Electrolytes for target ion transport

Abstract

The present invention provides zwitterionic plastic crystal (ZIPC) compounds in the form of a single molecule comprising at least one positively charged functional group having at least one positive charge and at least one negatively charged functional group having at least one negative charge, wherein the positively charged functional group and the negatively charged functional group are covalently linked to each other within the molecule, the net charge of the zwitterionic compound is zero, and the compound exhibits evidence of molecular disorder in the solid state.

Description

[Technical Field]

[0001] The present invention relates to a flexible crystalline compound having excellent target ion conduction ability, and can be used, for example, as an electrolyte in various applications where high-speed target ion conduction is desired. [Background technology]

[0002] A viscous crystal is a solid that has a long-range ordered crystalline structure along with short-range disorder resulting from the rotation or disorientation of individual molecules / ions within an ordered lattice. Short-range molecular rearrangement gives rise to the ability to deform under load (i.e., plasticity) and enhances the diffusivity of a second species within the viscous crystal lattice. Viscous crystalline electrolytes are primary / target ions (e.g., Li for lithium batteries). + , or for dye-sensitized solar cells, I - / I3 - It can be classified as a fast ion conductor in which ions move rapidly against a relatively static matrix background.

[0003] In recent years, the applicability of organic ionic flexible crystals (OIPCs) as novel solid-state ion conductors in lithium batteries, dye-sensitized solar cells, fuel cells, and sodium batteries has been demonstrated. This is achieved by doping OIPCs with appropriate cations, for example, by adding Li salts for their application in lithium batteries, or acids or bases for fuel cells. Furthermore, aprotic OIPCs offer good thermal and electrochemical stability and, due to their negligible volatility, significantly improve safety compared to current molecular solvent-based electrolytes. OIPCs can be structurally disordered salts, exhibiting flexible and plastic mechanical properties and significant ionic conductivity. The structural disorder within OIPCs promotes fast target ion conduction when OIPCs are used as a matrix and a second component (e.g., acid / base for fuel cells or Li or Na salt for Li / Na batteries) is introduced into the OIPC matrix, enabling their use as solid electrolytes in electrochemical devices. However, their inherent structures (i.e., separated cations and anions) are thought to allow undesirable movement of matrix OIPC ions. In an ideal electrolyte material, only target ions (e.g., Li, Na, H) would move.

[0004] However, target ion transport via OIPC is still insufficient and ultimately limits the achievable power output of the instrument. In fact, a low transport rate (the proportion of charge possessed by the active species), for example, t for OIPC, is insufficient. Li+ This is generally less than 0.2. This is because there are other charged transport species, including the cations and anions of OIPC and the counterions of lithium salts. The ideal transport number (t Li+ For =1), only Li ions need to move through the electrolyte at a very high speed. [Overview of the prefecture] [Problems the invention aims to solve]

[0005] While zwitterionic liquids and even zwitterionic liquid crystals are known, in rare cases, zwitterionic liquid crystals in combination with LiNTf2 and propylene carbonate can be used as liquid electrolytes, but leakage from the apparatus and the vapor pressure and flammability of this combination pose problems.

[0006] In the field of electrochemistry, organic ionic zwitterions utilize sulfonate structures because they can be synthesized relatively easily in one step via combinations of sulfones and methylpyrrolidines. However, these sulfonic acid zwitterions are crystalline solids that do not show evidence of plasticity and lack the flexible mechanical properties required for battery cells, making them unsuitable as standalone electrolyte matrix materials. 。

[0007] Ohno et al. (Phys. Chem. Chem. Phys. 2018, 20, 10978) describe an alkyl-substituted imidazolium zwitterion with a solid-solid transition at 165°C, lower than its own Tm. However, in addition to the low entropy of the molten material, there is no evidence that this zwitterion exhibits plastic behavior, and the viscous zwitterion needs to show evidence of disorder, preferably determined by NMR studies. 。

[0009] [Means for solving the problem] [Overview of the project]

[0010] This disclosure It exhibits plasticity as evidenced by molecular disorder in the solid state, as defined in claim 1, and can be used as a solid electrolyte. kill We provide organic zwitterionic compounds.

[0011] First reference In one embodiment, the present invention relates to a zwitterionic viscous crystal (ZIPC) compound in the form of a nonpolymer molecule, At least one positively charged functional group having at least one positive charge, At least one negatively charged functional group having at least one negative charge, Includes, The positively charged functional group and the negatively charged functional group are covalently linked to each other within the molecule, the net charge of the zwitterionic compound is zero, the compound exhibits molecular disorder in the solid state, and the compound is as follows: Thermal phase behavior including one or more solid-solid phase transitions before melting, In the aforementioned solid state, an NMR linewidth of 1 or more with a frequency of 20 kHz or less, The present invention provides a zwitterionic viscous crystal (ZIPC) compound exhibiting two or more of the following: a microstructure or morphology including slip planes and reflection planes observable by SEM analysis. Preferably, the NMR linewidth is 10 kHz or less, more preferably 5 kHz or less, and in some embodiments, 1 kHz or less.

[0014] The 1 In this embodiment, the present invention has the following structure Selected from , Zwitterionic flexible crystals Provides compounds. [ka]

[0015] The 2 In this embodiment, the present invention provides a solid-state solvent, the first 1 The invention provides the use of compounds in a particular manner.

[0016] The 3 In this embodiment, the present invention provides an electrolyte matrix, preferably a solid-state electrolyte matrix, as the first 1 The invention provides the use of compounds in a particular manner.

[0017] The 4 In this embodiment, the present invention provides a conductivity-enhancing additive for electrolytes, the first 1 The invention provides the use of a compound according to the embodiment, preferably the electrolyte being a polymer-based electrolyte or an ionic liquid-based electrolyte.

[0020] The 5 In this aspect, the present invention is the 1 The present invention provides a zwitterionic viscous crystal composition in liquid form, comprising a zwitterionic viscous crystal (ZIPC) compound according to the embodiment, and an ionic salt, acid, base, Li or Na functionalized polymer, or a combination thereof.

[0021] The 6 In this aspect, the present invention is the 1 The present invention provides a zwitterionic viscous crystal composition in solid form, comprising a zwitterionic viscous crystal (ZIPC) compound according to the embodiment, and an ionic salt, acid, base, Li or Na functionalized polymer, or a combination thereof.

[0022] The 2 of reference In some embodiments, the present invention relates to applications requiring ion conduction, such as electrochemical devices, preferably electrochemical batteries equipped with energy storage devices such as fuel cells, supercapacitors, dye-sensitized solar cells, or Na batteries or Li batteries, and the first 1 The present invention provides the use of a zwitterionic viscous crystal (ZIPC) compound according to the embodiment or a zwitterionic viscous crystal (ZIPC) composition according to the fifth or sixth embodiment.

[0025] The 7 In this aspect, the present invention is the 1 The present invention provides a solid-state electrolyte containing a zwitterionic viscous crystal (ZIPC) compound according to the embodiment.

[0026] The 8 In this aspect, the present invention is the 5 or the 6 The present invention provides a solid-state electrolyte comprising a solid-state composition in the manner of the present invention.

[0027] The 9 In one aspect, the present invention provides an energy storage device comprising an electrolyte containing a zwitterionic viscous crystal (ZIPC) matrix that is optionally doped with an ionic salt, an acid, a base, a Li or Na functionalized polymer, or a combination thereof. Place provide.

[0028] The 10In this aspect, the present invention is the 9 Energy storage device relating to the above Place The energy storage devices provided are sodium batteries or lithium batteries.

[0029] The 3 of reference In one embodiment, the present invention provides a fuel cell device comprising an electrolyte containing a zwitterionic viscous crystal (ZIPC) matrix that is optionally doped with an ionic salt, an acid, a base, a Li or Na functionalized polymer, or a combination thereof.

[0030] No prior art references herein to any patent document or any other matter should be construed as an acknowledgment that the document or other matter was well known or that the information contained herein was part of common knowledge at the priority date of any of the claims. Where the terms “comprise,” “comprises,” “comprises,” or “comprises,” or any or all thereof, are used in this specification (including in the claims), they shall be construed to identify the presence of a described feature, complete, step, or component, but not to preclude the presence of one or more other features, complete, step, or component. Embodiments of the present invention are described herein by reference only as examples. [Brief explanation of the drawing]

[0031] [Figure 1A] This figure shows the structures of numerous novel zwitterionic viscous crystals (ZIPCs) in comparison to numerous similar established OIPCs. Compounds 1, 2, 5, and 6 are novel compounds synthesized at the request of Boron Molecular. Novel compounds 3 and 4 were synthesized at Deakin University. Compounds 7, 8, and 9 are commercially available but have not been previously described as viscous crystals. [Figure 1B] This figure shows the thermal analysis information for pure ZIPC1, ZIPC2, ZIPC5, and ZIPC6. [Figure 1C] This figure shows the cations and anions for the combinations that form ZIPC. [Figure 2A] Figure 2A shows differential scanning calorimetry (DSC) heating traces of (a) ZIPC1 doped with 10 mol% LiFSI and (b) pure [C2mpyr][BF4]OIPC doped with 10 mol% LiFSI. The heating / cooling rate is ±10 K / min. [Figure 2B]This figure shows the DSC heating trace of ZIPC1 and an electrolyte mixture of 90 mol% LiFSI in ZIPC1. [Figure 3A] Figure 3A shows (a) SEM images and microstructure of pure ZIPC1 (slip steps, grain boundaries) (as a pellet) and (b) ZIPC1 with 10 mol% LiFSI. [Figure 3B] The image shows an SEM image of an electrolyte mixture containing 90 mol% LiFSI in ZIPC1. [Figure 3C] The image shows an SEM image of ZIPC6 (the pellet was prepared and the image was taken at room temperature). [Figure 3D] This shows a SEM image of the NaF surface. [Figure 3E] This image shows an SEM image of pure ZIPC5 pressed into a pellet at room temperature. [Figure 4A(a)] Figures 4A(a) to (c) show the ionic conductivity of pure ZIPC1 and [C2mpyr][BF4]OIPC and mixtures thereof with LiFSI as a function of temperature, with Figure 4A(a) showing the ionic conductivity of 10 mol% LiFSI in ZIPC1 and OIPC. [Figure 4A(b)] Figures 4A(a) to (c) show the ionic conductivity of pure ZIPC1 and [C2mpyr][BF4]OIPC and mixtures thereof with LiFSI as a function of temperature, and Figure 4A(b) shows their linewidth versus temperature. [Figure 4A(c)] Figures 4A(a) to (c) show the ionic conductivity of pure ZIPC1 and [C2mpyr][BF4]OIPC and mixtures thereof with LiFSI as a function of temperature, and Figure 4A(c) shows the ionic conductivity of pure ZIPC, OIPC and mixtures thereof with 10 mol% LiFSI. [Figure 4B] This figure shows the ionic conductivity as a function of temperature for an electrolyte mixture of pure ZIPC1 and ZIPC1 containing 90 mol% LiFSI. [Figure 5A(a)]Figure (a) on the left shows the variable temperature-static 7Li spectrum of OIPC doped with 10 mol% LiFSI, and Figure (b) on the right shows the variable temperature-static 7Li spectrum of ZIPC1 doped with 10 mol% LiFSI. [Figure 5A(b)] This figure shows a comparison of the linewidths of 7Li in ZIPC1 doped with 10 mol% LiFSI as a function of temperature. [Figure 5B(a)] Figure (a) on the left shows the variable temperature-static 7Li spectrum of a 90 mol% LiFSI and ZIPC1 electrolyte mixture, and Figure (b) on the right shows the VT-static 7Li spectrum of pure LiFSI. [Figure 5B(b)] This figure shows the VT-static 19F spectrum of a 90 mol% LiFSI and ZIPC1 electrolyte mixture. [Figure 5B(c)] The linewidths of 7Li (upper figure) and 19F (lower figure) in a 90 mol% LiFS and ZIPC1 electrolyte mixture are shown as a function of temperature. [Figure 5C] The figure on the left (a) shows the single-pulse spectrum of pure ZIPC5 at 1H. The figure on the right (b) shows the single-pulse spectrum of pure ZIPC5 at 19F versus temperature. [Figure 5D(a)] This figure shows the ionic conductivity of 10 mol% LiFSI in ZIPC5. [Figure 5D(b)] This figure shows the DSC trace of 10 mol% LiFSI in ZIPC5. [Figure 5D(c)] This figure shows an SEM image of 10 mol% LiFSI in ZIPC5. [Figure 6A] This figure shows the VT-static 19F spectra of ZIPC1 doped with 10 mol% LiFSI and OIPC doped with 10 mol% LiFSI at 20°C (left figure) and 60°C (right figure). [Figure 6B] This figure shows the line width of BF4 in OIPC and BF3 in ZIPC1 at 19F. [Figure 6C]This figure shows the linewidth of FSI as a function of temperature at 19F for ZIPC1 doped with 10 mol% LiFSI and OIPC doped with 10 mol% LiFSI. [Figure 6D] This figure shows the 19F spectrum of a single pulse for ZIPC1 as a function of temperature. [Figure 6E] For crystalline solids, the linewidth is very broad, exceeding 100 ppm. The upper figure shows the NMR linewidth of ZIPC1 for 19F as a function of temperature, while the lower figure shows the area fraction of the narrow peak of ZIPC1 at 19F as a function of temperature, obtained by inverse superposition integration of the static NMR spectrum of 19F. The blue dashed lines (vertically drawn dashed lines) separate different thermal phases as measured by DSC. [Figure 7A] This shows a comparison of the diffusion coefficients of 7Li, 19F, and 1H in 10 mol% LiFSI-doped ZIPC1 and 10 mol% LiFSI-doped OIPC at different temperatures, as measured by PFG-NMR. The red plots (appearing lower on the vertical axis) represent OIPC, and the black plots (appearing higher on the vertical axis) represent ZIPC1. [Figure 7B] This figure shows the diffusion coefficients of 7Li (black: top figure) and 19F (red: bottom figure) in a 90 mol% LiFSI and ZIPC1 electrolyte mixture at different temperatures, as measured by PFG-NMR. [Figure 8] This figure shows a cyclic voltammogram of ZIPC1 doped with 10 mol% LiFSI at 0.05 mVS-1 at 50°C. [Figure 9A] This figure shows the chronoamperometry of a ZIPC1 electrolyte Li battery doped with Li|10 mol% LiFSI at 50°C in a 10 mV potential step. [Figure 9B] This figure shows the chronoamperometry of a Li|ZIPC1 electrolyte mixture of 90 mol% LiFSI at 50°C with a potential step of 10 mV. [Figure 10A(a)]Figures 10A(a) to (c) show the Li|Li symmetric battery cycling of 10 mol% LiFSI in ZIPC1 at 50°C with a polarization time of 1 hour (10 cycles at each current density) at different current densities. [Figure 10A(b)] Figures 10A(a) to (c) show the Li|Li symmetric battery cycling of 10 mol% LiFSI in ZIPC1 at 50°C with a polarization time of 1 hour (10 cycles at each current density) at different current densities. [Figure 10A(c)] Figures 10A(a) to (c) show Li|Li symmetric battery cycling at 50°C with 10 mol% LiFSI in ZIPC1 at different current densities and a polarization time of 1 hour (10 cycles at each current density). [Figure 10B] This figure shows the symmetrical battery cycling performance of a 10 mol% LiFSI and ZIPC1 electrolyte mixture at 0.1 mA / cm2 and 50°C. [Figure 11] This figure shows the cycling performance of 10 mol% LiFSI|Li in (lithium iron phosphate) LFP|ZIPC1 at 50°C in the range of 2.8 to 3.8 V. [Figure 12] This figure shows the DSC trace of ZIPC7, which has three peaks during the heating cycle (T1=92°C, ΔH=26J / g, T2=106°C, ΔH=10J / g, T3=119°C, ΔHf=25J / g) (melting point of imidazole = 89°C), and the effect of imidazole doping at different concentrations. [Figure 13] This figure shows the conductivity of pure protic ZIPC7 and samples doped with different amounts of imidazole base. The conductivity of each sample was measured three times. [Figure 14] This figure shows the conductivity results for protic ZIPC7 doped with trifluic acid. [Figure 15]Figure 15 shows the conductivity and symmetric lithium battery performance of 50 mol% liquid LiFSI in ZIPC1 electrolyte, a) ionic conductivity and viscosity (inset - DSC trace of liquid electrolyte), b) voltage profile of Li│Li symmetric battery at 50°C with a polarization time of 1 hour at 0.2 mAcm⁻² per step, and c) Li│Li symmetric battery cycling at different current densities at 50°C with a polarization time of 1 hour per step. [Figure 16A] This figure shows the DSC traces of pure ZIPC1 and its mixtures with 10 mol% and 90 mol% LiBF4. [Figure 16B] b) is an SEM image of 10 mol% (liquid-like phase and grains) of LiBF4 in ZIPC1, and c) is an SEM image of 90 mol% (grain boundaries). [Figure 16C] Figures d) and e) show the static NMR spectra of 10 mol% and 90 mol% LiBF4 in ZIPC1, respectively, paired with temperature, using a 7Li single pulse. [Figure 16D] Figures f) and g) show the static NMR spectra of 10 mol% and 90 mol% LiBF4 in ZIPC1, respectively, paired with temperature, measured at 19F single pulse. [Figure 17A] This figure shows the ionic conductivity of pure ZIPC1 and its mixtures with 10 mol% and 90 mol% LiBF4. [Figure 17B] This figure shows the diffusion coefficients of 7Li and 19F for 10 mol% and 90 mol% LiBF4 in ZIPC1 at different temperatures. [Figure 18A] This figure shows a cyclic voltammogram of 10 mol% LiBF4 in ZIPC1 at 50°C, acquired at a scanning speed of 0.05 mVs-1 using a stainless steel working electrode versus a Li metal reference electrode. [Figure 18B] This figure shows a cyclic voltammogram of 90 mol% LiBF4 in ZIPC1 at 50°C, acquired at a scanning speed of 0.05 mVs-1 using a stainless steel working electrode versus a Li metal reference electrode. [Modes for carrying out the invention]

[0032] The inventors unexpectedly discovered that covalently linking specific cations and anions, preferably by OIPC, can form zwitterionic viscous crystal (ZIPC) compounds. Such ion linking reduces / eliminates net matrix ion movement observed for OIPC in an electric field. Ionic linking increases the transport of target ions through ZIPC, for example, through a ZIPC electrolyte matrix doped with a source of target ions. Viscous zwitterions address the problem of low target ion transportability observed in existing solid-state electrolyte matrices (e.g., OIPC electrolyte matrices resulting from the translational movement of OIPC matrix ions). The solution involves eliminating undesirable movement of matrix OIPC ions by using a ZIPC matrix in which positive and negative charges are linked together in net neutral molecules that do not move in an electric field, while allowing for high target ion conductivity due to the unexpected plasticity of ZIPC (resulting from the remarkable retention of overall disorder in ZIPC) when the ZIPC electrolyte matrix is ​​doped with a salt of the target ions. Since coupling was expected to reduce the opportunities for rotational and translational disorder, it was unexpected that coupling charges at the monomolecule level provided these advantages. It was also unexpected that compounds with specific ions coupled would exhibit plasticity, and that the ZIPCs of the present invention would exhibit sufficient disorder to enable better target ion transport in solid-state matrices. Since coupling ions is expected to reduce the number of possible disordered motions (rotational and translational), such ion coupling is usually expected to produce regular crystalline compounds; therefore, no prior studies have suggested that coupling ions in organic ionic viscous crystals forms viscous zwitterions, thereby teaching away from the zwitterionic viscous crystalline compounds of the present invention. Furthermore, such matrices are expected to lack usefulness in terms of assisting the dissociation of target ions from salts supplied to the electrolyte matrix. In the art, it is not suggested that the described zwitterions demonstrate better target ion transport rates than the corresponding OIPCs.

[0033] The ZIPC of the present invention simultaneously suppresses counterion transport, which was an important issue with OIPC, while presenting improved solid-state conductivity and transport of target ions (e.g., Li + , Na + , H + ). This is demonstrated by a high transport number, e.g., 0.7 for 90 mol% LiFSI in the ZIPC1 solid electrolyte mixture (t Li+ ). The typical transport number of Li salts in OIPC is less than 0.2. ZIPC is particularly suitable for use in batteries having a metal anode, such as a lithium or sodium metal anode.

[0034] Furthermore, protonic and aprotic ZIPC provide an improvement in proton conductivity over protonic and aprotic OIPC.

[0035] ZIPC is proposed as a new class of materials as (i) a solid-state electrolyte matrix material doped with a material containing a salt for a battery, particularly Li + or Na<​​​​​​​​​​​​​​​​or Na + ) provides other (charge-diffusing) negatively charged sites that interact with Li by salt + This can be achieved by competing with the interaction between it and its counterion, thereby increasing ionic dissociation.

[0037] In the field of polymer-based solid-state electrolytes, ZIPC as an additive improves the dissociation of charge carrier ions due to the polymer backbone (or the presence of other ionic species).

[0038] Using ZIPC in similar OIPC applications may offer the advantage of higher conductivity for specific target ions.

[0039] Furthermore, the ZIPC of the present invention, particularly the zwitterionic-BF3 - Those with the same structure are equivalent to the BF4 - It may be less susceptible to hydrolysis than seeds. Therefore, in battery applications, while electrolytes are generally used in an inert atmosphere, using ZIPC compounds in devices with electrochemical batteries may offer advantageous long-term device / battery stability due to their lower tendency to hydrolyze. This can be particularly important in relation to fuel cells.

[0040] The inventors extended this concept to protonated zwitterions (which have mobile protons) and demonstrated that protonated ZIPCs enable good proton conduction.

[0041] Preferably, the preferred ZIPC is non-volatile. Preferably, the preferred compound is neither flammable nor explosive, at least under the normal operating conditions of the fuel cell or energy storage device.

[0042] Preferably, ZIPC compounds exhibit long-range ordered crystalline structures along with short-range disorder resulting from molecular rotation or disorientation within the ordered lattice. With respect to ZIPC, solid-solid phase transitions are understood to be associated with the initiation of rotational motion of all or part of the ZIPC molecules. A combination of spectroscopic and modeling approaches provides a powerful pathway for further elucidating the interrelationships between chemistry, structure, and phase behavior in ZIPC and can act as predictors of plasticity behavior in zwitterions, as described herein.

[0043] The molecular disorder (and consequent plasticity) associated with ZIPC can be observed, for example, from unique features in at least two of the following studies: thermal studies, solid-state NMR studies, and SEM studies. In particular, one or more of these unique features may increase with increasing temperature.

[0044] One distinctive feature may include thermal phase behavior involving one or more solid-solid phase transitions (pre-melting or partially melted solid-solid phase transitions) before melting. Techniques for measuring and characterizing the solid-solid phase transition of ZIPC include differential scanning calorimetry, in which the solid-solid phase transition is characterized by a DSC plot in which a discontinuity in the heat flow (e.g., spikes) is observed in the partial melting temperature range, separate from the discontinuity caused by the solid-liquid (melting) transition of ZIPC.

[0045] Other unique features of molecular disorder in the solid state are determined from static solid-state NMR of the viscous ZIPC, which exhibits an NMR linewidth of 1 or more below 20 kHz. Preferably, the linewidth narrows further with increasing temperature. Preferably, the NMR linewidth is 10 kHz or less, preferably 5 kHz or less, and in some embodiments, 1 kHz or less.

[0046] Other unique features of molecular disorder in the solid state are determined by observation of the microstructure / morphology using SEM analysis. These unique features include observation of multiple grains with different orientations, observation of slip and projection planes in SEM analysis, sets of slip planes within different grains, and observation of grain boundaries by fracture surfaces of the material. Further evidence of plasticity increases with increasing temperature.

[0047] Other unique features include approximately 60JK -1 mol -1 Less than, more preferably about 50 JK -1 mol -1 Less than, more preferably about 40 JK -1 mol -1 Less than, more preferably about 30 JK -1 mol -1 Less than, more preferably about 20JK -1 mol -1 Entropy ΔS of melting f This may include demonstrating...

[0048] Other useful research methods include molecular modeling such as X-ray diffraction, Raman spectroscopy, synchrotron X-ray diffraction, and molecular dynamics (MD), or combinations thereof.

[0049] Suitable ZIPC compounds become plastic solids at applicable operating temperatures, e.g., approximately -100°C to approximately 200°C, approximately -50°C to approximately 100°C, and most preferably approximately -10°C to approximately 80°C. Particularly suitable compounds become plastic solids at least at room temperature. "Room temperature" means a temperature of approximately 20°C to approximately 25°C, preferably 25°C. Suitable ZIPC compounds have melting points of 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 150°C or higher, 200°C or higher, or 250°C or higher. Suitable compounds exhibit plastic behavior at temperatures of approximately -100°C to approximately 100°C. The melting point defines the upper limit of the normal operating temperature of the apparatus using ZIPC. "Melting point" means the extrapolated onset temperature related to the phase transition in melting from solid to liquid, as determined by differential scanning calorimetry (DCS). When a compound exhibits plasticity at very low temperatures, such as below 0°C, it generally indicates that the compound is also highly disordered at room temperature.

[0050] When used as an electrolyte, the flexible crystal is thought to provide an environment in which added target ions can move, for example, through vacancies, grain boundaries, and / or the formation of additional liquids or liquid amorphous phases. Indeed, SEM analysis of numerous electrolyte materials containing lithium salts shows that crystalline and intergranular regions contain mobile lithium-rich electrolytes, providing pathways for lithium ions that support lithium electrochemical activity and instrument cycling. Therefore, the solid material of the present invention, composed of ZIPC and doped salts, is thought to contain, for example, one or more of a salt-rich liquid, liquid phase, or amorphous phase. Thus, the material contains one or more phases. The target ion-rich liquid, target ion-rich liquid phase, or target ion-rich amorphous phase is thought to provide pathways for target ion diffusion and facilitate target ion transport through the electrolyte.

[0051] When some of the positively charged functional groups include alkyl chains, the melting temperature and the Phase II-Phase I transition temperature may decrease by 1 or more as the alkyl chain length increases.

[0052] ZIPCs can be classified into protic and aprotic types depending on the availability of dissociable protons in the cationic and / or anionic components of the zwitterionic molecule. Therefore, a suitable cation can be either a protic or aprotic cation, depending on the availability of unstable protons. Similarly, a suitable anion can be either a protic or aprotic anion, depending on the availability of unstable protons.

[0053] ZIPC formation ZIPC can be provided by covalently linking at least one cation and at least one anion starting from these. The provided combination of cations and anions to be linked together (i) yields a zwitterionic compound with a net neutral charge, and (ii) becomes a viscous crystal exhibiting molecular disorder (and consequently plasticity), which is observable, for example, from two or more distinctive features in thermal studies, solid-state NMR studies, and SEM studies, and the types of cations and associated counteranions that can be employed are not particularly limited.

[0054] In a suitable ZIPC compound, at least one of the positively charged functional groups of ZIPC originates from a small cationic component, such as a optionally substituted saturated or unsaturated heterocycle, e.g., pyrrolidine, morpholinium, piperidinium, thiolane, benzotriazole, or tetrahydrofuran. Preferably, at least one of the negatively charged functional groups of a suitable ZIPC originates from a charge-delocalized anionic group, such as a fluoroborate, oxalatoborate, sulfonylimide, fluorosulfonylimide (FSI), or bis(trifluoromethanesulfonyl)imide (TFSA). "Originating from" means that each cation or anion forms the basis of the corresponding functional group, which is covalently bonded to each other directly or via at least one atom or intermediate functional group, which can be, for example, a carbon bond, a hydrocarbon chain, or actually an additional functional group, ring, or chain. As a result of the interconnection of functional groups in the ZIPC molecule, it is understood that the corresponding functional groups derived from the cation and anion do not readily dissociate from each other, especially under the influence of an electric field.

[0055] Linking cationic components Some suitable cations can be di-cations or tri-cations. Preferred cations are symmetrical. In some embodiments, the cations are chiral cations.

[0056] Suitable cation examples include pyrrolidinium, imidazolium, phosphonium, and metallocenium cations, which may be unsubstituted or C 1-6 Alkyl, preferably methyl, ethyl or propyl, and one or more functional groups selected from CN, OMe, OEt and CN may be substituted.

[0057] Preferably, one or more of the positively charged functional groups are C such that n=2, 3, 4, 6 and m=1, 2, 3, 4, 6. n (N 2,2,m )2, N 2,1,1,1 , N 2,2,1,1 , N 2,2,2,1 , N 2,3,3,3 , N 2,2,3,3 , N 2,2,2,3 , N 4,4,4,4 , P 1,2,2,2 , N 1,2,3,i3 , N 2,2,2,2 , N 3,3,3,3 A cation consisting of C2epyr can be selected, and a particularly aprotic cation can be selected. A cation capable of rotational motion (e.g., tetramethylammonium) is particularly desirable.

[0058] Preferably, at least one of the positively charged functional groups having at least one positive charge is derived from an ammonium cation, a phosphonium cation, or a sulfonium cation containing positively charged nitrogen, positively charged phosphorus, and positively charged sulfur, respectively.

[0059] Preferably, at least one positively charged functional group having at least one positive charge contains nitrogen and is derived from a positively charged ammonium cation. A suitable ammonium cation is one of the general formulas [NR 4 R 3 R2 R 1 ] + It may have at least one positively charged functional group having at least one positive charge, which contains sulfur and is derived from a positively charged sulfonium cation. A suitable sulfonium cation is of the general formula [SR 3 R 2 R 1 ] + It may have at least one positively charged functional group having at least one positive charge, which includes phosphorus and is derived from a positively charged phosphonium cation. A suitable phosphonium cation is of the general formula [PR 4 R 3 R 2 R 1 ] + It may have.

[0060] In any of the above cases, R 1 ~R 4 Each of them may be the same or different, and may be independently selected from optionally substituted alkyls and optionally substituted aryls, or if one R group is selected from optionally substituted alkyls and optionally substituted aryls, and the remaining two R groups form an optionally substituted heterocycle together with P, 1 The phosphate group is selected from H, optionally substituted alkyl groups, and optionally substituted aryl groups. A suitable example of a phosphonium cation is tetra(C) 1-20 Alkyl)phosphonium, tri(C 1-9 Alkyl) Mono(C 10-20 Alkyl)phosphonium, tetra(C 6-24 This includes aryl)phosphonium, phosphoranium, phosphinanium, and phosphorinanium.

[0061] Preferably, at least one of the positively charged functional groups having at least one positive charge is derived from a morpholinium cation, pyrrolidinium cation, or imidazolium, each containing a positively charged nitrogen. The pyrrolidinium cation or imidazolium ring may be unsubstituted, or R 1 and R2 It may be replaced with one or more of the following. In any case, R 1 and R 2 Each of them may be the same or different, and may be independently selected from optionally substituted alkyls and optionally substituted aryls, or if one R group is selected from optionally substituted alkyls and optionally substituted aryls, and the remaining two R groups form an optionally substituted heterocycle together with P, 1 This is selected from H, optionally substituted alkyl, and optionally substituted aryl.

[0062] Other suitable cations that can be linked with appropriate anions include dialkylpyrrolidinium, pyrrolidinium, monoalkylpyrrolidinium, dialkylimidazolium, monoalkylammonium, imidazolium, tetraalkylammonium, quaternary ammonium, trialkylammonium, dialkylammonium, dialkylammonium, dialkanolalkylammonium, alkanoldialkylammonium, bis(alkylimidazolium), bis(dialkyl)ammonium, bis(trialkyl)ammonium, diallylammonium, dialkanolammonium, and This includes ammonium hydroxyalkanol, alkylallylammonium, guanidinium, diazabicyclooctane, tetraalkylphosphonium, trialkylphosphonium, trialkylsulfonium, tertiary sulfolinium, imidazolinium, corinium, formamidinium, formadinium, bicyclic (spiro)ammonium, pyrazolium, benzimidazolium, dibenzylammonium, caffeine, piperadinium, dialkyl(amino)ammonium, alkyl(diamino)ammonium, triaminoammonium, aminopyrrolidium, and aminoimidazolium.

[0063] Other cations to be linked can be selected from the group of cations shown in Figure 1C.

[0064] In one embodiment, preferably, at least one of the positively charged functional groups having at least one positive charge is derived from a cation by an ionic liquid, or more preferably by OIPC. Preferably, at least one of the negatively charged functional groups having at least one negative charge is derived from an anion by an ionic liquid or OIPC. Preferably, the ZIPC of the present invention can be formed by linking at least one cation by an ionic liquid or OIPC and at least one anion by an ionic liquid or OIPC within the same molecule. A skilled synthetic chemist can devise a suitable synthetic method to form a compound in which the desired groups are linked together.

[0065] Examples of OIPC cations and anions that can be used as a starting point for designing the ZIPC compounds of the present invention can be found in Trends in Chemistry, April 2019, Vol. 1, No. 1, J. Mater. Chem. 2010, 20, 2056-2062 and Phys. Chem. Chem. Phys. 2013, 15, 1339 (particularly Figures 1, 2, 3 and Table 1), and the entire content describing the cations and anions and OIPC is incorporated herein by reference. A preferred example of a known OIPC is [N 1,1,1,1 ][DCA], [C2mpyr][FSI], [C2mpyr][BF4], [P 1,2,2,2 [FSI], [P 1,2,2,i4 [PF6], [P 1,4,4,4 ][FSI], [H2im][Tf], [Hmim][Tf], [N 2,2,3,3 ][BBu4], [N 3,3,3、3 Includes [BF4], [C2epyr][TFSI], [C2epyr][FSI], [C2epyr][PF6], [C2epyr][BF4], [C1mpyr][(FH)2F], [C2mpyr][(FH)2F], [C4mpyr][TFSI], [(NH2)3][Tf], [2-Me-im][Tf] and [TAZm][PFBS].

[0066] Linking anionic components Preferably, at least one of the negatively charged functional groups having at least one negative charge may be derived from anions known to be produced by OIPC. Some suitable anions may be protic or aprotic, depending on the availability of unstable protons. Some suitable anions may be di-anions or tri-anions. Some suitable anions may be symmetrical. Some suitable anions may be chiral.

[0067] Suitable anions that can be used for linking may possess a “spherical” structure in which the anion has a constitutive shape that exhibits spherical symmetry around its center by rotation around an axis. Further anions suitable for linking in the ZIPC electrolyte composition of the present invention may have a diffusive or mobile negative charge that, when linked in the ZIPC compound, can be present or averaged across the anionic structure.

[0068] Preferably, one or more of the negatively charged functional groups are Tf, 1 ≤ n ≤ 3 (FH). n Anions consisting of F and TFSI can be selected from the group of anions, and especially aprotic anions. Other suitable anions that form one or more negatively charged functional groups can be selected from the group of anions consisting of I, Br, PF6, TFSI, BBu4, CrO3Cl, CrO3Br, BF4, FTFSI, DCA, FSI, and Tf. Centrosymmetric anions (e.g., hexafluorophosphates and tetrafluoroborates) are particularly preferred.

[0069] Preferably, at least one negative charge (F - At least one negatively charged functional group having ) is BF4 - PF6 - N(CN)2, (CF3SO2)2N - , (FSO2)2N - OCN, SCN - Dicyanomethanide, carbamoylcyano(nitroso)methanide, (C2F5SO2)2N - , (CF3SO2)3C, C(CN)3 - , B(CN)4- , (C2F5)3PF3 - , alkyl-SO3 - , perfluoroalkyl-SO3 - , aryl-SO3 - , I - , H2PO4 - , HPO4 2- , sulfates, sulfites, nitrates, trifluoromethanesulfonate, p-toluenesulfonate, bis(oxalato)borate, acetates, formates, gallates, glycolates, BF3(CN) - , BF2(CN)2 - , BF(CN)3 - , where R is an alkyl group (e.g., methyl, ethyl, propyl) of BF3(R) - , BF2(R)2 - , BF(R)3 - , cyclic sulfonylamides, bis(salicylato)borate, perfluoroalkyl trifluoroborate, chlorides, bromides and transition metal complex anions (e.g., [Tb(hexafluoroacetylacetonate)4]) and other anions derived from. Preferably, the anion is a fluorinated anion, for example, BF4 - , PF6 - , (CF3SO2)2N - , (FSO2)2N - , BF3(CN) - , BF2(CN)2 - , BF(CN)3 - , where R is an alkyl group (e.g., methyl, ethyl, propyl, butyl) of BF3(R) - , BF2(R)2 - , BF(R)3 - , (C2F5SO2)2N - , (C2F5)PF3 - , (C2F5PO2)2N, (CF3SO2)NCN, (CF3SO2)N(SO2F), (CF3CO)N(SO2F) and perfluoroalkyl-SO3 - is selected from the group consisting of.

[0070] Other anions to be linked can be selected from the group consisting of the anions shown in Figure 1C.

[0071] OIPC similar entity Known examples of OIPCs that can form the ZIPC according to the present invention by supplying cations and anions that link together in the same molecule include both protic and aprotic types, such as N,N-methylethylpyrrolidinium tetrafluoroborate, N,N-methylpropylpyrrolidinium tetrafluoroborate, dimethylpyrrolidinium tetrafluoroborate, dimethylpyrrolidinium thiocyanate, N,N-ethylmethylpyrrolidinium thiocyanate, tetramethylammonium dicyanamide, tetraethylammonium dicyanamide, N,N-methylethylpyrrolidinium bis(trifluoromethanesulfonyl)amide, diethyl(methyl)(isobutyl)phosphonium bis(fluorosulfonyl)amide, diethyl(methyl)(isobutyl)phosphonium tetrafluoroborate, diethyl(methyl)(isobutyl)phosphonium hexafluorophosphate, methyl(triethyl)phosphonium bis(fluorosulfonyl)amide, methyl(triethyl)phosphonium bis(trifluoromethylsulfonyl)amide, and triisobutyl(methyl)phosphonium Muhexafluorophosphate, triisobutyl(methyl)phosphonium bis(fluorosulfonyl)amide, triisobutyl(methyl)phosphonium tetrafluoroborate, triisobutyl(methyl)phosphonium thiocyanate, triethyl(methyl)phosphonium bis(fluorosulfonyl)imide, methylethylpyrrolidium bis(fluorosulfonyl)amide, dimethylpyrrolidinium bis(fluorosulfonyl)amide, choline dihydrogen phosphate, choline trifluoromethanesulfonate, NN-dimethylpropylenediammonium triflate, tri(isobutyl)phosphonium bis(trifluoromethanesulfonyl)amide, tri(isobutyl)phosphonium methanesulfonate, tri(isobutyl)phosphonium trifluoromethanesulfonate, tri(isobutyl)ammonium bis(trifluoromethanesulfonyl)amide, tri(isobutyl)phosphonium nitrate, tri(isobutyl)ammonium methanesulfonate, tri(isobutyl)ammonium trifluoromethanesulfonate, tri(isobutyl)ammonium nitrate, 1,This includes 2-bis[N-(N'-hexylimidazolium)ethanebis(hexafluorophosphate)] and combinations thereof.

[0072] OptimZIP Particularly suitable zwitterionic viscous crystal (ZIPC) compounds have the structure shown herein. Preferably, one or more of R', R'' and R''' are independently H, methyl, ethyl, or propyl. Preferably, R 1 , R 2 and R 3 Each of these is independently selected from H, methyl, ethyl, or propyl or halogen. Preferably, Y is methyl, ethyl, or propyl. Preferably, L is methyl, ethyl, or propyl. Preferably, one or more of R', R'' and R''' are independently methyl, ethyl, or propyl, and R 1 , R 2 , R 3 Each of them is F, Y is methyl, and L is methyl. Suitable compounds are [ka] Includes.

[0073] Particularly suitable zwitterionic viscous crystal (ZIPC) compounds have one of the following common structures: [ka] One or more of R', R'', and R'''' are replaced by H, and C is optionally substituted. 1-6 Alkyl, optionally substituted fluoroC 1-6 Independently selected from alkyl or halo groups, or one of R' and R'', R'' and R''', or R' and R''' forms an optionally substituted 5-membered or 6-membered saturated or unsaturated heterocycle, R 1 , R 2 and R 3 Each of these is H, and C is optionally substituted. 1-6 Alkyl, optionally substituted fluoroC 1-6C is independently selected from alkyl or halo, and Y is optionally substituted. 1-6 It is an alkyl group, and L is optionally substituted with C. 1-6 It is an alkyl group, and Z and Z' are independently O, S, NH, N, and C. 1-4 It is an alkyl group, where each of X and X'' is independently O, S, NH, N, C, or CH, and where present, the ring is optionally substituted, and the optionally substituted substituent is C 1-6 Alkyl, preferably selected from methyl, ethyl or propyl, CN, OMe, OEt and CN, one or more. Preferably, R 1 H is methyl, ethyl, or propyl, and R 2 , R 3 , R 4 Each of these is independently selected from H, methyl, ethyl, or propyl, and halogen, where Y is methyl, ethyl, or propyl, L is methyl, ethyl, or propyl, Z is methyl or ethyl, and X is O, S, NH, or CH. Preferably, R 1 R is methyl, ethyl, or propyl, 2 , R 3 , R 4 Each of these is F, Y is methyl, L is methyl, Z is methyl or ethyl, and X is O, S, NH or CH.

[0074] Particularly suitable zwitterionic viscous crystal (ZIPC) compounds have one of the following common structures: [ka] R' is methyl, ethyl, or propyl, 1 , R 2 , R 3 Each of these is F, Y is methyl, and X is O, S, NH or CH.

[0075] A suitable ZIPC compound has one of the following structures: [ka] [ka] [ka]

[0076] The ZIPC of the present invention can be used as a solid-state solvent.

[0077] Electrolyte composition / mixture The description also includes compositions comprising a zwitterionic viscous crystal (ZIPC) compound according to the first embodiment, doped with one or more polymers commonly used in electrolytes, such as salts, acids, bases, or Li or Na functionalized polymers. Preferably, such compositions may be solid or liquid compositions at room temperature, i.e., depending on the amount of salt, the properties of the salt used, and the properties of the ZIPC used. At least when the ZIPC is used as a matrix material of the composition / electrolyte, a solid composition is preferred.

[0078] For use as a solid-state electrolyte (for example, in batteries or fuel cells), target ions (e.g., Li) + na + or H + The ions need to be incorporated into the ZIPC matrix to support the charging / discharging process. Doping the ZIPC matrix with even small amounts of ionic salts can significantly increase the ionic conductivity of target ions in the ZIPC matrix. One explanation is that incorporating ionic salts into ZIPC creates additional vacancies / defects, resulting in higher concentrations of diffusible ions and therefore higher conductivity. An alternative mechanism is that a liquid phase with a mixed (Li salt and ZIPC) composition exists at the grain boundaries, with the rest being mostly bulk ZIPC.

[0079] Preferably, the composition comprises ZIPC and at least one ionic salt, the salt present at a concentration of at least about 5 mol%. Preferably, the ionic salt is present at concentrations of at least about 5 mol%, at least about 10 mol%, at least about 15 mol%, at least about 20 mol%, at least about 25 mol%, at least about 30 mol%, at least about 35 mol%, at least about 40 mol%, at least about 45 mol%, at least about 50 mol%, at least about 55 mol%, at least about 60 mol%, at least about 65 mol%, at least about 70 mol%, at least about 75 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, and at least about 95 mol%.

[0080] Preferably, the ionic salt is one or more alkali metal, alkaline earth, or transition metal salts. Preferred ionic salts include Li, Na, K, Ca, Al, Mg, and Zn salts. Preferably, the anions for these salts include bis(trifluoromethanesulfonyl)imide, TFSI; bis(fluorosulfonyl)imide, FSI; fluorosulfonyl(trifluoromethanesulfonyl)imide, FTFSI; trifluoromethanesulfonate; tetrafluoroborate, BF4; perfluorobutanesulfonate, PFBS; hexafluorophosphate, PF6; tetracyanoborate, B(CN)4; dicyanamide, DCA; thiocyanate, SCN; cyclic perfluorosulfonylamide, CPFSA, and carborane.

[0081] Preferably, the ionic salt is a lithium salt selected from the group consisting of, for example, LiBF4, LiFSI, lithium bis(trifluoromethanesulfonyl)imide (Li[TFSI]), lithium (bis(fluorosulfonyl)imide (Li[FSI]), lithium triflate (Li[OTf]), lithium perchlorate (LiClO4), lithium dicyanamide (LiDCA), lithium cyanate (LiOCN), lithium thiocyanate (LiSCN), lithium bis[(pentafluoroethyl)sulfonyl]imide, lithium 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM), lithium 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide (TSAC), lithium nonafluorobutanesulfonate (NF), lithium carborane, lithium difluoro(oxolato)borate, and combinations thereof.

[0082] Preferably, the doped salt is a Li salt such as LiNTf2, and the ZIPC composition has a transportity greater than 0.4, as determined electrochemically or by NMR. Such techniques are well known in the art. An example of an electrochemical method for ion transportity is the Bruce-Vincent method, which is well known in the art.

[0083] Preferably, the ionic salt is a sodium salt selected from the group consisting of, for example, NaBF4, NaFSI, sodium bis(trifluoromethanesulfonyl)imide (Na[TFSI]), sodium bis(fluorosulfonyl)imide (Na[FSI]), sodium triflate (Na[OTf]), sodium perchlorate (NaClO4), sodium dicyanamide (NaDCA), sodium cyanate (NaOCN), sodium thiocyanate (NaSCN), lithium bis[(pentafluoroethyl)sulfonyl]imide, sodium 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM), sodium 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide (NaTSAC), lithium nonafluorobutanesulfonate (NaNF), sodium carborane, sodium difluoro(oxolato)borate, and combinations thereof. Particularly preferred sodium salts include sodium bis(trifluoromethanesulfonyl)imide (Na[TFSI]), sodium bis(fluorosulfonyl)imide (Na[FSI]), sodium triflate (NaOTf), sodium perchlorate (NaClO4), sodium dicyanamide (NaDCA), sodium cyanate (NaOCN), sodium tetrafluoroborate (NaBF4), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0084] Preferably, the ionic salt is an iodide salt selected from the group consisting of AgI, NaI, KI, guanidinium iodide, Nme4I, N(Pr)4I, N(Et)4I, and combinations thereof. The iodide salt is usually a combination of I - / I3 - It is provided in combination with iodine so that it dissociates into pairs.

[0085] Preferably, the ZIPC composition is doped with an acid or base. Incorporating excess acid or base into the protic ZIPC promotes higher proton conductivity. Protons are thought to be transported primarily through the permeated grain boundary phase.

[0086] Preferably, the ZIPC composition comprises a ZIPC compound and an acid, the acid present at a concentration of at least about 5 mol%. Preferably, the acid is present at concentrations of at least about 5 mol%, at least about 10 mol%, at least about 15 mol%, at least about 20 mol%, at least about 25 mol%, at least about 30 mol%, at least about 35 mol%, at least about 40 mol%, at least about 45 mol%, at least about 50 mol%, at least about 55 mol%, at least about 60 mol%, at least about 65 mol%, at least about 70 mol%, at least about 75 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, and at least about 95 mol%. Suitable acids include trifluic acid, bis(trifluoromethanesulfonyl)amine, methanesulfonic acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, and tetrafluoroboric acid.

[0087] Preferably, the ZIPC composition comprises a ZIPC compound and a base, the base present at a concentration of at least about 5 mol%. Preferably, the base is present at concentrations of at least about 5 mol%, at least about 10 mol%, at least about 15 mol%, at least about 20 mol%, at least about 25 mol%, at least about 30 mol%, at least about 35 mol%, at least about 40 mol%, at least about 45 mol%, at least about 50 mol%, at least about 55 mol%, at least about 60 mol%, at least about 65 mol%, at least about 70 mol%, at least about 75 mol%, at least about 80 mol%, at least about 85 mol%, at least about 90 mol%, and at least about 95 mol%. Suitable bases include imidazole, methylamine, ethylamine, propylamine, butylamine, tert-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, dimethylamine, diethylamine, dibutylamine, N-methylbutylamine, N-ethylbutylamine, trimethylamine, triethylamine, tributylamine, N,N-dimethylethylamine, aniline, 2-fluoropyridine, 1-methylimidazole, or 1,2-dimethylimidazole. Preferred bases include imidazole.

[0088] Preferably, the solid-state composition further comprises one or more additive components selected from polymers, particularly lithium or sodium-functionalized polymers, binders such as PVDF, ionomers, dendrimers, and inorganic fillers, to form a tertiary composite. In one embodiment, the solid-state composition may be provided in the form of a film.

[0089] Preferred compounds, when doped with ionic salts such as alkali metals, alkaline earth elements, or transition metal ions, exhibit an ion transportity greater than 0.4 when measured electrochemically or by NMR. More preferably, the ion transportity, when measured electrochemically or by NMR, is greater than 0.4, greater than 0.45, greater than 0.5, greater than 0.55, greater than 0.6, greater than 0.65, greater than 0.7, greater than 0.75, greater than 0.8, greater than 0.85, greater than 0.85, greater than 0.9, and greater than 0.95.

[0090] A suitable ZIPC compound, when doped with lithium or sodium ions, exhibits a lithium ion transportity greater than 0.4, as determined electrochemically or by NMR. A more suitable ZIPC compound, when doped with lithium or sodium ions, exhibits an ion transportity greater than 0.5, 0.6, 0.7, 0.8, or 0.9. The most suitable ZIPC compound, when doped with lithium or sodium ions, exhibits an ion transportity of approximately 1.

[0091] A suitable ZIPC compound, when doped with a lithium salt to form a mixture, is measured by NMR at 25°C, as shown by 10 -13 ~10 -10 m 2 s -1 Preferably 10 -13 ~10 -8 m 2 s -1 , more 10 -13 ~10 -6 m 2 s -1The diffusion coefficient of lithium is shown in the range of . A suitable mixture of ZIPC compounds and lithium salts is measured by NMR at 25°C and is at least 10 -13 m 2 s -1 This shows the self-diffusion coefficient of lithium. The most suitable mixture of ZIPC compound and lithium salt is at least 10, as measured by NMR at 25°C. -6 m 2 s -1 This shows the self-diffusion coefficient of lithium.

[0092] The ZIPC compound and / or the electrolyte composition containing the ZIPC compound and at least an ionic salt preferably become solid, preferably up to at least 80°C and preferably over a wide concentration range of the ionic salt, while maintaining high ionic conductivity.

[0093] The electrolyte composition of the present invention advantageously exhibits higher ionic conductivity at lower temperatures compared to most polymer electrolytes. As a result, electrochemical batteries based on the electrolyte of the present invention can operate at lower temperatures than conventional solid-state batteries.

[0094] The electrolyte composition of the present invention is advantageous in that it can exist as a solid up to a desired temperature over a wide range of ionic salt concentrations. Preferably, the electrolyte comprising a matrix of ZIPC compounds and / or doped ZIPC compounds exists as a solid up to at least 30°C, at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, at least 170°C, at least 180°C, at least 190°C, at least 200°C, at least 210°C, at least 220°C, at least 230°C, at least 240°C, or at least 250°C.

[0095] In some embodiments, the ZIPC and / or electrolyte composition of the present invention is solid throughout the composition, meaning that the entire volume of the electrolyte composition is in a solid state. However, even if the ZIPC and / or electrolyte is present as a solid, a small amount of matrix / composition may still be in the liquid phase. There is no limitation on the degree of the proportion of matrix / composition in the liquid phase when the material / composite is present as a solid up to the desired temperature. Those skilled in the art will be able to determine an appropriate value for the volume fraction in the liquid phase for a given material based on the phase diagram of the material.

[0096] In some embodiments, the temperature at which the volume fraction of the electrolyte composition of the present invention is in the liquid phase is at least 30°C, at least 40°C, at least 50°C, at least 60°C, at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, at least 120°C, at least 130°C, at least 140°C, at least 150°C, at least 160°C, at least 170°C, at least 180°C, at least 190°C, at least 200°C, at least 210°C, at least 220°C, at least 230°C, at least 240°C, at least 250°C, at least 300°C, or at least 350°C.

[0097] There are no specific limitations regarding the concentration of ionic salts in the solid-state ZIPC composition of the present invention. However, preferably, the composition exists as a solid up to at least 50°C. In some embodiments, the ionic substance is present at a concentration of at least 5 mol%, at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 25 mol%, at least 30 mol%, at least 35 mol%, at least 40 mol%, at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 95 mol% based on the total number of moles of the combined ionic salt and ZIPC compound.

[0098] A preferred electrolyte composition of the present invention, when in a partially molten phase, contains at least 10 -9 It has an ionic conductivity of S / cm. In some embodiments, the ionic conductivity of the electrolyte composition is at least 10 at room temperature when measured by electrochemical impedance spectroscopy (EIS). -9 S / cm, at least 10 -8 S / cm, at least 10 -7 S / cm, at least 10 -6 S / cm, at least 10 -5 S / cm, at least 10 -4 S / cm, at least 10 -3 It is S / cm.

[0099] Electrochemical batteries and their applications The use of ZIPC compounds / matrices or ZIPC compositions in applications requiring ion conduction, including electrochemical devices such as fuel cells, energy storage devices, supercapacitors, or dye-sensitized solar cells, is described here.

[0100] Electrolytes comprising one or more ZIPC compounds of the present invention as a matrix or additive to an electrolyte, and / or one or more ZIPC compositions / composites of the present invention as an electrolyte, are described herein. Preferably, the ZIPC of the present invention can be used as an electrolyte matrix in an electrochemical battery or as an additive in an electrolyte material. The electrolyte may be, for example, a solid electrolyte or a liquid electrolyte at room temperature.

[0101] Preferably, the electrochemical battery or device is an energy storage device such as a Na battery or Li battery, in particular a rechargeable battery, i.e., a secondary battery. The materials described herein include, for example, Li / Li +It is particularly suitable for batteries involving high-voltage chemical reactions exceeding 4.5V. A fuel cell device comprising a zwitterionic viscous crystal (ZIPC) electrolyte matrix optionally doped with an acid, base, or salt dopant is described herein. The use of protonated zwitterionic viscous crystal (ZIPC) in applications requiring proton conduction, including fuel cells, is described herein. A base-doped ZIPC composition may be used as an anhydrous proton conductor, preferably an imidazole base.

[0102] Preferably, the present invention provides an energy storage device comprising an electrolyte containing a negative electrode, a positive electrode, and a ZIPC compound as a matrix or additive, or a ZIPC electrolyte composition / composite according to the present invention.

[0103] definition As used herein, the term "alkyl" describes a group consisting of at least one carbon atom and one hydrogen atom, and can be linear, branched, or cyclic alkyl, e.g., C 1-20 Alkyl, for example, C 1-10 or C 1-6This shows that. Examples of linear and branched alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl , nonyl, 1-,2-,3-,4-,5-,6- or 7-methyloctyl, 1-,2-,3-,4- or 5-ethylheptyl, 1-,2- or 3-propylhexyl, decyl, 1-,2-,3-,4-,5-,6-,7- and 8-methylnonyl, 1-,2-,3-,4-,5- or 6-ethyloctyl, 1-,2-,3- or 4-propylheptyl, undecyl, 1-,2-,3-,4-,5-,6-,7-,8- or 9-methyldecyl, 1-,2-,3-,4- These include 5-,6- or 7-ethylnonyl, 1-,2-,3-,4- or 5-propyloctyl, 1-,2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-,2-,3-,4-,5-,6-,7-,8-,9- or 10-methylundecyl, 1-,2-,3-,4-,5-,6-,7- or 8-ethyldecyl, 1-,2-,3-,4-,5- or 6-propylnonyl, 1-,2-,3- or 4-butyloctyl, 1-2-pentylheptyl, and the like. Examples of cyclic alkyls include monocyclic or polycyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. When alkyl groups are generally referred to as "propyl" or "butyl," it is understood that this can refer to any of the linear, branched, or cyclic isomers, as appropriate.Alkyl groups can be optionally substituted with one or more substituents, including substituents in which the carbon is replaced by a heteroatom (such as O, N, or S), as defined herein.

[0104] Examples of optional substituents include alkyl groups (e.g., methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl C). 1-6 C(alkyl), hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g., methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, etc.), alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, etc.) 1-6 Alkoxy), halo, trifluoromethyl, trichloromethyl, tribromomethyl, hydroxy, phenyl (which itself is, for example, C 1-6 Alkyl, halo, hydroxy, hydroxy C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 (which can be further substituted with alkyl and amino compounds), benzyl (benzyl itself is, for example, C 1-6 Alkyl, halo, hydroxy, hydroxy C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 (which can be further substituted with alkyl and amino compounds), phenoxy (phenyl itself is, for example, C 1-6 Alkyl, halo, hydroxy, hydroxy C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 (can be further substituted with alkyl and amino), benzyloxy (benzyl itself is, for example, C 1-6 Alkyl, halo, hydroxy, hydroxy C 1-6 Alkyl, C 1-6 Alkoxy, Halo C1-6 Alkyl, cyano, nitro OCC(O)C 1-6 C (which can be further substituted with alkyl and amino), amino, alkylamino (e.g., methylamino, ethylamino, propylamino, etc.) 1-6 Alkyl), dialkylamino (e.g., dimethylamino, diethylamino, dipropylamino, etc.) 1-6 Alkyl), acylamino (e.g., NHC(O)CH3), phenylamino (phenyl itself is, for example, C 1-6 Alkyl, halo, hydroxy, hydroxy C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 (Can be further substituted with alkyl and amino compounds), nitro, formyl, -C(O)-alkyl (e.g., C such as acetyl) 1-6 Alkyl), OC(O)-alkyl (e.g., acetyloxy C) 1-6 Alkyl), benzoyl (the phenyl group itself is, for example, C 1-6 Alkyl, halo, hydroxy, hydroxy C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 C=O can be further substituted with alkyl and amino compounds, CO2H, CO2 alkyl, and CH2 substitution (e.g., C=O, CO2H, CO2 alkyl, etc.) 1-6 Alkyl), CO2 phenyl (phenyl itself is, for example, C 1-6 Alkyl, Halo, Hydroxy, Hydroxyl C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 (Further substitutions may be made with alkyl and amino compounds), CONH2, CONHphenyl (phenyl itself is, for example, C 1-6 Alkyl, Halo, Hydroxy, Hydroxyl C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6Alkyl, cyano, nitro OCC(O)C 1-6 (can be further substituted with alkyl and amino), CONH benzyl (benzyl itself is, for example, C 1-6 Alkyl, Halo, Hydroxy, Hydroxyl C 1-6 Alkyl, C 1-6 Alkoxy, Halo C 1-6 Alkyl, cyano, nitro OCC(O)C 1-6 (Can be further substituted with alkyl and amino compounds), CONH alkyl (e.g., methyl esters, ethyl esters, propyl esters, butylamides, etc.) 1-6 Alkyl), CONH dialkyl (for example, C 1-6 Alkyl), aminoalkyl (e.g., HNC) 1-6 Alkyl-, C 1-6 Alkyl HN-C 1-6 Alkyl- and (C 1-6 Alkyl)2N-C 1-6 Alkyl-), thioalkyl (e.g., HSC) 1-6 Alkyl-), carboxyalkyl (e.g., HO2CC) 1-6 Alkyl-), carboxyester alkyl (e.g., C 1-6 Alkyl O2CC 1-6 Alkyl-), amide alkyl (e.g., H2N(O)CC) 1-6 Alkyl-, H(C 1-6 Alkyl)N(O)CC 1-6 Alkyl-), formylalkyl (e.g., OHCC) 1-6 Alkyl-), acylalkyl (for example, C 1-6 Alkyl(O)CC 1-6 Alkyl-), nitroalkyl (e.g., O2NC) 1-6 Alkyl-), sulfoxide alkyl (for example, R f As defined here, for example, C 1-6 Alkyl(O)SC 1-6 Alkyl- and other alkyl groups, R f (O)SC 1-6 Alkyl), sulfonyl alkyl (for example, R f As defined here, for example, C 1-6 Alkyl(O)2SC1-6 As alkyl such as alkyl, Rf(O)2SC 1-6 alkyl), sulfonamidoalkyl (e.g., R f is as defined herein, for example, H(C 1-6 alkyl)N(O)SC 1-6 As alkyl such as alkyl, 2HR f N(O)SC 1-6 alkyl).

[0105] The term "halogen" ("halo") refers to fluorine, chlorine, bromine or iodine (fluoro, chloro, bromo or iodo). Preferred halogens are chlorine, bromine or iodine.

[0106] The heterocyclyl group may be saturated or partially unsaturated, i.e., it may have one or more double bonds. Particularly preferred heterocyclyls are 5- to 6-membered and 9- to 10-membered heterocyclyls. Suitable examples of heterocyclyl groups include aziridinyl, oxiranyl, thiaranyl, azetidinyl, oxetanyl, thietanyl, 2H-pyrrolyl, pyrrolidinyl, pyrrolinyl, piperidyl, piperazinyl, morpholinyl, indolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, thiomorpholinyl, dioxanyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyrrolyl, tetrahydrothiophenyl, pyrazolinyl, dioxalanyl, thiazolidinyl, isoxazolidinyl, dihydropyranyl, oxazinyl, thiazinyl, thiomorpholinyl, oxathianyl, dithianyl, trioxanyl, thiadiazinyl, dithiazinyl, trithianyl, azepinyl, oxepinyl, thiepinyl, indenyl, indanyl, 3H-indolyl, isoindolinyl, 4H-quinorazinyl, chromenyl, chromanyl, isochromanyl, pyranyl and dihydropyranyl. The heterocyclyl group may be optionally substituted by one or more optional substituents as defined herein. The term "heterocyclylene" is intended to denote the divalent form of heterocyclyl.

[0107] The term "heteroaryl" includes any of monocyclic, polycyclic, fused or conjugated hydrocarbon residues, where one or more carbon atoms are replaced by heteroatoms to provide an aromatic residue. Suitable heteroaryls have 3 to 20 ring atoms, for example 3 to 10. Particularly suitable heteroaryls are bicyclic ring systems of 5 to 6 members and 9 to 10 members. Suitable heteroatoms include O, N, S, P and Se, particularly O, N and S. When two or more carbon atoms are replaced, this can be by two or more identical heteroatoms or different heteroatoms. Suitable examples of heteroaryl groups include pyridyl, pyrrolyl, thienyl, imidazolyl, furanyl, benzothienyl, isobenzothienyl, benzofuranyl, isobenzofuranyl, indolyl, isoindolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, quinolyl, isoquinolyl, phthalazinyl, 1,5-naphthyridinyl, quinazolinyl, quinoxalinyl, cinnolinyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl, triazolyl, oxadiazolyl, oxatriazolyl, triazinyl and furazanyl. The heteroaryl group can be optionally substituted by one or more optional substituents as defined herein. The term "heteroarylene" is intended to denote the divalent form of heteroaryl.

[0108] The term "sulfoxide", alone or in a compound word, refers to the R f -S(O)R f group, where Rf is selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocyclyl and aralkyl. Suitable examples of R f include C 1-20 alkyl, preferably C 1-6 alkyl, most preferably C 1-3 alkyl, phenyl and benzyl.

[0109] The term "sulfonyl", alone or in a compound word, refers to the S(O)2-R f group, where R fThe R is selected from hydrogen, halides, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocykyl and aralkyl. f An example is C 1-20 Contains alkyl, phenyl, and benzyl.

[0110] The term "sulfonamide" can be used alone or in a compound word as S(O)NR f R f It refers to the base, and each R f R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carbocykyl and aralkyl. f An example is C 1-20 It includes alkyl, phenyl, and benzyl. In preferred embodiments, at least one R f It becomes hydrogen. In other forms, R f Both will become hydrogen.

[0111] The term "heteroatom" or "hetero," as used herein, refers in its broadest sense to any atom other than a carbon atom that can be a member of a cyclic organic group. Specific examples of heteroatoms include nitrogen, oxygen, sulfur, phosphorus, boron, silicon, selenium, and tellurium, more specifically nitrogen, oxygen, and sulfur.

[0112] The present invention will be described with reference to the following examples. It should be understood that these examples are illustrative of the present invention as described herein, and not limiting it.

[0113] One of the compounds is ZIPC1(BF3 - The physical, thermal, and electrochemical properties of the charged compound 1) in Figure 1A were compared with similar OIPCs (i.e., those with distant cations and anions) to explore the advantageous effects of linking ionic species. This species was selected as similar OIPCs [C2mpyr][BF4] and [C2mpyr][NTf2] (Figure 1A), whose effectiveness as electrolytes in lithium metal batteries has been effectively demonstrated.

[0114] BF3 is used as the first material. - Instead, the use of a more charge-diffusive and hydrolyzably stable sulfonyliimide group was expected to be more beneficial in reducing coordination with Li or Na salts and to make the material more disordered. Similar structures 8 and 9 (Figure 1A) having a fluorosulfonyliimide group can be synthesized in zwitterionic viscous crystals, particularly using morpholinium and piperidinium moieties (Figure 1A), and other cations in ethyl-substituted pyrrolidinium. [Examples]

[0115] Examples of non-protic ZIPCs and protic ZIPCs Figure 1A shows numerous examples of zwitterionic viscous crystals (ZIPCs) compared with similar established OIPCs. For use as proton conductors, ZIPC compounds maintain their immobility as matrix materials while H + These facilitate the conduction of ions (protons). They are doped with acids or bases. From the standpoint of proton conduction, base doping is more effective and preferable. [ka] To investigate the effectiveness of these materials as electrolytes for lithium batteries, zwitterionic ZIPC1 was combined with lithium salts, LiFSI, or LiBF4 in the form of salt-doped ZIPC compositions. Salt-doped ZIPC compositions were investigated at both 10 mol% (Example 1) and 90 mol% (Example 2) concentrations. High lithium salt content resulted in a large number of free anions (FSI) competing with the transport rate of Li cations. - Or BF4 - ) is introduced, but high concentrations of Li ions are very advantageous for the performance of the device (for example, by reducing polarization), and ZIPC1 uses Li +It is thought that ZIPC assists in the dissociation of each counteranion, resulting in increased lithium ion transport compared to OIPC electrolytes with comparablely high lithium salt content. This demonstrates the general advantages of adding ZIPC, even when used in small proportions of conventional electrolyte mixtures as an additive to facilitate the dissociation of target ions. The ionic conductivity of pure ZIPC1 and [C2mpyr][BF4]OIPC, as well as their equivalent mixtures with LiFSI, was investigated as a function of temperature and is reported below.

[0116] Proof of the concept of electrolytes Preliminary DSC, NMR, conductivity, battery cycling, and transport rate data for many of these electrolytes are available. The tests and results are described in more detail below. In particular, the inventors investigated the following electrolytes. <ZIPC1 electrolyte doped with 10 mol% LiFSI (Example 1)> This is compared with 10 mol% LiFSI in a similar [C2mpyr][BF4]OIPC, which has been extensively studied in previous research by the inventors' research group, in order to further demonstrate the advantageous effect of linking cations and anions. <ZIPC electrolyte doped with 90 mol% LiFSI (Example 2)> This is compared to a pure (neat) ZIPC. This higher lithium salt concentration is likely to result in better battery performance. <Protic ZIPC electrolyte (Example 3)> To investigate the advantages of protic ZIPC as an anhydrous proton conductor, ZIPC was doped with an acid or a base. ZIPC1 and its mixture with 10 mol% and 90 mol% LiBF4 (Example 4) Figure 16A, a DSC analysis, shows that the melt transition temperature and fusion entropy of 10 mol% LiBF4 in ZIPC1 are suppressed compared to pure ZIPC1. This effect has also been observed in mixtures with other viscous crystalline Li or Na salts, resulting in the formation of eutectic compositions or the generation of more defects. Increasing the LiBF4 concentration to 90 mol% forms a phase with a higher melting point (220°C) and lower fusion entropy (4.9 J / molK). Figure b of the SEM (Figure 16B) shows the morphology of 10 mol% LiBF4 in ZIPC1, which has granules connected by amorphous or liquid phases that can form pathways that facilitate ion movement within the electrolyte. The morphology with 90 mol% LiBF4 (Figure 16B, figure c) is significantly different, having more granules and grain boundaries that explain the plasticity of this solid-state electrolyte. Figures d and e in Figure 16C show the static solid state of 10 mol% and 90 mol% LiBF4 in ZIPC1, measured over a temperature range of 20–60°C, below the melting point. 7 This shows the NMR spectrum of Li. Generally, solid samples have a broad linear shape due to the strong homonuclear interaction between Li-Li atoms. 7 This gives a Li spectrum. However, the presence of a mobile component leads to a narrowing of the linearity due to increased disorder or the presence of an amorphous phase. Single pulse of 10 mol% LiBF4 in ZIPC1 7 The Li spectrum shows a narrow linear shape, suggesting that the dipole interaction is well averaged. However, the 90 mol% LiBF4 in ZIPC1 7 The Li spectrum shows a narrow component superimposed on a broad component, attributed to the presence of both mobile and low-mobility Li ions, respectively. Figures f and g of Figure 16D show the static single-pulse results of 10 mol% and 90 mol% LiBF4 in ZIPC1. 19 The NMR spectrum of F is shown. (Measured by ZIPC1) 19 The peak of F is due to their close chemical shifts, BF4 -This gives a broad line that overlaps with the linear shape. In both samples, the width of the broader component (relatively narrower compared to what would be expected for a perfectly regular material) and the substantial amount of the narrower component are in BF4 in ZIPC1. - Anion and -BF3 - Both groups exhibit substantial mobility / disorder. The ionic conductivity of the mixture with LiBF4 is approximately three orders of magnitude higher than that of pure ZIPC1 due to the presence of higher concentrations of charge carriers in the electrolyte (Figure 17A). 7 Li and 19 The self-diffusion coefficient of F was measured using pulsed-field gradient (PFG) NMR at different temperatures shown in Figure 17B. In 10 mol% LiBF4 in ZIPC1, BF4 - The spread of anions 7 It is faster than the diffusion of Li cations. By increasing the salt concentration to 90 mol%, 7 Li cations diffuse most rapidly. This is expected to be beneficial to the performance of electrolytes in lithium batteries. The compatibility and electrochemical stability of these novel electrolytes with Li metal were investigated using cyclic voltammetry (CV). Both 10 mol% and 90 mol% LiBF4 in the ZIPC1 electrolyte showed stable cycling behavior, as well as clear Li deposition and stripping peaks with small peak separation. This indicates that this novel type of electrolyte exhibits Li / Li cation interaction without substantial parasitic side reactions. + This demonstrates that it can support fast, stable, and reversible reduction and oxidation reactions. The peak current for the 10 mol% LiBF4 sample (Figure 18A) is lower than that for the 90 mol% sample (Figure 18B), as expected from the lower ion concentration in the electrolyte. thermal research Table 1 shows the thermal properties of pure ZIPC, various lithium-doped composites, and protic ZIPC. Table 1 is (T s-s The presence of a solid-solid phase transition (in which) explains some of the thermal properties of ZIPCs, which is one piece of evidence of potential structural disorder. In particular, compared to the protonated salt, ring alkylation is T s-sThis results in a favorable reduction, while on the other hand, T for both ZIPCs after doping. m It is maintained above room temperature, which is important for its use as a solid-state electrolyte. [Table 1]

[0117] BF3 - The presence of ZIPC groups demonstrates the existence of solid-solid phase transitions in both compounds 1 and 2 (Figure 2, Table 1). This behavior (if observed by at least one other characteristic indicator, e.g., NMR or SEM) represents an important measure of plasticity, as these transitions indicate the initiation of disordering mechanisms (e.g., rotation of specific functional groups) closely related to vacancy formation and increased conductivity in the material.

[0118] The DSC trace of ZIPC1 (C2mpyrBF3) in Figure 1Ba shows the onset temperature and entropy change for each transition. As can be seen from the figure, thermal analysis shows one distinct solid-solid phase transition peak differentiating the two solid phases before melting at 98°C. The solid-solid phase transition for ZIPC1 is 13 JK. -1 mol -1 This shows a relatively low entropy change. The entropy change of the melting transition is 21.4 JK. -1 mol -1 This is the 20 JK required by the Timmermans criterion for viscous crystal behavior. -1 mol -1 It is close to this and shows significant disorder in the material in Phase I (the highest temperature solid phase before melting).

[0119] The onset temperature and entropy change for each transition, which are the DSC traces of ZIPC2, are shown in Fig. 1Bb. As can be seen from the figure, ZIPC2 also shows a solid-solid phase transition at 45 °C this time. The existence of this phase transition represents the onset of molecular rotation within the material, through which the material can be disordered. The increase in the length of the alkyl chain substituent results in a decrease in the melting point from 98 °C in ZIPC1 (C2mpyrBF3) to 60 °C in ZIPC2 (C2epyrBF3).

[0120] For ZIPC6, the onset temperature and entropy change for each transition, which are the DSC traces of ZIPC6, are shown in Fig. 1Bd. ZIPC6 shows a peak at 105 °C in the DSC trace. Visually monitoring this sample at temperatures above 100 °C (as can be seen from the photograph in Fig. 1B) revealed that the peak at 105 °C is not a melting transition since the sample remains solid even at 145 °C. It is a solid-solid transition.

[0121] Each of ZIPC1, ZIPC2, ZIPC5, and ZIPC6 shows a solid-solid phase transition prior to melting. The existence of this transition, together with the low entropy of melting of ZIPC1, is a well-known feature of viscoelastic crystalline behavior. Usually, sufficiently regular crystalline organic salts do not have a solid-solid phase transition in the solid phase and have ΔSm > 60 J K -1 mol -1 .

[0122] Example 1 Thermal Behavior ZIPC1 Electrolyte Doped with 10 mol% LiFSI The thermal behavior of ZIPC1 and ZIPC1 doped with 10 mol% LiFSI is compared in Fig. 2A with that of pure [C2mpyr][BF4] OIPC and [C2mpyr][BF4] OIPC doped with 10 mol% LiFSI. ZIPC1 shows a solid-solid phase transition (at 54 °C), which is an important feature of viscoelastic crystalline behavior. ZIPC has a melting onset at 98 °C with a melting entropy ΔS of 21.4 J K -1 mol -1 and. f ΔS fThe value is very close to the Timmermans criterion for viscous crystalline behavior and smaller than that of many known OIPCs. A similar OIPC [C2mpyr][BF4] decomposes at 250°C before melting. Therefore, thermal analysis (and the NMR data described later) supports the positioning of this novel zwitterionic structure as a viscous crystal. Doping ZIPC1 with 10 mol% LiFSI results in 10 JK -1 mol -1 small ΔS f by T m The temperature was reduced to 59°C. A glass transition (Tg) was also observed at -66°C, indicating the appearance of an amorphous phase in the mixture. The addition of 10 mol% LiFSI to [C2mpyr][BF4]OIPC introduced additional novel peaks at low temperatures below the transition from phase IV to phase III (-95°C and -70°C) and at 83°C after the transition from phase II to phase I, suggesting the formation of a novel phase at low temperatures (Figure 2A(b)). The formation of a novel phase after lithium salt addition has been observed in other Li mixtures of OIPC with pyrrolidinium and is not unique to ZIPC. The first indication is that the material formed by the OIPC and Li salt combination is a novel homogeneous solid, rather than a solid / liquid combination as formed by the ZIPC and salt combination. Consequently, in the OIPC electrolyte, a slower Li + Transport of is expected (as it moves through a solid rather than a liquid or amorphous phase), and this is supported by the broader linewidths observed in the NMR spectra described later (Figures 4A, 4B, and 5).

[0123] Example 2 Thermal phase behavior of a 90 mol% LiFSI and ZIPC electrolyte mixture Figure 2B shows the DSC heating trace of ZIPC1 and the electrolyte mixture of 90 mol% LiFSI in ZIPC1. Adding only 10 mol% ZIPC1 to LiFSI is T m The temperature was lowered to 77°C. Furthermore, a glass transition (Tg) was observed at -66°C, indicating the appearance of an amorphous phase.

[0124] SEM analysis ZIPC1 SEM images of ZIPC1 show slip steps and / or projection surfaces that are normally observed in OIPC due to their plasticity, which is not seen in normal organic / inorganic crystals such as hard and brittle sodium fluorite (Figure 3D). Since the SEM images were taken at room temperature, the material is expected to increase its plasticity at higher temperatures. 19 The NMR spectrum of 1F shows a gradual narrowing of the linewidth, with a small narrow component appearing at 40°C and increasing proportionally with increasing temperature, providing strong evidence of higher levels of plasticity at higher temperatures. All of these results indicate that ZIPC1 has intrinsic rotational motion of the molecule, forming a disordered phase in ZIPC.

[0125] Furthermore, the microstructure / morphology of the ZIPC1 pellet surface provides evidence of plasticity, as several grains with different orientations may be observed. Additionally, multiple sets of slip surfaces may be found within different grains. These slip steps are also observed in the viscous OIPC system. Grain boundaries are clearly detected from the fracture surface of ZIPC6. Slip steps that maintain consistency to the end of the grain boundary also contribute to plasticity. If SEM images of the second phase (not the highest temperature solid phase) of two ZIPCs are obtained at room temperature, this suggests that higher levels of plasticity exist at higher temperatures. This is accompanied by the temperature increase described later. 19 This is consistent with the slight increase in the mobile component observed in NMR measurements of 1F.

[0126] SEM Analysis Example 1: ZIPC1 electrolyte doped with 10 mol% LiFSI Figure 3A shows the SEM analysis of pure ZIPC1 / ZIPC1 with 10 mol% LiFSI. The microstructure of the ZIPC1 pellet surface provides evidence of plasticity, as several particles with different orientations can be observed (Figure 3A(a)). Furthermore, multiple sets of slip surfaces can be seen within different particles. These slip steps are also observed in the viscous OIPC system. SEM images of ZIPC1 doped with 10 mol% LiFSI also suggest that the particles in the ZIPC1 electrolyte are connected by a novel liquid phase (Figure 3A(b)). Based on the MNR data (below), it is proposed that this phase has a high concentration of LiFSI. Therefore, this phase is thought to provide a pathway for Li ion diffusion, facilitating target ion transport through the electrolyte. SEM images of this mixture also suggest this idea and that the particles in the ZIPC1 electrolyte are connected by this novel liquid phase. Based on the MNR data (below), it is thought that this phase has a high concentration of LiFSI. Therefore, this phase provides a pathway for Li ion diffusion and facilitates target ion transport through the electrolyte.

[0127] SEM Analysis Example 2: 90 mol% LiFSI and ZIPC1 Electrolyte Mixture Figure 3B shows an SEM image of the 90 mol% LiFSI electrolyte mixture in ZIPC1. The SEM image of the 90 mol% LiFSI electrolyte mixture in ZIPC1 shows that the crystalline and intergranular regions contain a mobile lithium-rich electrolyte, supplying pathways for lithium ions that support lithium electrochemical activity and instrument cycling.

[0128] Example 3: ZIPC5 and 10 mol% LiFSI in ZIPC5 Since a narrow linewidth exists even at 30°C, the static state of pure ZIPC5 (methylated morpholinium compound) 1 H and 19The NMR spectrum of 1F shows evidence of disorder, with the level of disorder increasing at higher temperatures and demonstrated by a narrower linewidth and an increased proportion of narrow components. This disorder (Figure 5D(a)-(c)) is consistent with the material becoming a viscous crystal. The DSC trace of pure ZIPC5 shows a broad peak around 25°C that may be due to a solid-solid phase transition and a sharp melting peak at 120°C. The SEM image of ZIPC5 shows grain boundaries, which are not seen in perfectly regular crystalline materials and therefore may be evidence of plasticity. The presence of grain boundaries in the structure of ZIPC may aid in ionic conduction. All of these results indicate that ZIPC5 has a disordered structure consistent with being a viscous crystal.

[0129] The solid-solid phase transition around 25°C was more pronounced in the ZIPC5 sample containing 10 mol% LiFSI. Adding only 10 mol% LiFSI to ZIPC5 lowered the melting point to 92°C. Furthermore, a glass transition (Tg) was observed at -29°C, indicating the emergence of an amorphous phase. SEM images of 10 mol% LiFSI in ZIPC5 reveal a novel amorphous phase that provides a pathway for Li ion diffusion, facilitating target ion transport through the electrolyte, and potentially proving highly beneficial for the application of this material as an electrolyte in Li batteries. The ionic conductivity of 10 mol% LiFSI in ZIPC5 showed a sharp increase at 50°C, suggesting increased mobility of Li and FSI ions after the solid-solid phase transition of ZIPC5, similar behavior observed in other viscous crystalline materials. Since the ionic conductivity of pure ZIPC5 is not measurable, this ionic conductivity may be attributable to the mobility of FSI anions and Li cations.

[0130] Transport and electrochemical properties of ZIPC1 as a quasi-solid electrolyte The evaluation of the electrochemical properties and interfacial behavior of novel electrolytes, including ZIPC, was based on (i) voltammetry characterization of the behavior of a three-electrode battery with Li metal as the working electrode, and (ii) constant current and EIS characterization of a symmetric Li metal coin cell to demonstrate the applicability of these unique electrolyte materials.+ The transport fraction was measured electrochemically using chronoamperometry and, where applicable, compared with NMR results. The t between ZIPC and OIPC was also measured. Li+ The comparison provides important preliminary confirmation of the zwitterionic advantage for improved target ion transport.

[0131] Ionic conductivity and NMR linewidth Example 1 ZIPC1 electrolyte doped with 10 mol% LiFSI The ionic conductivity of the [C2mpyr][BF4] electrolyte doped with 10 mol% LiFSI is approximately an order of magnitude higher than that of the ZIPC1 / LiFSI mixture (Figures 4A(a) to (c)). This high conductivity was expected because, in the ZIPC1 electrolyte, 90% of the ionic components are coupled and therefore cannot move in an electric field where only Li and FSI ions can move, whereas the OIPC electrolyte is composed entirely of individual ions. Indeed, the fact that the conductivity of the ZIPC electrolyte is very close to that of OIPC is highly noteworthy and demonstrates significant mobility of Li cations and FSI anions in the doped ZIPC matrix material. This was further analyzed by NMR, as described later.

[0132] Measuring the linewidth of a static NMR spectrum reveals the relative mobility of NMR-active nuclei. Therefore, although OIPC is a solid material, its inherent disorder (e.g., significant rotational motion of cations and / or anions) results in very narrow lines, similar to those commonly observed in crystalline solids. It should be noted that completely liquid samples also yield very narrow lines, as all species are fully mobile by both translational and rotational motion. In particular, the static NMR linewidth of Li is much broader in a [C2mpyr][BF4]OIPC electrolyte doped with 10 mol% LiFSI than in a comparable 10 mol% LiFSI-doped ZIPC1 electrolyte. Overall, electrolytes with OIPC are ionically more conductive because they contain more free ions, but the mobility of doped lithium ions is much lower than in a salt-doped ZIPC1 electrolyte.

[0133] On the other hand, regarding OIPC electrolytes doped with LiFSI... 7 The Li spectrum showed a relatively broad single peak at 20°C, with a very small proportion of a second, narrower component appearing at 30°C and increasing only slightly at 60°C (Figure 5A(a)a). This is because, 7 This suggests the presence of a very small proportion of diffusible Li ions (though not sufficient to measure the diffusion coefficient of Li). In contrast, for LiFSI-doped ZIPC electrolytes... 7 The Li spectrum shows only a narrow signal (linewidth below approximately 0.3 kHz) across the entire temperature range and remains almost constant even as the temperature increases (Figure 5A(a)b). This indicates that most Li ions in the LiFSI / ZIPC1 mixture have very high mobility, which is consistent with the hypothesis of a lithium-rich liquid phase in the LiFSI / ZIPC electrolyte. The linewidth for Li is significantly wider in the OIPC electrolyte doped with 10 mol% LiFSI than in the electrolyte doped with equivalently doped ZIPC1 (Figure 5A(b)c). Therefore, although the OIPC electrolyte as a whole is more conductive, the lithium ions appear to have much lower mobility than in the ZIPC1 electrolyte due to the presence of more free ions.

[0134] This is also shown in Figure 5B(b) 19 Supported by NMR of 14F. Briefly, LiFSI-doped OIPC electrolyte at 20°C 19 The F spectrum shows one broad peak for BF4 and one very small broad peak for FSI ions. However, at 60°C, the spectrum shows two different BF4 environments, representing a relatively mobile component and a low-mobility component. On the other hand, the BF3 group in LiFSI-doped ZIPC1 electrolyte... 19 The F spectrum shows the presence of both mobile and low-mobility components at all temperatures studied. Furthermore, the FSI anions in LiFSI-doped ZIPC1 electrolyte 19The F spectrum has only one narrow peak across the entire temperature range tested (i.e., representing one mobile component). This suggests that almost all FSI anions are diffusive, with 3 × 10⁻⁶ peaks across the studied temperature range. -13 ~4.6×10 -12 m 2 s -1 This is supported by the measured diffusion coefficient of FSI, which increases up to a certain point.

[0135] About ZIPC1 electrolyte doped with 10% LiFSI 1 The H spectrum (not shown) also supports the two-phase hypothesis. However, the spectrum is dominated by a narrow, sharp line at all temperatures, suggesting that most of the cations are mobile in the liquid phase. Meanwhile, regarding the LiFSI-doped OIPC electrolyte mixture... 1 The H spectrum also shows the presence of cations with significant mobility, but these are present in a narrow component at very low concentrations, for example, only 2% at 40°C, compared to 60% in the LiFSI-doped ZIPC1 electrolyte.

[0136] Figure 6A shows that the peak gradually narrows (the linewidth decreases) as the temperature increases, from 21.5 kHz at 20°C to 14.1 kHz at 60°C. This indicates that the "mobility" of the -BF3 species (due to rotational irregularity) increases as the material is heated. A second, narrower peak (with a linewidth of approximately 1.2 kHz) above the first broad peak becomes distinguishable from 40°C, suggesting the presence of a small but increasing proportion of dynamic anions at higher temperatures (in the first phase) (Figures 6D-E). The presence of broad and narrow components is not unique to ZIPC, but it is a clear measure of the irregularity within the viscous crystal.

[0137] Ionic conductivity and NMR linewidth Example 2 90 mol% LiFSI and ZIPC electrolyte mixture The ionic conductivity of an electrolyte mixture of pure ZIPC1 and 90 mol% LiFSI in ZIPC1 is shown as a function of temperature in Figure 4B. Since both pure LiFSI and pure ZIPC have very low ionic conductivity, this result indicates that the addition of only 10 mol% ZIPC1 significantly increased the ionic conductivity of this mixture. 7 Li spectrum, pure LiFSI 7 Li spectrum and 90 mol% LiFS and ZIPC1 electrolyte mixture 19 F spectrum and 90 mol% LiFSI and ZIPC1 electrolyte mixture 7 Li and 19 The linewidth of F as a function of temperature is shown in Figures 5B(a) to (d) for a 90 mol% LiFSI and ZIPC1 mixture. 7 The Li spectrum shows only a narrow signal (below approximately 0.3 kHz) across the entire temperature range and remains almost constant even as the temperature increases (Figure 5B(a)a). This indicates that most Li ions have very high mobility in this electrolyte. On the other hand, for pure LiFSI... 7 The Li spectrum shows a broad single peak over the entire temperature range and exhibits very low mobility (Figure 5Ba, Figure 5b). 90 mol% LiFSI and ZIPC1 electrolyte mixture FSI anion 19 The F spectrum has only one narrow peak (i.e., the mobile component) across the entire temperature range (Figure 5B(b)c). This suggests that almost all FSI anions are diffusible, supported by the measured diffusion coefficients of the FSIs. 7 Li and 19 Both line widths of F are small in the 90 mol% LiFSI and ZIPC1 electrolyte mixture, indicating very high mobility (Figure 5B(c), d).

[0138] Diffusion coefficient Example 1 ZIPC1 electrolyte doped with 10 mol% LiBF4 The diffusion coefficients indicate that Li and FSI diffuse faster in LiFSI-doped ZIPC1 electrolyte than in LiFSI-doped OIPC electrolyte (Figure 7A). This is consistent with the fact that their anions are mainly in the liquid phase in LiFSI-doped ZIPC1 electrolyte. In LiFSI-doped OIPC electrolyte, only a small proportion of ions are sufficiently mobile to be measured. 19 It is also important to note that the NMR of 14F can only be measured above 50°C. The diffusion coefficient indicates that Li diffusion is not measurable even at high temperatures of 60°C in the OIPC-doped electrolyte. The diffusion of FSI ions is measurable above 50°C, which is consistent with the NMR linewidth indicating that only a small proportion of FSI ions above 50°C had sufficient mobility to diffuse in the OIPC-doped electrolyte. The significantly higher diffusion rate in the LiFSI-doped ZIPC1 electrolyte clearly demonstrates the usefulness of ZIPC for lithium battery applications, which will be further explored below.

[0139] Diffusion coefficient Example 2 90 mol% LiFSI and ZIPC1 electrolyte mixture Figure 7B shows the results of PFG-NMR measurements of a 90 mol% LiFSI and ZIPC1 electrolyte mixture at different temperatures. 7 Li and 19 The diffusion coefficient of F is shown. The diffusion coefficient is in a 90 mol% LiFSI and ZIPC1 electrolyte mixture. 19 F 7 This indicates that Li diffuses rapidly. This suggests a high Li transport rate in this electrolyte.

[0140] Electrochemical Research Example 1: ZIPC1 electrolyte doped with 10 mol% LiFSI The lithium plating (negative scan) and stripping (positive scan) behavior of ZIPC1 electrolyte doped with 10 mol% LiFSI was investigated using cyclic voltammetry (CV). The CV data (Figure 8) demonstrate the success of Li metal stripping and plating, indicating stability and reversibility, and that the current density remains stable during continuous cycling. Electrochemical stability of the electrolyte is a crucial factor for electrochemical devices. The results show that ZIPC1 doped with 10 mol% LiFSI maintains a 5V anodic limit (vs. Li / Li). + This indicates that this electrolyte has a wide enough electrochemical window to be used in batteries with high-voltage cathode materials. Furthermore, this indicates that Li / Li + The ability of this electrolyte to support pairwise reversible stripping and plating is demonstrated. Electrochemical activity is further tested below. Chronoamperometry of Li|ZIPC1 electrolyte doped with 10 mol% LiFSI|Li battery at 50°C in a 10 mV potential step (Figure 9A). Lithium transport rate (t Li+ The value of ) was found to be 0.3. These are Li + This is a significant transposition rate. Li+ It should be noted that this cannot be measured with OIPC doped with 10 mol% LiFSI.

[0141] Electrochemical Research Example 2: 90 mol% LiFSI and ZIPC1 electrolyte mixture Figure 9B shows the chronoamperometry study of a Li|ZIPC1 electrolyte mixture|Li battery at a potential step of 10 mV at 50°C. The inset shows the Nyquist profiles of the electrochemical impedance spectroscopic response of the battery before polarization and after steady-state current. Lithium transport number (t Li+ The value of ) was found to be 0.7. This is Li + The transport rate is significantly higher, demonstrating the promising potential of zwitterionic viscous crystalline compounds for electrolyte formation.

[0142] Cycling Research Example 1: ZIPC1 electrolyte doped with 10 mol% LiFSI Subsequently, the ZIPC1 electrolyte doped with 10 mol% LiFSI was tested in a symmetric lithium metal battery (Figure 10A(a)). The battery polarization increased with increasing current density, as is normal behavior. However, the voltage profile remained symmetric and reversible at all current densities. Therefore, the results indicate that the electrolyte has high compatibility with reactive lithium electrodes, at 0.2 mAhcm². -2 This shows that Li ion transport can be supported even at a charge of 0.2 mAcm². Figure 10A(a) shows that the electrolyte can support Li ion transport at a higher applied current density (0.2 mAcm²). -2 ) indicates that it cycled well even in this case. These results indicate that this electrolyte is a good candidate to act as an electrolyte for lithium batteries, supporting the high-voltage electrochemical action of lithium and providing easy lithium ion transport and (b) 10 mol% LiFSI doped in ZIPC1, 0.1 mA / cm 2 This shows the symmetrical battery cycling performance at 50°C. The charge-discharge interval was maintained at 1 hour. The inset in Figure 10A(b) is a magnified view of the voltage profile at 50–70 cycles. Thus, this electrolyte demonstrates stable cycling at low polarization potential for 100 cycles. The electrolyte also exhibits 0.1 mAcm for 100 cycles. -2Even at the applied current density, the battery demonstrated excellent stability and reversibility (Figure 10A(b)), demonstrating superior battery performance. A 10mol% LiFSI|Li battery in LFP|ZIPC1, a complete battery consisting of a lithium metal anode with a lithium iron phosphate (LFP) cathode, was cycled at 50°C in the range of 2.8–3.8V (Figure 11). This battery showed stable, long-term cycling at 50°C and C / 20. The battery showed an increase in reversible capacity with cycling. It achieved a reversible discharge capacity of 5mAh / g in the first cycle and reached 24mAh / g in the 70th cycle. The increase in reversible capacity is assumed to be a result of internal temperature rise during cycling, which may cause melting of the electrolyte near the electrode interface, leading to better wettability of the electrode material with the electrolyte. A capacity retention rate of 90% was achieved beyond 30 cycles with a Coulomb efficiency of 98%. These results demonstrate promising preliminary charge-discharge cycling performance for LFP|10mol% LiFSI-doped ZIPC1 electrolyte|Li batteries at 50°C. Unoptimized batteries exhibit remarkable efficiency (average efficiency of 98%), which is crucial for battery performance.

[0143] Cycling Research Example 2: 90 mol% LiFSI and ZIPC electrolyte mixture Figure 10B shows the 0.1 mA / cm² electrolyte mixture of 90 mol% LiFSI and ZIPC1. 2 This shows the symmetrical battery cycling performance at 50°C. The charge-discharge interval was maintained at 1 hour. The inset in Figure 10A(c) is a magnified view of the voltage profile at 50–60 cycles. This electrolyte demonstrated stable cycling with low polarization potential over 480 cycles.

[0144] Figure 12 shows that the DSC trace of ZIPC7 exhibits three peaks during the heating cycle (T1 = 92°C, ΔH f =26J / g, T2=106℃, ΔH f =10J / g, T3=119℃, ΔH f=25J / g) (The melting point of imidazole is 89°C). The DSC of ZIPC7 / imidazole 50 / 50 mixture is ΔH f It shows one broad melting peak with =25 J / g at 97°C. This is different from the trace of pure ZIPC7, and there is no peak for pure imidazole (T m (=89°C). Therefore, the altered melting behavior confirmed the interaction between imidazole and zwitterions.

[0145] Figure 13 shows the conductivity of (a) samples doped with pure protic zwitterion ZIPC7 and imidazole base. The conductivity of each sample was measured three times. Pure imidazole showed the lowest conductivity of all samples. In all cases, conductivity increased with temperature. Addition of a small amount (10%) of zwitterion to imidazole gave a 10-fold increase in conductivity. The highest conductivity was obtained when 20% zwitterion was added to imidazole. In this case, at room temperature, the conductivity was approximately 1000 times that of pure imidazole. The conductivity of the 90 / 10 mixture was similar to that of the 50 / 50 mixture.

[0146] Protonated ZIPC electrolyte To investigate the advantages of protic ZIPC as an anhydrous proton conductor, ZIPC is doped with an acid or a base. For example, ZIPC7 was doped with trifluic acid. The conductivity after trifluic acid doping was 10 -6 ~10 -5 Scm -1 It was identified that CV showed a certain electrochemical (H) activity that is very important for fuel cell applications. On the other hand, doping with the solid base imidazole appeared to be more promising (see Figure 13), which is summarized below. The DSC of the 50 / 50 mixture (see Figure 12) showed ΔH f It shows a single broad melting peak with =25 J / g at 97°C. The sample has only one peak and appears different from a pure zwitterion. A pure imidazole peak is also absent (T m(=89°C). The altered melting behavior allowed us to confirm the interaction between imidazole and zwitterions.

[0147] Comparison of conductivity using different combinations Pure imidazole exhibits the lowest conductivity among all samples (the bottom set of circles in Figure 13). In all cases, conductivity increases with temperature. The addition of a small amount (10%) of the zwitterion ZIPC7 to imidazole increases conductivity tenfold (2.01 × 10⁻⁶). -7 S / cm to 10 -6 The conductivity increases to S / cm (the set of circles in the center of Figure 13). The highest conductivity was obtained when 20% zwitterions were added to imidazole (the set of triangles at the top of Figure 13). In this case, the conductivity is already 2.23 × 10⁻¹⁰ at room temperature, which is about 1000 times that of pure imidazole. -4 The conductivity was S / cm. The conductivity of the 90 / 10 mixture (the set of circles in the center of Figure 13) is similar to that of the 50 / 50 mixture (the set of diamonds behind the circles for I:ZI 90:10).

[0148] Consequently, base-doped ZIPC7 exhibits significantly higher conductivity than pure imidazole (pure ZI is too low to be measurable). This conductivity is good for solid-state anhydrous proton conductors. Since pure imidazole is often used for proton conduction, this means that, in terms of proton conduction, this protic ZIPC may offer a significant improvement over pure imidazole.

[0149] Zwitter ions in liquid electrolytes To explore the effectiveness of using zwitterions as non-volatile media for high target ion conduction in liquid electrolytes, a high lithium salt content was used in combination with pyrrolidinium ZIPC1. With 50 mol% LiFSI in ZIPC1, T250°C was achieved. gIt exists only (inset in Figure 15a), and the material is liquid at room temperature. Therefore, this zwitterion forms a liquid electrolyte with a high salt content. This zwitterion electrolyte is non-volatile and does not involve the movement of competing cations. Previous studies on the development of zwitterionic liquids as electrolyte media have mainly used sulfonates or sulfonylimid anions in combination with imidazolium cations, and the best results have been achieved using linkers between 5-7 CH2 groups. Smaller ZIPC1 molecules and charge-diffusing BF3 - It was thought that the use of certain parts could enhance conductivity and transportability. In fact, the conductivity of the new material was 1.4 × 10⁻⁶. -4 Scm -1 (30°C) (Figure 15a) is the same as or higher than other reported liquid non-viscous zwitterionic electrolytes, and it also has a high transport fraction of 0.55 ± 0.05 at 50°C. The novel zwitterionic liquid electrolyte exhibits excellent stability against lithium metal cycling (Figure 15b), and is considered the first demonstration of lithium metal cycling in a liquid zwitterionic electrolyte. 0.5 mAcm -2 The current density range up to was applied for 1 hour over 5 cycles at each current. Lithium stripping and plating were performed at 0.5 mAcm². -2 However, this is due to good stability and a low polarization potential. Importantly, the current density is 0.05 mAcm². -2 When returned to its original state, the low overvoltage was restored. This stability was 0.2 mAcm. -2 (0.2mAhcm -2 The overvoltage was maintained even during prolonged cycling. The overvoltage remained low and stable at approximately 80mV, even after dropping to approximately 70mV after 65 cycles. This is due to low internal resistance and is consistent with the formation of a conductive SEI layer.

[0150] Synthesis of ZIPC3 [ka] 1-(chloromethyl)-1-methylpyrrolidine-1-ium iodide A solution of 1-methylpyrrolidine (1 equivalent) in ethyl acetate was reacted with chloroiodomethane (1 equivalent) and stirred at room temperature under an inert atmosphere for 16 hours. The ethyl acetate was then removed under vacuum, and the solid was washed with diethyl ether to obtain the product as a light brown solid (yield 98%). 1 H NMR(run07 / 02 / 2018)(400MHz,CDCl3):5.80(s,2H,NC H 2Cl),4.15-4.21(m,2H,C H 2-5(Pyr)), 3.88-3.93(m,2H,C H 2-2 (Pyr), 3.50 (s, 3H, NC H 3), 2.32-2.45(m,4H,C H 2-3,4 (Pyr). 13 C NMR(run12 / 03 / 2018)(100.6MHz,CDCl3):68.98,64.35,49.18,22.37 1-(aminomethyl)-1-methylpyrrolidine-1-ium iodide 1-(chloromethyl)-1-methylpyrrolidine-1-ium iodide was reacted with an aqueous ammonia solution (28%) and stirred at room temperature for 36 hours. The solvent was removed under vacuum, the resulting residue was washed with dichloromethane, and dried under vacuum to obtain the target structure as a brown resin (yield approximately 30%). 1 H NMR(run2 / 09 / 2019)(400MHz,CDCl3):5.61(s,2H,NC H 2NH2), 4.17-4.19(m,2H,C H 2-5(Pyr)),3.84-3.88 3.88-3.93(m,2H,C H 2-2(Pyr)), 3.46(s, 3H, NC H 3), 2.37-2.46(m,4H,C H 2-3,4(Pyr)) ((1-methylpyrrolidine-1-ium-1-yl)methyl)((trifluoromethyl)sulfonyl)amide A dehydrated acetonitrile solution of 1-(aminomethyl)-1-methylpyrrolidine-1-ium iodide (1 equivalent) was reacted with an acetonitrile solution of trifluoromethylsulfonyl chloride (1.5 equivalents) at approximately 0°C. The mixture was then stirred at room temperature under an inert atmosphere for 4 days and dried under vacuum. The resulting residue was purified with dichloromethane / water and dried under vacuum to obtain the target structure as a brown resin. 1 H NMR(19 / 12 / 19)(400MHz,CDCl3):5.44(s,2H,NC H 2NHS), 3.95-3.99(m,2H,C H 2-5(Pyr)), 3.74-3.79(m,2H,C H 2-2(Pyr)), 3.37(s, 3H, NC H 3), 2.34-2.39(m,4H,C H 2-3,4 (Pyr). 19 F NMR(19 / 12 / 19)(376.5MHz CDCl3):-78.60

[0151] Synthesis of ZIPC4 [ka] 1-((chlorosulfonyl)methyl)-1-methylpyrrolidine-1-ium chloride A solution of N-methylpyrrolidine (1 equivalent) in dehydrated dimethylformamide was reacted with cold chloromethanesulfonyl chloride (1.2 equivalents), and the solution was stirred at room temperature under an inert atmosphere for 3 days. The product was then dried under vacuum and washed with diethyl ether to obtain black tar. Due to the high reactivity of the sulfonyl chloride portion, the tar was immediately moved to the next step. (((1-methylpyrrolidine-1-ium-1-yl)methyl)sulfonyl)(2,2,2-trifluoroethyl)amide A solution of 1-((chlorosulfonyl)methyl)-1-methylpyrrolidine-1-ium chloride (1 equivalent) in anhydrous dichloromethane was reacted with a suspension of 1,1,1-trifluoroethylamine (1.2 equivalents) and sodium bicarbonate (1.8 equivalents) in anhydrous dichloromethane. The reaction mixture was stirred at room temperature under an inert atmosphere for 48 hours, after which the solid was filtered off and organic matter was removed from the filtrate under vacuum. The resulting residue was washed three times with diethyl ether and dried under vacuum to obtain the target structure as a brown solid (yield approximately 50%). 1 H NMR(6 / 8 / 2018)(400MHz,CDCl3):5.61(s,2H,NC H 2SO2), 4.34(s, 2H, NC H 2CF3),4.01-4.07(m,2H,C H 2-5(Pyr)),3.77-3.83,3.74-3.79(m,2H,C H 2-2(Pyr)), 3.39(s, 3H, NC H 3), 2.27-2.39(m,4H,C H 2-3,4 Pyr)). 19 F NMR(6 / 8 / 2018)(376.5MHz,CDCl3):-69.5

[0152] Electrochemical impedance spectroscopy (EIS) The conductivity of liquid and solid samples was measured according to the procedure described in Makhlooghiazad et al., J. Mater. Chem, A, 2017, 5, 5770, Chapter 2.2.2, which is incorporated herein by reference.

[0153] Solid-state nuclear magnetic resonance spectroscopy (NMR) Solid-state NMR experiments were performed using a commercially available Bruker AVANCE III 500WB NMR spectrometer with a 2.5 mm zirconia rotor, following the standard procedure described in Mater.Adv.2021, 2, page 1686, which is incorporated here by reference.

[0154] Cycling of symmetrical batteries Li symmetric electrochemical coin cells were constructed, and the ability of electrolytes to cycle Li metal efficiently and without degradation was investigated using 10 mol% or 50 mol% LiFSI in ZIPC1. These were measured at 0.1 mAcm² for each polarization at 50°C. -2 or 0.2 mAcm -2 The batteries were cycled for 1 hour at the specified current density. A Biologic VMP3 / Z potentiostat was used to cycle the batteries at a constant current, and data were collected using EC-lab software version 11.27. The type of separator used for battery cycling, transport rate measurement, and complete battery cycling is specified in the figure headings. The separators were dried overnight under vacuum and saturated with a liquid electrolyte (50 mol% LiFSI in ZIPC1). For 10 mol% LiFSI in ZIPC1, the sample was melted at 90°C, and the separator was saturated with the molten electrolyte. After the separator was sufficiently wet, the temperature was reduced to 50°C to solidify the electrolyte. These electrolytes were then sandwiched between two 8 mm diameter Li metal discs and assembled in a stainless steel battery case (Hohsen) using a 1 mm spacer and a 1.4 mm spring to provide uniform contact between the electrodes and electrolyte in the battery. The battery assembly was performed in an argon-filled glove box. I stored the battery at 50°C for 24 hours before cycling.

[0155] Cyclic voltammetry Cyclic voltammetry (CV) was performed to investigate the redox behavior of Li in 10 mol% LiFSI in ZIPC1. CV was performed using Biologic VMP3 / Z potentiostat driven by EC-lab software at 50°C and 0.05 mVs. -1The scan was performed at a certain speed using a two-electrode setup. A fiberglass separator was saturated with molten electrolyte and then sandwiched between a stainless steel working electrode and an 8mm diameter lithium metal disc (Sigma Aldrich) as the reference / counter electrode, assembling it into a stainless steel coin cell. The entire battery assembly process was carried out in a glove box under an argon atmosphere.

[0156] transportation number Li-symmetric batteries containing 10 mol% and 50 mol% LiFSI in ZIPC1 were prepared using the same procedure as the Li-cycling test, and Li-symmetric batteries were prepared at 50°C using the method described by Evans, Bruce, and Vincent. + The transport factor was measured. A small constant potential of 10mV was applied to polarize the battery, and the initial and steady currents were identified. Impedance spectra were obtained before and after polarization. Several symmetric batteries were prepared to obtain reproducible and reliable values. Batteries showing either a very sharp increase in current or a short circuit were discarded, and the reported results are the average values ​​from the others. All experiments were performed and impedance data fitting was carried out using VMP3 / Z Multi Potentiostat (Bio-Logic Science Instruments) and EC-Lab software version 11.27.

[0157] Fully battery-powered cycling The cycling performance of 10 mol% LiFSI in ZIPC1 was studied at 50°C at lower and upper cutoff voltages of 2.8 V and 3.8 V, respectively, using a 2032 coin-type battery with a LiFePO4 (LFP) cathode and a Li metal disk (8 mm in diameter) as the anode. The LFP cathode was prepared by mixing 80 wt% LFP powder, 10 wt% carbon black, and 10 wt% polyvinylidene difluoride (PVDF) with N-methylpyrrolidone (NMP). The prepared slurry was uniformly coated onto an aluminum current collector and dried overnight at room temperature. The cathode electrode was further dried in a vacuum oven at 110°C for 16 hours. The load mass of the active material on the electrode was approximately 1.8 mg cm². -2 The electrolyte was prepared using the same procedure as in the Li symmetric cycling test. The entire battery assembly process was carried out in an argon-filled glove box. The battery was stored at 50°C for 24 hours prior to the electrochemical test to ensure complete absorption of the electrolyte into the electrodes. Constant current charge-discharge studies were performed in an oven at 50°C using the Biologic VMP-3 battery test system.

Claims

1. Select from the following: Zwitterionic viscous crystal (ZIPC) compounds.

2. Use of the compound according to claim 1 as a solid solvent.

3. Use of the compound according to claim 1 as an electrolyte matrix.

4. Use of the compound according to claim 1 as a solid-state electrolyte matrix.

5. Use of the compound according to claim 1 as a conductivity-enhancing additive in an electrolyte.

6. A zwitterionic viscous crystal composition in liquid or solid form, comprising the zwitterionic viscous crystal (ZIPC) compound described in claim 1, and an ionic salt, acid, base, Li or Na functionalized polymer, or a combination thereof.

7. The zwitterionic viscous crystalline composition according to claim 6, wherein the ZIPC is present in a concentration of at least 5 mol%.

8. The zwitterionic viscous crystalline composition according to claim 6, wherein the ionic salt is one or more of alkali metal salts, alkaline earth metal salts, or transition metal salts.

9. The zwitterionic viscous crystalline composition according to claim 6, wherein the ionic salt is either a lithium salt or a sodium salt, or both.

10. The aforementioned ionic salt is LiBF ４ , LiFSI, LiNTf ２ Lithium bis(trifluoromethanesulfonyl)imide (Li[TFSI]), lithium (bis(fluorosulfonyl)imide (Li[FSI]), lithium triflate (Li[OTf]), lithium perchlorate (LiClO ４ The zwitterionic viscous crystalline composition according to claim 6, wherein the alkali metal salt is selected from one or more of the following: lithium dicyanamide (LiDCA), lithium cyanate (LiOCN), lithium bis[(pentafluoroethyl)sulfonyl]imide, lithium 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM), lithium 2,2,2-trifluoro-N-(trifluoromethylsulfonyl)acetamide (TSAC), lithium nonafluorobutanesulfonate (NF), lithium carborane, and lithium difluoro(oxolato)borate.

11. The zwitterionic viscous crystalline composition according to claim 6, wherein the acid is trifluic acid and the base is imidazole.

12. A solid-state electrolyte comprising the zwitterionic viscous crystal (ZIPC) compound described in claim 1.

13. A solid-state electrolyte comprising the solid-state composition described in claim 6.

14. An energy storage device comprising an electrolyte containing the zwitterionic viscous crystal (ZIPC) compound described in claim 1.

15. The energy storage device according to claim 14, wherein the electrolyte further comprises an ionic salt, an acid, a base, a Li or Na functionalized polymer, or a combination thereof.

16. The energy storage device according to claim 15, wherein the energy storage device is a Na battery or a Li battery.

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