediamine was added and the solution was stirred at a temperature of about 22 ℃ for about 4 hours. The solvent was then evaporated to dryness.
The synthesis was performed in a glove box by adding all reagents to a pre-cleaned and dried round bottom flask equipped with a magnetic stirrer. The flask was dried at a temperature of 120 ℃ for at least 3 hours to remove any residual water prior to adding the reagents.
The round bottom flask equipped with reflux condenser was heated to a preselected temperature under an inert atmosphere of nitrogen and stirred at 500rpm for at least 4 days. The resulting mixture was then cooled and the pH measured to ensure that the mixture was under alkaline (alkaline (basic)) conditions. The mixture was then evaporated to dryness in vacuo at a temperature below 50 ℃. The residue was then dissolved in 45 ml DCM, washed four times with water and then twice with brine. The solution thus obtained is then filtered and the filtrate is evaporated to dryness. The two phases thus formed were separated using a separating funnel. The lower phase (pale yellow phase) was recovered and concentrated. The viscous solid was then vacuum distilled at 160 ℃ for about 12 hours to remove volatile contaminants. The viscous solid became a solid at room temperature.
A tetracyclic ion plastic crystal (plastic crystal 30) was obtained using the method of this example. The equivalent numbers of the reagents and synthesis conditions are presented in table 12.
TABLE 12 Synthesis of Plastic Crystal 30
(b) Characterization of tetracyclic ion Plastic Crystal (Plastic Crystal 30)
FIG. 22 shows a mass spectrum obtained by HPLC TOF ESI-MS on plastic crystal 30 as described in example 6 (a). Displayed in ESI - And ESI (electronic service interface) + The following results. The eluent used for HPLC TOF ESI-MS was (95% methanol, 4.9% water and 0.1% formic acid) at a flow rate of 0.1ml/min.
Fig. 23 shows DSC results obtained for plastic crystals 30 as described in example 6 (a). Isothermal measurements (at 100.00 ℃ and-20.00 ℃) and non-isothermal measurements (2.00 ℃/min ramp) were performed.
Repeated DSC heat-cool cycle measurements were performed using the following thermal procedure: 2.00 ℃/min ramp from-20.00 ℃ to 100.00 ℃ (1), isothermal 3min at 100.00 ℃,2.00 ℃/min ramp from 100.00 ℃ to-20.00 ℃ (2), isothermal 3min at-20.00 ℃,2.00 ℃/min ramp from-20.00 ℃ to 1090.00 ℃ (3), isothermal 3min at 100.00 ℃,2.00 ℃/min ramp from 100.00 ℃ to-20.00 ℃ (4). The DSC results are presented in Table 13.
TABLE 13 DSC analysis of Plastic Crystal 30
EXAMPLE 7 Synthesis and characterization of polycationic ion Plastic crystals
(a) Synthesis of Multi-cationic ion Plastic Crystal (Plastic Crystal 31)
A tetracationic ion plastic crystal was prepared by the method as shown in scheme 8:
The synthesis of the tetracationic ion plastic crystals was performed by adding 20.0 ml anhydrous DCM and 1.35 ml DBU in a 50 ml round bottom flask, pre-cleaned and dried with a magnetic stirrer, in a glove box. The mixture was then cooled outside the glove box to a temperature of about 4 ℃. The mixture was then stirred and 1.0 g of 1,2,4, 5-tetrakis (bromomethyl) benzene was added.
The mixture was then placed under an inert atmosphere at room temperature for at least 4 days. The white precipitate thus obtained was then removed by centrifugation (5000 rpm, about 10 minutes) and washed three times with 15 ml of DCM. The white solid was then dried under vacuum at a temperature of about 45 ℃ for 3 hours. The reaction yield was 1.624 g.
1.624 g of the solid thus obtained, 1.71 g of LiFSI and 100 ml of absolute ethanol were added in a glove box to a pre-cleaned and dried 250 ml round bottom flask equipped with a magnetic stirrer.
The mixture was then stirred at room temperature under an inert atmosphere for about 3 days. The mixture is then centrifuged, the solids separated and recovered. The solid was transferred to an 80 ml beaker and 50 ml methanol was added. The suspension was stirred at room temperature for 15 minutes. The solids were separated and recovered by centrifugation. The solid was then dried under vacuum at a temperature of about 45 ℃ for about 48 hours. The reaction yield was 1.62 g and the purity was 96%.
(b) Characterization of the Tetracationic ion Plastic Crystal (Plastic Crystal 31)
To the plastic crystal 31 1 H and 19 longitudinal relaxation time of F nuclei (T 1 ) Is a reverse recovery measurement of (1).
Use of MAS X +.1.3 mm equipped 1 H/ 19 500. 500MHz WB Bruker AVANCE NEO of F NMR Probe TM The spectrometer was subjected to NMR experiments at a magic angle of 67kHz at maximum rotational speed. T is carried out at MAS=60 kHz in the temperature range from-10 ℃ to 60 DEG C 1 And (5) measuring. The recovery time delay was from 50 μs to 20s in 12 steps (for 19 F) And to 50s (for 1 H) And (3) a change. FIGS. 24 and 25 show the results obtained for the tetracationic ion plastic crystals prepared in example 7 (a), respectively 1 H NMR 19 F NMR spectrum. FIG. 26 is a graph showing the relaxation time (T) of the tetracationic ion plastic crystal prepared in example 7 (a) 1 ) vs. temperature profile. Perfect description with single exponential decay over the entire temperature range 19 F and F 1 H coreWhich means that the sample is substantially uniform. 1 H and 19 t of F 1 The values are presented in table 13.
Table 13. 1 H and 19 t of F 1 Value of
T,℃ -10 0 10 20 30 40 50 60
19 F:T 1 ，s 0.47 0.49 0.51 0.53 0.55 0.57 0.59 0.60
1 H:T 1 ，s 4.87 -- 4.27 -- 3.76 -- 3.35 3.17
1 H and 19 t of F 1 The values show an opposite trend with respect to temperature, meaning that the cations form a "solid" type fixed framework, whereas the FSI anions can move in a "liquid" type manner. The tetra-cationic ion plastic crystals of this example were compared with plastic crystals 1 and 30. The transition from "solid phase" to "liquid phase" is observed at a temperature of 17 ℃ for the anions of plastic crystal 1 and 40 ℃ for the cations of plastic crystal 1. The cations and anions of the plastic crystal 30 compact tightly over a temperature range of 20 ℃ to 60 ℃ with very limited movement. Finally, the results obtained for the tetra-cationic ion plastic crystal (plastic crystal 31) of this example show that in the temperature range of-10 ℃ to 60 ℃, the cations form a "solid" fixed framework, while the FSI anions can move in a "liquid" type manner.
Example 8 Plastic Crystal-based Positive electrode
(a) Preparation and characterization of Plastic Crystal based Positive electrode films (electrodes 1 to 4)
Plastic crystal-based anodes with different formulations and processing conditions were prepared and characterized. The electrochemically active material is lithium nickel manganese cobalt oxide (NMC). The different positive electrode compositions are presented in table 14.
TABLE 14 Positive electrode film composition based on Plastic Crystal
Scanning Electron Microscopy (SEM) images of electrode 1 were obtained using a TESCAN LYRA focused ion beam field emission scanning electron microscope (FIB-FESEM). Fig. 27 shows an SEM image obtained for the electrode 1, which shows the porosity and pore size distribution of the electrode. The cyan color in the right plot represents the aperture of the electrode and corresponds to the majority of the darker areas in the left plot.
It should be noted that the positive electrode performance may be limited by the porosity, since the pores of the plastic crystal-based positive electrode may act as a resistance to lithium ion transport. It should also be noted that the ratio of active material to catholyte based on plastic crystals must be rather large to ensure a porosity of the positive electrode below 5% and thus obtain very high positive electrode performance.
The different positive electrode film compositions are presented in table 15.
TABLE 15 Positive electrode composition based on Plastic Crystal
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(b) Preparation and characterization of a Plastic Crystal-based Positive electrode film (electrode 5)
A positive electrode based on plastic crystals is obtained by a method as described above, more particularly as shown in fig. 1 or fig. 2.
CBS was prepared by adding 0.252 g PVDF, 0.010 g PVP, and 5.836 g NMP to a container. The vessel and its contents were placed in a roller mill for more than 10 hours until dissolved. 10 g of 3mm grinding beads, 1.260 g Denka TM Carbon black and 0.42 grams of VGCF were added to the vessel. The mixture is then treated with SPEX TM The mixing mill was milled 4 times for 5 minutes to obtain CBS.
A diluted PCr catholyte solution was prepared by adding 1.934 grams of plastic crystals 24, 0.120 grams of LiFSI to 1.908 grams of NMP. The solution was then mixed using a vortex mixer.
By adding 1/4 of the diluted PCr catholyte solution to the CBSPost-use SPEX TM The mixture was ground for 5 minutes by a mixing mill to prepare a PCr-CBS solution. This step was performed three more times (i.e., until the diluted PCr catholyte solution was fully added and mixed with CBS).
A PCr-based positive electrode slurry was obtained by adding 7.685 grams of PCr-CBS solution and 5.130 grams of NCM 811 to the container. The mixture was then stirred with a vortex mixer for 5 min twice, then with a homogenizer (IKA TM T-10 Basic) was stirred for 2 minutes three times.
The PCr-based positive electrode slurry thus obtained was then applied onto a carbon-coated aluminum current collector using a blade coating system with a fixed gap size of 150 μm.
The PCr-based positive electrode film was then dried in a vacuum oven at a temperature of 120 ℃ for more than 10 hours to remove any residual solvent.
The dried PCr-based positive electrode film was then roll pressed with a thickness reduction target of about 17%. The temperature setting of the roller press is adjusted so that the roller surface temperature is below the melting point of the plastic crystals 24.
The composition of the PCr-CBS solution and the PCr-based positive electrode are presented in tables 16 and 17, respectively.
TABLE 16 composition of PCr-CBS solution
TABLE 17 composition of PCr-based Positive electrode (electrode 5)
Fig. 28 shows a photograph of the surface of the plastic crystal-based positive electrode obtained by the conventional mixing method in (a), and shows a photograph of the surface of the plastic crystal-based positive electrode (electrode 5) obtained by the method of the present example in (B). It should be noted that these images present a direct environment embodied on the surface of the membrane, which is not part of the electrode membrane. As can be seen in fig. 28 (a), the surface of the plastic crystal-based positive electrode obtained by the conventional mixing method includes carbon agglomerates, which enclose one example thereof. This is attributable to the fact that carbon is easily agglomerated in highly polar solvents due to its hydrophobic surface properties. As can be seen in fig. 28 (B), the surface of the plastic crystal-based positive electrode obtained by the method of the present example appeared to be substantially clean and smooth, and was substantially or completely free of carbon agglomerates.
(c) Preparation and characterization of Plastic Crystal-based Positive electrode (electrode 6) and electrochemical cell (cell 12)
A plastic crystal-based cathode film having the composition given in table 18 was prepared using the mixing method described in example 8 (b).
TABLE 18 composition of PCr-based cathode film (electrode 6)
The plastic crystal-based positive electrode film (electrode 6) is then coated with a ceramic-polymer composite layer. A ceramic-polymer composite layer was applied on a plastic crystal-based positive electrode film (electrode 6) using a doctor blade system with a fixed gap of 65 μm. The composition of the ceramic-polymer composite layer and its preparation method are presented in table 19.
TABLE 19 composition and mixing conditions of ceramic-polymer composite layers
* The components of the ceramic-polymer composite layer are added in the order shown.
The electrochemical cell (cell 12) was assembled according to the configuration shown in table 20.
Table 20. Electrochemical cell configuration (cell 12)
Fig. 29 is a graph of the discharge capacity vs. cycle number obtained in 40 charge and discharge cycles of the battery 12. The discharge capacities of the first 25 cycles were recorded at a temperature of 35 ℃, the discharge capacities of cycles 26 to 39 were recorded at a temperature of 50 ℃, and the discharge capacity of the 40 th cycle was recorded at a temperature of 25 ℃.
Example 9-Cyclic Charge Discharge (CCD) measurement
CCD measurements were obtained to test the properties and cycle life of the plastic crystal compositions shown in Table 21.
Table 21. Battery configuration (batteries 13 to 16)
Fig. 30 is a graph of the current density and the potential vs. time of the battery 13 described in the present embodiment. The battery 7 is cycled between 3.5V and 5.0V in 0.1V increments at a temperature of 50 ℃.
Fig. 31 is a graph of the current density and the potential vs. time of the battery 14 described in the present embodiment. The cell 14 was cycled between-0.10V and 0.10V at 1C at a current density of 3mA/cm2 and a temperature of 25 ℃. The current density is indicated by the dashed line.
Fig. 32 is a graph of current density and potential vs. time of the batteries 15 and 16 described in the present embodiment. Batteries 15 and 16 cycled between-0.15V and 0.15V at 1C at a current density of 3mA/cm2 and a temperature of 35 ℃. The current density is indicated by the dashed line.
EXAMPLE 10 NMR diffusion Studies of Polymer electrolytes
NMR diffusion studies of polymer electrolyte lifetime were performed on the plastic crystal compositions shown in table 22.
TABLE 22 Synthesis of Plastic crystals 32 and 33
For a pair of 1 H、 7 Li and Li 19 F nuclei were subjected to pulsed field gradient NMR diffusion measurement experiments.
Using a high power NMR diffusion probe equipped with Diff50 7 Li- 19 F and F 1 H- 19 500MHz WB Bruker AVANCE NEO of F Dual resonance Radio Frequency (RF) Module TM NMR spectroscopy NMR experiments were performed.
Diffusion measurements were performed at a temperature of 50 ℃. Gradient pulses range from 0.6ms to 2.0ms and diffusion times range from 40ms to 400ms, depending on the core. Gradient strength varied from 100G/cm to 2500G/cm in 16 increments.
The diffusion measurement is accompanied by T 2 Relaxation experiments using a Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence with an echo delay between 0.06ms and 0.6 ms. Up to 64 echoes were recorded per experiment.
The signal intensity in NMR experiments decays exponentially after the excitation pulse:
wherein, the liquid crystal display device comprises a liquid crystal display device,
I 0 is the signal intensity immediately after excitation, T 2 Is a characteristic time representing the interaction between adjacent cores. When the average internuclear interactions are present, the length T 2 The value corresponds to a movable core. Conversely, short T 2 The value corresponds to a static kernel.
Relaxation times represent information about the local environment of the observed nuclei, so they can act as tools for NMR signal assignment and deconvolution even when their chemical shifts overlap. For example, arbi, K. Et al report LATP 7 Lateral and longitudinal relaxation times of Li NMR signals (Arbi, K. Et al, chemistry of materials 16.2.16.2 (2004): 255-262). They correspond to the times observed for the LATP in this example and enable separation of lithium in the LATP (and its diffusion coefficient) from lithium in the polymer.
The results of plastic crystals 32 and 33 are presented in tables 23 and 24, respectively.
TABLE 23 NMR diffusion studies on Plastic Crystal 32 acquisition
It can be noted that the fastest protons in plastic crystals 32 are assigned to NH. The other protons may separate into two phases (i.e. "mobile phase" and "stationary phase") with a relative ratio of 2:8.
The obtained values of the lithium diffusion coefficient in LATP are in a similar range as those in LAGP reported previously by Hayamizu, K. Et al (Hayamizu, K. Et al Physical Chemistry Chemical Physics 19.34.34 (2017): 23483-23491).
TABLE 24 NMR diffusion studies on Plastic Crystal 33 obtained
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7 Li、 19 F and F 1 The diffusion coefficient of H is shown in tables 23 and 24. Two particle types with different diffusivities were identified for each core: li in LATP and Li associated with a Plastic Crystal-LiTFSI mixture + The method comprises the steps of carrying out a first treatment on the surface of the FSI and TFSI anions; main part of plastic crystal (CH 2 ) And mobile protons (NH) that can participate in hydrogen bonding.
FIG. 33 shows the logarithm of the diffusion coefficient (D), vs.1/k B Arrhenius plot of T, which shows CH 2 (. Sub.m.), NH (X), FSI (. Sub.solid.), TFSI (. Sub.t.), LATP (delta.) and Li + (■) temperature dependence of diffusion rate.
As can be seen in fig. 33, the Arrhenius curve corresponding to Li in LATP is linear over the entire temperature range with a diffusion activation energy of 0.26±0.02eV.
In contrast, the Arrhenius curve of ions associated with the plastic crystal-LiTFSI mixture is linear at temperatures above about 25 ℃. Li (Li) + 、TFSI - 、FSI - And the activation energy of NHIn the range of about 0.34eV to about 0.41eV, and the activation energy of the plastic crystal-LiTFSI mixture is about 0.50eV. At temperatures below 25 ℃, all diffusivities drop rapidly, which may be due to phase transformation of the plastic crystals.
Many modifications to any of the embodiments described above may be made without departing from the scope of the invention as contemplated. References, patent or scientific literature referred to herein is incorporated by reference in its entirety for all purposes.

Claims (190)

1. An ion plastic crystal comprising at least one delocalized anion paired with at least one cation derived from a guanidine, amidine, or phosphazene organic superbase.
2. The ionic plastic crystal according to claim 1, wherein the ionic plastic crystal is a polycationic ionic plastic crystal comprising at least two delocalized anions paired with at least two cations derived from guanidine, amidine or phosphazene organic superbase.
3. An ionic plastic crystal according to claim 1 or 2, wherein the delocalised anion is selected from the group consisting of trifluoromethylsulfonate (or trifluoromethylsulfonate) [ TfO ]-, bis (trifluoromethanesulfonyl) imide [ TFSI] - Bis (fluorosulfonyl) imide [ FSI ]] - 2-trifluoromethyl-4, 5-dicyanoimidazo [ TDI ]] - Hexafluorophosphate [ PF ] 6 ] - And tetrafluoroborate [ BF ] 4 ] - An anion.
4. An ionic plastic crystal according to claim 3, wherein the delocalised anion is [ TFSI ]] - 。
5. An 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 super-base is selected from 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-dimethylperfhydro-1, 3, 2-diazaphosphol (BEMP), tert-butylimino-tris (pyrrolidino) phosphane (BTPP), and tert-butylimino-tris (dimethylamino) phosphane (P) 1 -t-Bu)。
7. The ionic plastic crystal according to any one of claims 1 to 6, wherein the cation is selected from cations derived from guanidine, amidine or phosphazene organic superbases of formulae 2 to 8:
wherein, the liquid crystal display device comprises a liquid crystal display device,
the ion plastic crystal is a single cation ion plastic crystal, and R 1 Is a hydrogen atom or is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-acrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates and carbonyloxy-C 1 -C 10 Linear or branched substituents of alkyl-acrylates; or (b)
The ion plastic crystal is a polycationic ion plastic crystal, and R 1 Is an optionally substituted organic bridging group separating at least two cations and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
8. The ionic plastic crystal according to claim 7, wherein R 1 Is a hydrogen atom, and the ion plastic crystal is a proton ion plastic crystal.
9. The ionic plastic crystal according to claim 7, wherein R 1 Is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates and carbonylamino-C 1 -C 10 A linear or branched substituent of an alkyl-acrylate, and the ionic plastic crystal is a cross-linked ionic plastic crystal.
10. An ion plastic crystal according to any one of claims 7 to 9, wherein the ion plastic crystal is selected from ion plastic crystals of formulae 10 to 16:
Wherein, the liquid crystal display device comprises a liquid crystal display device,
X - is selected from [ TfO ]] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Is a delocalized anion of (a); and
the ion plastic crystal is a single cation ion plastic crystal, and R 1 Is a hydrogen atom or is selected from C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates, carbonylamino-C 1 -C 10 Alkyl-acrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates and carbonyloxy-C 1 -C 10 Alkyl-propenesLinear or branched substituents of the acid esters; or (b)
The ion plastic crystal is a polycationic ion plastic crystal, and R 1 Is an optionally substituted organic bridging group separating at least two cations and is selected from linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
11. An ionic plastic crystal according to claim 10, wherein the delocalized anion is selected from [ TFSI ]] - And [ FSI ]] - An anion.
12. An ionic plastic crystal according to claim 11, wherein the delocalized anion is [ FSI ]] - 。
13. An ion plastic crystal composition comprising at least one ion 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, plasticizers, and combinations of at least two thereof.
15. An ionic plastic crystal composition according to claim 14, wherein the inorganic particles comprise a compound having a garnet, NASICON, LISICON, thio-LISICON, LIPON, perovskite, inverse perovskite or suchlike type structure, or a compound comprising M-P-S, M-P-S-O, M-P-S-X, M-P-S-O-X type (wherein M is an alkali metal or alkaline earth metal and X is F, cl, br, I or a combination of at least two thereof), being a crystalline phase, an amorphous phase and/or a glass ceramic phase, or a mixture of at least two thereof.
16. An ionic plastic crystalline composition according to claim 15, wherein the inorganic particles comprise 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 Al a Ti 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 For example 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 For example 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 For example 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 For example 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 )；
MZISO (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 X d For example 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 e )；
-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 e )；
MZIPSOX (e.g. M a Zn b P c S d O e X f )；
-M 3 OX；
-M 2 HOX；
-M 3 PO 4 ；
-M 3 PS 4 The method comprises the steps of carrying out a first treatment on the surface of the And
-M a PO b N c (wherein a=2b+3c-5);
a crystalline phase, an amorphous phase, a glass ceramic phase, or a combination thereof;
wherein, the liquid crystal display device comprises a liquid crystal display device,
m is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and wherein when M comprises an alkaline earth metal ion, the amount of M is adjusted to achieve electroneutrality;
x is selected from F, cl, br, I or a combination thereof;
a. b, c, d, e and f are non-0 values and are independently selected among the formulae to achieve electroneutrality; and
v, w, x, y and z are non-0 values and are independently selected in the formulae to obtain stable compounds.
17. An ionic plastic crystalline composition according to claim 16, wherein the inorganic particles are ceramic or glass-ceramic.
18. An ionic plastic crystalline composition according to claim 17, wherein the ceramic or glass-ceramic is an oxide-type ceramic, a sulfide-type ceramic, an oxysulfide-type ceramic or a combination of at least two thereof.
19. An ionic plastic crystal composition according to claim 18, wherein the sulfide ceramic is selected from Li 10 GeP 2 S 12 、Li 6 PS 5 Cl、Li 2 S–P 2 S 5 、Li 7 P 3 S 11 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li 9.6 P 3 S 12 And Li (lithium) 3.25 P 0.95 S 4 。
20. The ionic plastic crystal composition according to claim 19, wherein the sulfide ceramic is Li 6 PS 5 Cl。
21. An ion plastic crystal composition according to any one of claims 17 to 20, wherein the ceramic or glass-ceramic is present in the ion plastic crystal composition at a concentration of at least 50% by weight.
22. An ion plastic crystal composition according to claim 21, wherein the ceramic or glass-ceramic is present in the ion plastic crystal composition at a concentration of about 50 wt.% to about 95 wt.%, or about 55 wt.% to about 95 wt.%, or about 60 wt.% and about 95 wt.%, or about 65 wt.% to about 95 wt.%, or about 70 wt.% to about 95 wt.%, or about 75 wt.% to about 95 wt.%, or about 80 wt.% to about 95 wt.%, or about 85 wt.% to about 95 wt.%, or about 90 wt.% to about 95 wt.%, inclusive.
23. An ion plastic crystal composition according to claim 22, wherein the ceramic or glass-ceramic is present in the ion plastic crystal composition at a concentration of about 90% by weight.
24. An ion plastic crystal composition according to claim 23, wherein the plastic crystals are present in the ion plastic crystal composition at a concentration of about 10% by weight.
25. An ionic plastic crystal composition according to claim 14, wherein the inorganic particles are selected from titanium dioxide (TiO 2 ) Alumina (Al) 2 O 3 ) And silicon dioxide (SiO) 2 ) Filler additives for particles or nanoparticles.
26. An ionic plastic crystalline composition according to any one of claims 13 to 25, wherein the polymer is linear or branched.
27. An ionic plastic crystalline composition according to any one of claims 13 to 26, wherein the polymer is cross-linked.
28. An ionic plastic crystal composition according to any one of claims 13 to 27, wherein the polymer is present in the ionic plastic crystal composition at a concentration of at least 10% by weight.
29. An ion plastic crystal composition according to any one of claims 13 to 27, wherein the polymer is present in the ion plastic crystal composition at a concentration of about 5 wt% to about 45 wt%, or about 10 wt% to about 45 wt%, or about 15 wt% to about 45 wt%, or about 20 wt% to about 45 wt%, or about 25 wt% to about 45 wt%, or about 30 wt% to about 45 wt%, or about 35 wt% to about 45 wt%, or about 40 wt% to about 45 wt%, inclusive.
30. An ionic plastic crystalline composition according to any one of claims 13 to 29, wherein the polymer is a polyether polymer.
31. An ionic plastic crystalline composition according to claim 30, wherein the polyether polymer is a polyethylene oxide (PEO) based polymer.
32. An ionic plastic crystalline composition according to any one of claims 13 to 31, wherein the polymer is a block copolymer consisting of at least one lithium ion solvating segment and optionally at least one crosslinkable segment, the lithium ion solvating segment being selected from homo-or copolymers having repeating units of formula 32:
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 3 selected from hydrogen atoms, C 1 -C 10 Alkyl or- (CH) 2 -O-R 4 R 5 ) A group;
R 4 is (CH) 2 -CH 2 -O) m ；
R 5 Selected from hydrogen atoms and C 1 -C 10 An alkyl group;
y is an integer selected from 10 to 200,000; and
m is an integer selected from 0 to 10.
33. An ionic plastic crystalline composition according to claim 32, wherein the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group which is multi-dimensionally crosslinkable by irradiation or heat treatment.
34. An ionic plastic crystal composition according to any one of claims 13 to 33, wherein the ionic plastic crystal composition is an electrolyte composition based on ionic plastic crystals.
35. An adhesive comprising an ion plastic crystal composition as defined in any one of claims 13 to 33.
36. An electrochemical cell comprising an ion plastic crystal composition as defined in any one of claims 13 to 34.
37. A supercapacitor comprising an ionic plastic crystalline composition as defined in any one of claims 13 to 34.
38. The supercapacitor according to claim 37, wherein the supercapacitor is a carbon-carbon supercapacitor.
39. An electrochromic material comprising an ionic plastic crystalline composition as defined in any one of claims 13 to 33.
40. A solid electrolyte composition comprising an ionic plastic crystal as defined in any one of claims 1 to 12 or an ionic plastic crystal composition as defined in any one of claims 13 to 33 and at least one salt or at least one additional component.
41. The solid electrolyte composition of claim 40 wherein said salt is an ionic salt.
42. The solid electrolyte composition of claim 41 wherein said ionic salt is selected from the group consisting of lithium, sodium, potassium, calcium and magnesium salts.
43. The solid electrolyte composition of claim 42 wherein said ionic salt is a lithium salt.
44. The solid electrolyte composition according to claim 43, wherein said lithium salt is selected from the group consisting of sixLithium fluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiLiFeSI), (fluorosulfonyl) (trifluoromethanesulfonyl) imide) lithium (Li (FSI) (TFSI)), lithium 2-trifluoromethyl-4, 5-dicyanoimidazole (LiTDI), lithium 4, 5-dicyano-1, 2, 3-triazole (LiDCTA), lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), lithium difluorophosphate (LiDFP), 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 triflate (LiSO) 3 CF 3 ) (LiOTf), lithium fluoroalkyl phosphate Li [ PF ] 3 (CF 2 CF 3 ) 3 ]Lithium tetrakis (trifluoroacetoxy) borate Li [ B (OCOCF) 3 ) 4 ]Lithium (LiTFAB), bis (1, 2-benzenediol (2-) -O, O') borate Li [ B (C) 6 O 2 ) 2 ](LiBBB), lithium difluoro (oxalate) borate (LiBF 2 (C 2 O 4 ) (LiFeB), liBF 2 O 4 R x (wherein R is x ＝C 2-4 Alkyl) and combinations of at least two thereof.
45. The solid electrolyte composition of any of claims 40 to 44 wherein the additional component is selected from the group consisting of ion conductive materials, inorganic particles, glass particles, ceramic particles, plasticizers, other similar components, and combinations of at least two thereof.
46. The solid electrolyte composition of claim 45 wherein said ceramic particles are nanoceramics.
47. The solid electrolyte composition of claim 45 or 46 wherein said additional component is selected from the group consisting of NASICON, LISICON, thio-LISICON-type compounds, garnet, in crystalline and/or amorphous form, and combinations of at least two thereof.
48. A solid electrolyte comprising a solid electrolyte composition as defined in any one of claims 40 to 47, wherein the solid electrolyte is optionally crosslinked.
49. A solid electrolyte comprising an ionic plastic crystal as defined in any one of claims 1 to 12, wherein the solid electrolyte is optionally crosslinked.
50. An electrode material comprising an electrochemically active material and an ion plastic crystal composition as defined in any one of claims 13 to 33, wherein the ion plastic crystal composition is optionally crosslinked.
51. An electrode material comprising an electrochemically active material and an ion plastic crystal as defined in any one of claims 1 to 12, wherein the ion plastic crystal is optionally crosslinked.
52. The electrode material of claim 50, wherein said ion plastic crystal composition is a binder.
53. The electrode material according to claim 51, wherein the ion plastic crystal is a binder.
54. An electrode material according to any one of claims 50 to 53, wherein the electrochemically active material is in the form of particles.
55. An electrode material according to any one of claims 50 to 54, wherein the electrochemically active material 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 (e.g., metal fluorides), lithium metal halides (e.g., lithium metal fluorides), sulfur, selenium, and combinations of at least two thereof.
56. The electrode material according to claim 55, wherein the metal of the electrochemically active material is selected from the group consisting of titanium (Ti), iron (Fe), magnesium (Mg), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), and combinations of at least two thereof.
57. An electrode material according to any one of claims 50 to 56, wherein the electrode material further comprises at least one electronically conductive material.
58. The electrode material of claim 57, wherein the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and combinations of at least two thereof.
59. The electrode material according to claim 58, wherein the electronically conductive material is acetylene black.
60. An electrode material according to any one of claims 50 to 59, wherein the electrode material has an ion-plastic crystal ratio of electrochemically active material of less than about 6, or less than about 5, or less than about 4, or less than about 3, preferably less than about 4.
61. The electrode material according to any one of claims 50 to 60, wherein the electrode material has a porosity of less than about 8%, or less than about 7%, or less than about 6%, or less than about 5%, or less than about 4%, or less than about 3%, or less than about 2%, or less than about 1%, preferably less than about 5%.
62. An electrode comprising an electrode material as defined in any one of claims 50 to 61 on a current collector.
63. 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 any one of claims 1 to 12, wherein the ionic plastic crystal is optionally crosslinked.
64. 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 an ionic plastic crystal composition as defined in any one of claims 13 to 33, wherein the ionic plastic crystal composition is optionally crosslinked.
65. 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 62.
66. An electrochemical cell comprising a negative electrode, a positive electrode and a solid electrolyte as defined in claim 48 or 49.
67. An electrochemical accumulator comprising at least one electrochemical cell as defined in any one of claims 63 to 66.
68. The electrochemical energy accumulator of claim 67, wherein said electrochemical energy accumulator is a battery selected from the group consisting of a lithium battery, a lithium ion battery, a sodium ion battery, a magnesium battery, and a magnesium ion battery.
69. The electrochemical accumulator of claim 68, wherein the battery is a lithium battery or a lithium ion battery.
70. A process for preparing an ion plastic crystal as defined in any one of claims 1 to 12 or an ion plastic crystal composition as defined in any one of claims 13 to 33, the process comprising the steps of:
(i) Reacting at least one guanidine, amidine, or phosphazene organic superbase with at least one proton source to form at least one complex comprising a protonated guanidine, amidine, or phosphazene organic superbase-derived cation and a counter ion; and
(ii) A complex comprising a protonated guanidine, amidine, or phosphazene organic superbase derived cation and a counterion is reacted with at least one ionic salt.
71. The method according to claim 70, wherein the guanidine, amidine, or phosphazene organic super base is selected from the group consisting of DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu。
72. The method of claim 71, wherein the guanidine, amidine, or phosphazene organic super base is BEMP.
73. The method of claim 71, wherein the guanidine, amidine, or phosphazene organic super base is DBU.
74. A method according to any one of claims 70 to 73, wherein said ionic salt comprises a salt selected from [ TfO] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Delocalized anions of anions.
75. The method according to claim 74, wherein the delocalized anion is [ TFSI ]] - 。
76. The method according to claim 74, wherein the delocalized anion is [ FSI ]] - 。
77. The method of any one of claims 70 to 77, wherein the ionic salt is an alkali metal or alkaline earth metal salt.
78. The method of claim 77, wherein said alkali metal or alkaline earth metal salt is a lithium, sodium, potassium, calcium, or magnesium salt.
79. The method according to claim 78, wherein the alkali or alkaline earth metal salt is a lithium salt.
80. The method according to any one of claims 70 to 79, wherein steps (i) and (ii) are carried out sequentially, simultaneously or partially overlapping each other in time.
81. The method according to claim 80, wherein steps (i) and (ii) are performed sequentially and the step of reacting the guanidine, amidine, or phosphazene organic superbase with a proton source is performed prior to the step of reacting a complex comprising a protonated guanidine, amidine, or phosphazene organic superbase derived cation and a counter ion with an ionic salt.
82. The method according to any one of claims 70 to 81, wherein guanidine, amidine or phosphazene organic superbase, proton source and ionic salt are mixed together and reacted.
83. The method according to any one of claims 70 to 82, wherein steps (i) and (ii) are performed in the presence of a solvent.
84. The method according to claim 83, wherein the solvent is selected from the group consisting of methylene chloride, dimethyl carbonate, acetonitrile, ethanol, and miscible combinations of at least two thereof.
85. The method according to claim 84, wherein the solvent is acetonitrile.
86. The method according to any one of claims 83 to 85, wherein the solvent is the proton source of step (i).
87. The method according to any one of claims 70 to 86, wherein the proton source of step (i) is a first proton source and steps (i) and (ii) are performed in the presence of a second proton source.
88. The method according to claim 87, wherein the second proton source is an acid selected from the group consisting of carboxylic acids (e.g., formic acid, acetic acid, propionic acid, lactic acid, and trifluoroacetic acid), p-toluenesulfonic acid, sulfuric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, nitric acid, and hydrofluoric acid.
89. The process according to any one of claims 70 to 88, wherein steps (i) and (ii) are carried out in the presence of an activator and/or stabilizer, and the process further comprises forming a stabilized intermediate ion neutral complex.
90. The method of claim 89, wherein the activator and/or stabilizer is a bis-silylated compound of formula 17:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z is a substituted or unsubstituted organic group selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, linear or branched polyether, linear or branched polycarbonate, linear or branched polythiocarbonate, linear or branched polyamide, linear or branched polyimide, linear or branched polyurethane, linear or branched polysiloxane, linear or branched thioether, linear or branched polyphosphazene, linear or branched polyester, and linear or branched polythioester; and
R 2 independently and at each occurrence is selected from alkyl, aryl, and arylalkyl.
91. The method of claim 90, wherein the method further comprises the step of preparing a bis-silylated compound of formula 17.
92. The method of claim 91, wherein the step of preparing the bis-silylated compound of formula 17 is performed by silylation reaction of a compound comprising at least two hydroxyl groups with a silylating agent.
93. The method of claim 92, wherein the compound comprising at least two hydroxyl groups is selected from the group consisting of glycerol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-propanediol, 1, 2-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 2-ethyl-1, 3-hexanediol, p-menthyl-3, 8-diol, 2-methyl-2, 4-pentanediol, polycaprolactone diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentylene glycol, polyethylene glycol, 2,3, 4, 5-octafluoro-1, 6-hexanediol, and combinations of at least two thereof.
94. The method of claim 93 wherein the bis-silylated compound of formula 17 is bis-silylated diethylene glycol.
95. The method of claim 93 wherein the bis-silylated compound of formula 17 is bis-silylated glycerol.
96. The process according to any of claims 92 to 95, wherein the silylation reaction is carried out by a base-catalyzed silylation reaction and involves the use of (R 2 ) 3 The Si-group replaces the acidic or active hydrogen on the hydroxyl group.
97. The process according to any of claims 92 to 96, wherein the silylation reaction is carried out in the presence of a base.
98. A process according to claim 97, wherein said base is 4-dimethylaminopyridine.
99. A method according to claim 97, wherein said base is imidazole.
100. The process according to any of claims 92 to 99, wherein the silylation reaction is carried out in the presence of an aprotic solvent.
101. The method according to claim 100, wherein the aprotic solvent is dichloromethane.
102. The method according to claim 100, wherein the aprotic solvent is tetrahydrofuran.
103. The process according to any of claims 92-102, wherein the silylating agent is selected from the group consisting of trialkylsilyl chloride, trimethylsilyl chloride (TMS-Cl), triethylsilyl chloride (TES-Cl), isopropyldimethylsilyl chloride (ipms-Cl), diethylisopropylsilyl chloride (deeps-Cl), tert-butyldimethylsilyl chloride (TBDMS-Cl or TBS-Cl), tert-butyldiphenylsilyl chloride (TBDPS-Cl or TPS-Cl) and triisopropylsilyl chloride (TIPS-Cl), nitrogen-containing silyl ethers, N, O-bis (tert-butyldimethylsilyl) acetamide (BSA), N-methyl-N- (trimethylsilyl) trifluoroacetamide (MSTFA), N- (trimethylsilyl) dimethylamine (TMS-dea), N- (trimethylsilyl) imidazole (TMSI or TSIM), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) and N-methyl-N- (trimethylsilyl) acetamide (MSA).
104. The method of claim 103, wherein the silylating agent is trimethylsilyl chloride (TMS-Cl).
105. The method of claim 103, wherein the silylating agent is t-butyldimethylsilyl chloride (TBDMS-Cl or TBS-Cl).
106. The method of any one of claims 92 to 105, wherein the silylating agent is added at a molar ratio of "OH groups to be derivatized: silyl" of about 1:0.9.
107. The process according to any one of claims 92 to 105, wherein the silylating agent is added in a "to-be-derivatized-OH-group-to-silyl" molar ratio of about 1:1.
108. The method of any of claims 92 to 105, wherein the silylating agent is added in excess relative to the number of hydroxyl groups on the compound comprising at least two hydroxyl groups.
109. The method of any of claims 92 to 105 wherein the amount of silylating agent is in the range of about 2 equivalents to about 5 equivalents, including upper and lower limits, per equivalent of compound comprising at least two hydroxyl groups.
110. The method of claim 109, wherein the amount of silylating agent is in the range of about 2 equivalents to about 4.5 equivalents, or about 2 equivalents to about 4 equivalents, or about 2 equivalents to about 3.75 equivalents, or about 2 equivalents to about 3.5 equivalents, including upper and lower limits, per unit of compound comprising at least two hydroxyl groups.
111. The method according to any one of claims 92 to 110, wherein the silylation reaction is carried out at room temperature.
112. The method according to any one of claims 70 to 111, wherein steps (i) and (ii) are carried out at a temperature of about 20 ℃ to about 200 ℃, including an upper limit and a lower limit.
113. The method of claim 112, wherein steps (i) and (ii) are performed at a temperature of from about 40 ℃ to about 80 ℃, or from about 45 ℃ to about 75 ℃, or from about 50 ℃ to about 70 ℃, or from about 55 ℃ to about 65 ℃, including upper and lower limits.
114. A method according to any one of claims 70 to 113, wherein steps (i) and (ii) are carried out for at least 4 days.
115. The method according to any one of claims 70 to 114, wherein the method further comprises a purification step.
116. The method of claim 115, wherein the purifying step is performed by extraction, distillation, or evaporation.
117. The method according to any one of claims 70 to 116, wherein the method further comprises a functionalization step.
118. The method according to claim 117, wherein the functionalizing step is performed by a reaction between a protonated guanidine, amidine, or phosphazene organo-super-base derived cation-NH functional group and at least one crosslinkable functional group precursor.
119. The method according to claim 118, wherein said crosslinkable functional group is selected from the group consisting of C 1 -C 10 Alkyl-acrylate, C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-methacrylates, carbonyloxy-C 1 -C 10 Alkyl-acrylates, carbonylamino-C 1 -C 10 Alkyl-methacrylates and carbonylamino-C 1 -C 10 Alkyl-acrylate groups.
120. A method as set forth in any one of claims 70 to 119 wherein the method further comprises the step of coating the substrate with the ion plastic crystal composition or a suspension comprising ion plastic crystals.
121. The method according to claim 120, wherein said coating step is performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method.
122. The method of claim 121, wherein the coating step is performed by at least one of a knife coating process or a slot die coating process.
123. The method according to any one of claims 120 to 122, wherein the method further comprises drying the composition or suspension.
124. The method of claim 123, wherein the drying and coating steps are performed simultaneously.
125. A method according to any one of claims 70 to 124, wherein the method further comprises a cross-linking step.
126. The method of claim 125, wherein the step of crosslinking is performed by ultraviolet radiation, by heat treatment, by microwave radiation, under an electron beam, by gamma irradiation, or by X-ray irradiation.
127. The method of claim 126, wherein the step of crosslinking is performed by ultraviolet radiation, heat treatment, or under an electron beam.
128. The method of any of claims 125 to 127, wherein the crosslinking step is performed in the presence of a crosslinking agent, a thermal initiator, a photoinitiator, a catalyst, a plasticizer, or a combination of at least two thereof.
129. The method of claim 128, wherein the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone (Irgacure) TM 651)。
130. A stabilized intermediate ion neutral complex obtained by reacting at least one cation derived from a guanidine, amidine or phosphazene organic superbase and at least one bis-silylated compound of formula 17:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z is a substituted or unsubstituted organic group selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, linear or branched polyether, linear or branched polycarbonate, linear or branched polythiocarbonate, linear or branched polyamide, linear or branched polyimide, linear or branched polyurethane, linear or branched polysiloxane, linear or branched thioether, linear or branched polyphosphazene, linear or branched polyester, and linear or branched polythioester; and
R 2 Independently and at each occurrence is selected from alkyl, aryl, and arylalkyl.
131. The stabilized intermediate ion neutral complex according to claim 130, wherein the cation derived from guanidine, amidine, or phosphazene organic superbase is selected from protonated 1, 8-diazabicyclo [5.4.0 ]]Undec-7-ene [ H-DBU ]] + Protonated 1, 5-diazabicyclo [4.3.0]Non-5-ene [ H-DBN] + Protonated 7-methyl-1, 5, 7-triazabicyclo [4.4.0]Dec-5-ene [ H-MTBD] + Protonated 2-t-butylimino-2-diethylamino-1, 3-dimethylperfhydro-1, 3, 2-diazaphospho-English [ H-BEMP] + Protonated t-butylimino-tris (pyrrolidine) phosphane [ H-BTPP] + And protonated t-butylimino-tris (dimethylamino) phosphane [ P 1 -t-Bu] + 。
132. The stabilized intermediate ion neutral complex according to claim 130 or 131, wherein the stabilized intermediate ion neutral complex has formulae 25 to 31:
wherein, the liquid crystal display device comprises a liquid crystal display device,
z and R 2 As defined in claim 130; and
X - is selected from [ TfO ]] - 、[TFSI] - 、[FSI] - 、[TDI] - 、[PF 6 ] - And [ BF ] 4 ] - Is a delocalized anion of (a).
133. A process for preparing an ion plastic crystal as defined in any one of claims 1 to 12 or an ion plastic crystal composition as defined in any one of claims 13 to 33, the process comprising the steps of:
(i) Reacting a guanidine, amidine, or phosphazene organic superbase with an organic bridging compound to form a polycationic complex comprising at least two organic superbase-based cationic moieties separated by an optionally substituted organic bridging group and paired with a counter ion; and
(ii) Reacting the polycationic complex with at least one ionic salt.
134. The method according to claim 133, wherein said guanidine, amidine, or phosphazene organic super base is selected from DBU, DBN, MTBD, BEMP, BTPP and P 1 -t-Bu。
135. The method of claim 134, wherein the guanidine, amidine, or phosphazene organic super base is BEMP.
136. The method of claim 134, wherein the guanidine, amidine, or phosphazene organic super base is DBU.
137. The method according to any one of claims 133 to 136, wherein the organic bridging compound comprises an optionally substituted organic bridging group and at least two anionic leaving groups.
138. The method according to claim 137, wherein the anionic leaving group is a halide.
139. The method according to claim 138, wherein said halide ion is selected from the group consisting of F - 、Cl - 、Br - And I - 。
140. The method of claim 138, wherein the halide is Br - 。
141. The method according to any one of claims 133 to 140, wherein said optionally substituted organic bridging group is selected from the group consisting of linear or branched C 1 -C 10 Alkylene, straight-chain or branched C 1 -C 10 Alkyloxy C 1 -C 10 Alkylene, straight or branched poly (C) 1 -C 10 Alkyleneoxy) C 1 -C 10 Alkylene, straight-chain or branched polyether, straight-chain or branched polyester, C 6 -C 12 Arylene group, C 5 -C 12 Heteroarylene, C 3 -C 12 Cycloalkylene and C 3 -C 12 Heterocycloalkylene group.
142. The method according to any one of claims 133-141, wherein the organic bridging group is 1,2,4, 5-tetrakis (bromomethyl) benzene.
143. A method as in any of claims 133-142, wherein the ionic salt comprises a compound selected from [ TfO] - 、[TFSI] - 、[FSI]-、[TDI]-、[PF 6 ] - And [ BF ] 4 ] - Is a delocalized anion of (a).
144. The method according to claim 143, wherein said delocalized anion is [ TFSI] - 。
145. The method according to claim 143, wherein said delocalized anion is [ FSI] - 。
146. The method according to any one of claims 133 to 145, wherein the ionic salt is an alkali metal or alkaline earth metal salt.
147. The method of claim 146, wherein the alkali metal or alkaline earth metal salt is a lithium, sodium, potassium, calcium, or magnesium salt.
148. The method of claim 147, wherein the alkali metal or alkaline earth metal salt is a lithium salt.
149. A method according to any of claims 133 to 148, wherein steps (i) and (ii) are carried out sequentially, simultaneously or partially overlapping each other in time.
150. The method of claim 149, wherein steps (i) and (ii) are performed sequentially and the step of reacting the guanidine, amidine, or phosphazene organic superbase with the organic bridging compound is performed prior to the step of reacting the polycationic complex with the ionic salt.
151. The method according to any one of claims 133 to 150, wherein the guanidine, amidine or phosphazene organic superbase, the organic bridging compound and the ionic salt are mixed together and reacted.
152. The process according to any of claims 133-151, wherein steps (i) and (ii) are carried out in the presence of a solvent.
153. The method of claim 152, wherein the solvent is selected from the group consisting of methylene chloride, dimethyl carbonate, acetonitrile, ethanol, and miscible combinations of at least two thereof.
154. The method of claim 153, wherein the solvent is dichloromethane.
155. The method according to any one of claims 133 to 154, wherein the step of reacting the guanidine, amidine, or phosphazene organic superbase with the organic bridging compound is performed in the presence of a base.
156. A process according to claim 155, wherein the base is triethylamine (Et 3 N)。
157. A process according to any one of claims 133 to 156, wherein steps (i) and (ii) are carried out at room temperature.
158. The method according to any one of claims 133 to 157, wherein the step of reacting the guanidine, amidine, or phosphazene organic superbase with the organic bridging compound is performed for about 4 days.
159. The method according to any one of claims 133 to 158, wherein the step of reacting the polycationic complex with the ionic salt is performed for about 3 days.
160. The method according to any one of claims 133-159, wherein the method further comprises a purification step.
161. The method of claim 160, wherein the purifying step is performed by extraction, distillation, or evaporation.
162. A method as in any of claims 133-161 wherein the method further comprises the step of coating the ion plastic crystal composition or suspension comprising ion plastic crystals on the substrate.
163. The method according to claim 162, wherein said coating step is performed by at least one of a knife coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method.
164. The method of claim 163, wherein the coating step is performed by at least one of a knife coating method or a slot die coating method.
165. The method of any one of claims 162 to 164, wherein the method further comprises drying the composition or suspension.
166. The method according to claim 165, wherein said drying and coating steps are performed simultaneously.
167. A method of producing an electrode material as defined in any one of claims 50 to 61, the method comprising the steps of:
(i) Preparing a carbon and binder slurry;
(ii) Preparing a catholyte solution based on ionic plastic crystals; and
(iii) Ion plastic crystals, carbon and binder slurries were prepared.
168. The method of claim 167, wherein the step of preparing the carbon and binder slurry comprises dispersing the carbon in a binder composition.
169. The method of claim 168, further comprising preparing an adhesive composition.
170. The method of claim 168 or 169, wherein the carbon comprises carbon black.
171. The method of any of claims 168 to 170, wherein the carbon comprises vapor grown carbon fiber.
172. The method according to any one of claims 168 to 171, wherein the adhesive composition comprises an adhesive and optionally a solvent and/or a carbon dispersant.
173. The method of claim 172, wherein said binder comprises a fluoropolymer.
174. The method of claim 173 wherein the fluoropolymer is polytetrafluoroethylene, polyvinylidene fluoride, or poly (vinylidene fluoride-co-hexafluoropropylene).
175. The method of claim 174 wherein the fluoropolymer is polyvinylidene fluoride.
176. A process as set forth in any of claims 172 to 175 wherein said solvent is N-methyl-2-pyrrolidone.
177. The method of any of claims 172 to 176 wherein the carbon dispersant is polyvinylpyrrolidone.
178. The method of any one of claims 169 to 177, wherein the step of preparing the adhesive composition is performed by mixing the adhesive with a solvent and/or a carbon dispersant.
179. The method of claim 178, wherein the step of mixing is performed by a rolling process.
180. The method as recited in any one of claims 167 to 179, wherein the step of preparing the ion plastic crystal catholyte solution comprises diluting the ion plastic crystal and the ion salt in a solvent.
181. The method according to claim 180, wherein the solvent is N-methyl-2-pyrrolidone.
182. A method as set forth in any one of claims 167 to 181 wherein the step of preparing the ion plastic crystal, the carbon, and the binder slurry comprises gradually adding the ion plastic crystal catholyte solution to the carbon and binder slurry.
183. The method of any of claims 167 to 182, wherein the method further comprises adding an electrochemically active material to the ion plastic crystal, the carbon, and the binder slurry.
184. The method according to claim 183, wherein the electrochemically active material is lithium nickel manganese cobalt oxide (NMC).
185. The method of any of claims 167 to 184, wherein the method further comprises coating the ion plastic crystal, carbon, and binder slurry on a current collector to obtain the ion plastic crystal, carbon, and binder electrode film on the current collector.
186. The method according to claim 185, wherein said coating step is performed by at least one of a blade coating method, a comma coating method, a reverse-comma coating method, a printing method such as a gravure coating method or a slot die coating method.
187. The method of claim 186, wherein the coating step is performed by a knife coating process.
188. The method of any one of claims 184 to 187, wherein the method further comprises drying the ion plastic crystal, binder, and carbon electrode film.
189. The method of any of claims 184-188, wherein the method further comprises calendaring the ion plastic crystal, binder, and carbon electrode film.
190. A method as in claim 189, wherein the calendaring step is performed by a roll process.
CN202280013197.5A 2021-02-05 2022-02-04 Ionic plastic crystals, compositions comprising the same, methods of manufacture and uses thereof Pending CN116806221A (en)

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