Elastomeric electrolytes for high-energy solid-state metal batteries

Abstract

and b) a plurality of plastic crystals dispersed within said matrix to form a three-dimensionally interconnected phase of plastic crystals; and wherein the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20° C. Also disclosed herein are electrochemical cells comprising same and methods of making and using same.

Description

[Technical Field]

[0001] This application relates generally to metal and metal-ion batteries with stable solid electrolytes.

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 209,140, ​​filed June 10, 2021, U.S. Provisional Application No. 63 / 242,156, filed September 9, 2021, and U.S. Provisional Application No. 63 / 285,687, filed December 3, 2021, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Rechargeable batteries based on metallic anodes, including lithium (Li), sodium (Na), and zinc (Zn), show great potential for achieving high energy density.

[0004] Unfortunately, the electrochemical interface of a metal anode is not suitable for metal deposition: metal nucleation is uneven on its surface, inducing the growth of metal dendrites (resin-like crystals) and the formation of an unstable solid-electrolyte interface (SEI) that cannot protect the metal from side reactions with the electrolyte.

[0005] Therefore, much research has been conducted using porous scaffolds, artificial SEI layers, and solid-state electrolytes (SSEs) to address these issues. In particular, solid-state LMBs based on inorganic or organic SSEs have emerged as promising candidates, significantly improving safety by eliminating flammable organic solvents. Considering compatibility with the current roll-to-roll manufacturing process for lithium-ion batteries, solid polymer electrolytes (SPEs) have attracted considerable interest due to their low manufacturing cost, non-toxicity, and relative flexibility, which allows for smooth interface formation with electrodes. Among various polymers, poly(ethylene oxide) (PEO)-based SPEs have been the subject of intensive research, but such polymers have not demonstrated sufficient ionic conductivity and stability for stable operation of LMBs. A common approach to improving ionic conductivity is to mix additives, such as organic and inorganic charging materials, into the polymer matrix to form gel or hybrid SPEs.

[0006] However, the ionic conductivity and / or mechanical properties of such gels and hybrid SPEs must be further improved for the feasibility of high-energy LMBs. Synthetic rubbers, or elastomers, are widely used in consumer goods and advanced technologies (wearable electronics and soft robotics) due to their excellent mechanical properties. Elastomers can provide an excellent matrix for dispersing functional components while maintaining both mechanical resilience and functionality. For example, important properties of mixtures, such as electrical and ionic conductivity, can be well maintained when dispersed components are three-dimensionally connected within the elastomer matrix. Polymerization-induced phase separation (PIPS) is a process that controls the domain size and connectivity of phase-separated structures to form bicontinuous nanostructures. However, there have been no attempts to develop ion-conducting phases within elastic systems using PIPS.

[0007] Thus, there is a need for new approaches and methods for providing stable solid-polymer electrolytes and batteries using the same. These and other needs are met, at least in part, by the present disclosure. Summary of the Invention Means to solve the problem

[0008] The present disclosure relates to a polymer composition comprising: a) a matrix comprising an elastomeric polymer; b) a plurality of plastic crystals dispersed within the matrix so as to form a three-dimensionally interconnected phase of plastic crystals, and wherein the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20°C.

[0009] The present disclosure further relates to a polymer composition formed by polymerizing a mixture comprising: a) one or more monomers of formula (I); b) a plurality of plastic crystals; and c) a salt AB. [ka] where R1, R2 and R3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently selected from C1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 optionally substituted with one or more of: heterocycloalkenyl, aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or null, wherein Y is OR, R, R'OR'', C(O)R, N(R)(R'"), or CN; where R4 is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R4 is independently and optionally selected from one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4' is (-O-CH2-CH2-)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; wherein R4′ is independently and optionally one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4'' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R is independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Or, where R4'' is P(O)(OR4''')2; where R4''' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein n is 1 to 200; and wherein A is selected from Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof; and wherein B is bistriflimide (TFSI), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl. - ), bis(fluorosulfonyl)imide (FSI - ), triflate (OTf - ), hexafluorophosphate (PF6 - ), hexafluoroarsenate (AsF6 - ), aluminum tetrachloride (AlCl4 - ), boron tetrachloride (BCl4 - ), boron tetrafluoride (BF4 - ), iodide (I - ), chlorate (ClO3 - ), bromate (BrO3 - ), iodate (IO3 - ), difluoro(oxalato)borate (DFOB - ), bis(oxalato)borate (BOB -- ), difluorophosphate (DFP), or a combination thereof.

[0010] Also disclosed herein are embodiments where the mixture further comprises a cross-linking agent. In other embodiments, the cross-linking agent may comprise one or more of the following: [ka]

[0011] In yet another embodiment, the plurality of plastic crystals originates from one or more of the following: [ka]

[0012] Also disclosed herein are solid electrolytes comprising any of the polymer compositions disclosed herein.

[0013] The present disclosure further relates to electrochemical cells containing solid electrolytes comprising the polymer compositions disclosed herein.

[0014] In certain embodiments disclosed herein, an electrochemical cell includes an anode electrode and a cathode electrode; wherein the anode electrode and the cathode electrode are in electrical communication with any of the solid electrolytes disclosed herein. In this exemplary, non-limiting embodiment, the metallic material may include Li, Ca, Na, K, Mg, Zn, Al, alloys thereof, or combinations thereof. In yet another embodiment, the electrochemical cell disclosed herein comprises a battery.

[0015] Additional advantages will be set forth in part in the following description, and in part will be obvious from the description, or may be learned by practice of the embodiments described hereinafter. The advantages described below will be realized and attained by the chemical compositions, methods, and combinations particularly pointed out in the appended claims. It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. [Brief explanation of the drawings]

[0016] [Figure 1A] 1A-1E show the design of an elastomeric electrolyte with embedded plastic crystals. FIG. 1A shows a schematic diagram of the design and structure for a PCEE. The structure of the PCEE is composed of a 3D interconnected plastic crystal phase ( [ka] ) is the elastomer phase ( [ka] ) surrounding the crystalline plastic phase. The plastic crystalline phase supports fast ion-conducting pathways, while the elastomeric phase provides excellent mechanical extensibility. Figure 1B shows a three-dimensional tomographic image of the PCEE fabricated by X-ray microscopy. Figure 1C shows a SEM cross-sectional image of the PCEE film. Figure 1D shows a TEM cross-sectional image of the PCEE film. Figure 1E shows electron energy loss spectroscopy elemental mapping of the TEM image of Figure 1D. [Figure 1B] Figure 1B shows a three-dimensional tomographic image of a PCEE prepared using an X-ray microscope. [Figure 1C] Figure 1C shows an SEM cross-sectional image of the PCEE film. [Figure 1D] Figure 1D shows a cross-sectional TEM image of the PCEE film. [Figure 1E] FIG. 1E shows electron energy loss spectroscopy elemental mapping of the TEM image of FIG. 1D. [Figure 2A] Figures 2A-2C show the fabrication process of in situ-polymerized PCEE in an electrochemical cell. Figure 2A shows a digital photographic image of a homogeneous solution composed of BA, SBN, LiTFSI, PEGDA, and AIBN for in situ polymerization (left) and the hazy-colored PCEE at the bottom of a glass vial after polymerization at 70 °C (right). Figure 2B shows a photographic image of the PCEE, which exhibits mechanical elasticity. Figure 2C shows a schematic diagram of the in situ polymerization process. The solution was injected into an electrochemical cell and then heated in an oven for in situ polymerization. [Figure 2B]Figures 2A-2C show the fabrication process of in situ-polymerized PCEE in an electrochemical cell. Figure 2A shows a digital photographic image of a homogeneous solution composed of BA, SBN, LiTFSI, PEGDA, and AIBN for in situ polymerization (left) and the hazy-colored PCEE at the bottom of a glass vial after polymerization at 70 °C (right). Figure 2B shows a photographic image of the PCEE, which exhibits mechanical elasticity. Figure 2C shows a schematic diagram of the in situ polymerization process. The solution was injected into an electrochemical cell and then heated in an oven for in situ polymerization. [Figure 2C] Figures 2A-2C show the fabrication process of in situ-polymerized PCEE in an electrochemical cell. Figure 2A shows a digital photographic image of a homogeneous solution composed of BA, SBN, LiTFSI, PEGDA, and AIBN for in situ polymerization (left) and the hazy-colored PCEE at the bottom of a glass vial after polymerization at 70 °C (right). Figure 2B shows a photographic image of the PCEE, which exhibits mechanical elasticity. Figure 2C shows a schematic diagram of the in situ polymerization process. The solution was injected into an electrochemical cell and then heated in an oven for in situ polymerization. [Figure 3A] Figures 3A-3C show scanning electron microscope (SEM) images of PCEE at various magnifications showing its detailed morphology. [Figure 3B] Figures 3A-3C show scanning electron microscope (SEM) images of PCEE at various magnifications showing its detailed morphology. [Figure 3C] Figures 3A-3C show scanning electron microscope (SEM) images of PCEE at various magnifications showing its detailed morphology. [Figure 4]Figure 4 shows differential scanning calorimetry (DSC) measurements of BA100, SN100, and embedded PCEE. The original elastomer (BA100), produced by polymerization of BA and PEGDA, has a low glass transition temperature (Tg) of -32°C. SN100 has a plastic crystalline phase (positional order but orientational disorder) in the temperature range from the plastic crystallization temperature (TPC) of -39°C to the melting temperature (Tm) of 25°C. The embedded PCEE exhibits the thermal properties of both BA100 and SN100, indicating the formation of separate phases. [Figure 5A] Figures 5A-5D show thermogravimetric analysis (TGA) measurements of BA100 (Figure 5D), SN100 (Figure 5C), and embedded PCEE (Figures 5A and 5B). The onset temperature of decomposition for SN100 was ~105 °C, indicating low thermal stability. Conversely, thermal decomposition of BA100 began at a high temperature of ~316 °C. PCEE exhibited improved thermal stability compared to pure SN100, indicating the important role of the elastomer as a protective layer for the plastic crystalline SN phase. [Figure 5B] Figures 5A-5D show thermogravimetric analysis (TGA) measurements of BA100 (Figure 5D), SN100 (Figure 5C), and embedded PCEE (Figures 5A and 5B). The onset temperature of decomposition for SN100 was ~105 °C, indicating low thermal stability. Conversely, thermal decomposition of BA100 began at a high temperature of ~316 °C. PCEE exhibited improved thermal stability compared to pure SN100, indicating the important role of the elastomer as a protective layer for the plastic crystalline SN phase. [Figure 5C] Figures 5A-5D show thermogravimetric analysis (TGA) measurements of BA100 (Figure 5D), SN100 (Figure 5C), and embedded PCEE (Figures 5A and 5B). The onset temperature of decomposition for SN100 was ~105 °C, indicating low thermal stability. Conversely, thermal decomposition of BA100 began at a high temperature of ~316 °C. PCEE exhibited improved thermal stability compared to pure SN100, indicating the important role of the elastomer as a protective layer for the plastic crystalline SN phase. [Figure 5D]Figures 5A-5D show thermogravimetric analysis (TGA) measurements of BA100 (Figure 5D), SN100 (Figure 5C), and embedded PCEE (Figures 5A and 5B). The onset temperature of decomposition for SN100 was ~105 °C, indicating low thermal stability. Conversely, thermal decomposition of BA100 began at a high temperature of ~316 °C. PCEE exhibited improved thermal stability compared to pure SN100, indicating the important role of the elastomer as a protective layer for the plastic crystalline SN phase. [Figure 6] Figure 6 shows the Fourier transform infrared spectroscopy (FT-IR) spectra of the BA-based solution, BA100, SN100, and incorporated PCEE. The incorporated PCEE exhibits vibrational peaks originating from the main components (BA, SN, and LiTFSI). The vibrational peak corresponding to the C=N stretching of SN and incorporated PCEE appeared at 2246 cm-1. The C=C stretching vibrational peak of the BA monomer at 1620 cm-1 disappeared due to the conversion of C=C to C-C- upon polymerization. [Figure 7A] Figures 7A–7D show a comparison of the morphology, ionic conductivity, and mechanical properties between the polymerization-derived PCEE and the blend system. Figure 7A shows the morphology of the PCEE. SEM images of the PCEE show continuously connected SN phases within an elastic matrix uniformly developed over a large area through PIPS. Figure 7B shows the morphology of a blend of LiTFSI with an elastic polymer (crosslinked poly(butyl acrylate) and PEGDA) and plastic crystals (SN). The blends were prepared from a mixture of the elastic polymer and SN-LiTFSI in chloroform and then dried. Identical weight ratios of BA, SN, PEGDA, and LiTFSI were used to construct the PCEE and blend system. SEM images of the blends show macrophase separation on the order of μm or greater. Figures 7C–7D compare the ionic conductivity (Figure 7C) and roughness (Figure 7D) between the PCEE and the blend system. [Figure 7B]Figures 7A–7D show a comparison of the morphology, ionic conductivity, and mechanical properties between the polymerization-derived PCEE and the blend system. Figure 7A shows the morphology of the PCEE. SEM images of the PCEE show continuously connected SN phases within an elastic matrix uniformly developed over a large area through PIPS. Figure 7B shows the morphology of a blend of LiTFSI with an elastic polymer (crosslinked poly(butyl acrylate) and PEGDA) and plastic crystals (SN). The blends were prepared from a mixture of the elastic polymer and SN-LiTFSI in chloroform and then dried. Identical weight ratios of BA, SN, PEGDA, and LiTFSI were used to construct the PCEE and blend system. SEM images of the blends show macrophase separation on the order of μm or greater. Figures 7C–7D compare the ionic conductivity (Figure 7C) and roughness (Figure 7D) between the PCEE and the blend system. [Figure 7C] Figures 7A–7D show a comparison of the morphology, ionic conductivity, and mechanical properties between the polymerization-derived PCEE and the blend system. Figure 7A shows the morphology of the PCEE. SEM images of the PCEE show continuously connected SN phases within an elastic matrix uniformly developed over a large area through PIPS. Figure 7B shows the morphology of a blend of LiTFSI with an elastic polymer (crosslinked poly(butyl acrylate) and PEGDA) and plastic crystals (SN). The blends were prepared from a mixture of the elastic polymer and SN-LiTFSI in chloroform and then dried. Identical weight ratios of BA, SN, PEGDA, and LiTFSI were used to construct the PCEE and blend system. SEM images of the blends show macrophase separation on the order of μm or greater. Figures 7C–7D compare the ionic conductivity (Figure 7C) and roughness (Figure 7D) between the PCEE and the blend system. [Figure 7D]Figures 7A–7D show a comparison of the morphology, ionic conductivity, and mechanical properties between the polymerization-derived PCEE and the blend system. Figure 7A shows the morphology of the PCEE. SEM images of the PCEE show continuously connected SN phases within an elastic matrix uniformly developed over a large area through PIPS. Figure 7B shows the morphology of a blend of LiTFSI with an elastic polymer (crosslinked poly(butyl acrylate) and PEGDA) and plastic crystals (SN). The blends were prepared from a mixture of the elastic polymer and SN-LiTFSI in chloroform and then dried. Identical weight ratios of BA, SN, PEGDA, and LiTFSI were used to construct the PCEE and blend system. SEM images of the blends show macrophase separation on the order of μm or greater. Figures 7C–7D compare the ionic conductivity (Figure 7C) and roughness (Figure 7D) between the PCEE and the blend system. [Figure 8A] Figures 8A–8F show the properties of the embedded PCEE. Figure 8A shows the Arrhenius plots of the embedded PCEE and its components (BA100 and SN100) based on measurements of ionic conductivity (σ) versus temperature (T). Figure 8B shows the stress-strain curves of the embedded PCEE and BA100 at an elongation rate of 100 mm min-1. The tensile properties of SN100 could not be measured due to its brittleness. Figure 8C shows photographic images and a construction chart of the ex-situ and embedded PCEE. Figure 8D shows a cross-sectional SEM image of the embedded PCEE in the Li metal anode phase. Figure 8E shows the interfacial adhesion test between the embedded PCEE and Cu foil. The red dotted line indicates the average force per width. Figure 8F shows Nyquist plots of prepared symmetric Li cells constructed with various electrolytes. The solid line corresponds to the equivalent circuit fit. [Figure 8B]Figures 8A–8F show the properties of the embedded PCEE. Figure 8A shows the Arrhenius plots of the embedded PCEE and its components (BA100 and SN100) based on measurements of ionic conductivity (σ) versus temperature (T). Figure 8B shows the stress-strain curves of the embedded PCEE and BA100 at an elongation rate of 100 mm min-1. The tensile properties of SN100 could not be measured due to its brittleness. Figure 8C shows photographic images and a construction chart of the ex-situ and embedded PCEE. Figure 8D shows a cross-sectional SEM image of the embedded PCEE in the Li metal anode phase. Figure 8E shows the interfacial adhesion test between the embedded PCEE and Cu foil. The red dotted line indicates the average force per width. Figure 8F shows Nyquist plots of prepared symmetric Li cells constructed with various electrolytes. The solid line corresponds to the equivalent circuit fit. [Figure 8C] Figures 8A–8F show the properties of the embedded PCEE. Figure 8A shows the Arrhenius plots of the embedded PCEE and its components (BA100 and SN100) based on measurements of ionic conductivity (σ) versus temperature (T). Figure 8B shows the stress-strain curves of the embedded PCEE and BA100 at an elongation rate of 100 mm min-1. The tensile properties of SN100 could not be measured due to its brittleness. Figure 8C shows photographic images and a construction chart of the ex-situ and embedded PCEE. Figure 8D shows a cross-sectional SEM image of the embedded PCEE in the Li metal anode phase. Figure 8E shows the interfacial adhesion test between the embedded PCEE and Cu foil. The red dotted line indicates the average force per width. Figure 8F shows Nyquist plots of prepared symmetric Li cells constructed with various electrolytes. The solid line corresponds to the equivalent circuit fit. [Figure 8D]Figures 8A–8F show the properties of the embedded PCEE. Figure 8A shows the Arrhenius plots of the embedded PCEE and its components (BA100 and SN100) based on measurements of ionic conductivity (σ) versus temperature (T). Figure 8B shows the stress-strain curves of the embedded PCEE and BA100 at an elongation rate of 100 mm min-1. The tensile properties of SN100 could not be measured due to its brittleness. Figure 8C shows photographic images and a construction chart of the ex-situ and embedded PCEE. Figure 8D shows a cross-sectional SEM image of the embedded PCEE in the Li metal anode phase. Figure 8E shows the interfacial adhesion test between the embedded PCEE and Cu foil. The red dotted line indicates the average force per width. Figure 8F shows Nyquist plots of prepared symmetric Li cells constructed with various electrolytes. The solid line corresponds to the equivalent circuit fit. [Figure 8E] Figures 8A–8F show the properties of the embedded PCEE. Figure 8A shows the Arrhenius plots of the embedded PCEE and its components (BA100 and SN100) based on measurements of ionic conductivity (σ) versus temperature (T). Figure 8B shows the stress-strain curves of the embedded PCEE and BA100 at an elongation rate of 100 mm min-1. The tensile properties of SN100 could not be measured due to its brittleness. Figure 8C shows photographic images and a construction chart of the ex-situ and embedded PCEE. Figure 8D shows a cross-sectional SEM image of the embedded PCEE in the Li metal anode phase. Figure 8E shows the interfacial adhesion test between the embedded PCEE and Cu foil. The red dotted line indicates the average force per width. Figure 8F shows Nyquist plots of prepared symmetric Li cells constructed with various electrolytes. The solid line corresponds to the equivalent circuit fit. [Figure 8F]Figures 8A–8F show the properties of the embedded PCEE. Figure 8A shows the Arrhenius plots of the embedded PCEE and its components (BA100 and SN100) based on measurements of ionic conductivity (σ) versus temperature (T). Figure 8B shows the stress-strain curves of the embedded PCEE and BA100 at an elongation rate of 100 mm min-1. The tensile properties of SN100 could not be measured due to its brittleness. Figure 8C shows photographic images and a construction chart of the ex-situ and embedded PCEE. Figure 8D shows a cross-sectional SEM image of the embedded PCEE in the Li metal anode phase. Figure 8E shows the interfacial adhesion test between the embedded PCEE and Cu foil. The red dotted line indicates the average force per width. Figure 8F shows Nyquist plots of prepared symmetric Li cells constructed with various electrolytes. The solid line corresponds to the equivalent circuit fit. [Figure 9] Figure 9 shows the ionic conductivity of the polymer electrolyte as a function of BA:SN (vol%) composition. The ionic conductivity was measured at a gradual increase in SN of 10 vol% from BA100 (matrix phase) to SN100 (core phase). The results showed that the ionic conductivity increased with increasing SN. Although the ionic conductivity was not maximized at the 5:5 point, the increase in conductivity was relatively gradual after BA50SN50 (5:5 point). Therefore, considering the combined contributions of the elastic properties and high ionic conductivity (~10-3 Scm-1), BA50SN50 was selected as the optimal composition. [Figure 10] FIG. 10 shows the X-ray diffraction (XRO) spectra of BA100, SN100, and PCEE. [Figure 11] Figure 11 shows the PCEE flame retardant. It is a photographic image of the flammability test of PCEE. [Figure 12]Figure 12 shows the interfacial adhesion test between ex-situ PCEE and Cu foil. The ex-situ PCEE was sandwiched between two Cu foils. Two free arms of the Cu foil were stretched in a 180-degree peeling test. The adhesion energy is determined by the stable value of the force per width required for extension. The adhesion energy of the ex-situ PCEE was only 2.7 J m-2, which is an order of magnitude lower than that of the embedded PCEE (21.5 J m-2). [Figure 13] Figure 13 shows the cumulative capacity of the symmetric Li cell with the built-in PCEE. The symmetric Li cell was run at a high current density of 10 mAh cm-2 and a capacity of 10 mA cm-2 for all Li plating / stripping (Li ratio passed per cycle: 0.15) at 20 °C. [Figure 14A] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14B]Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14C] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14D] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14E]Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14F] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14G] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14H]Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14I] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 14J] Figures 14A-14J show the built-in PCEE of symmetric Li and asymmetric Li||Cu batteries. Figure 14C shows the cycling performance of symmetric Li batteries with various electrolytes. Inset: Zoomed-in voltage profiles over various times. Figures 14B-14D show plan-view SEM images of SN100 after battery failure (Figure 14B), Li metal anode with 10 mAh cm-2 capacity and ex-situ PCEE after 100 cycles at a current density of 10 mAh cm-2 (Figure 14C), and built-in PCEE (Figure 14D). Inset: Zoomed-in plan-view SEM image. Figure 14E shows the Coulombic efficiency for asymmetric Li||Cu batteries with 4 mAh cm-2 and 10 mAh cm-2 capacities and built-in PCEE at current densities of 2 mA cm-2 and 5 mA cm-2, respectively. Figure 14F shows the corresponding zoomed-in voltage profile. Figures 14G-14I show SEM cross-sectional images of pristine (Figure 14G), Li-plated (Figure 14H), and Li-stripped (Figure 14I) Cu electrodes assembled with built-in PCEEs. Figure 14J shows a schematic of Li-plating and stripping in various electrolytes. [Figure 15A] Figures 15A-15F show the electrochemical characteristics of a symmetric Li battery with an integrated PCEE. Figure 15C shows the time-dependent Nyquist plot of a symmetric Li battery with an integrated PCEE. Figure 15B shows the Nyquist plot of a symmetric Li battery with an integrated PCEE after 25, 75, and 100 cycles. Figure 15C shows the cycling performance of a symmetric Li battery with an integrated PCEE at different current densities. Figure 15D shows the Li plating / stripping voltage hysteresis for an integrated PCEE compared to previously reported literature data. Figure 15E shows the Nyquist plot of a symmetric Li battery before and after 10 mV polarization. Figure 15F shows normal-state current measurements of a symmetric Li battery under 10 mV polarization for 10 hours. EIS was measured at an open-circuit voltage ranging from 10° to 10° Hz with an amplitude of 10 mV. [Figure 15B]Figures 15A-15F show the electrochemical characteristics of a symmetric Li battery with an integrated PCEE. Figure 15C shows the time-dependent Nyquist plot of a symmetric Li battery with an integrated PCEE. Figure 15B shows the Nyquist plot of a symmetric Li battery with an integrated PCEE after 25, 75, and 100 cycles. Figure 15C shows the cycling performance of a symmetric Li battery with an integrated PCEE at different current densities. Figure 15D shows the Li plating / stripping voltage hysteresis for an integrated PCEE compared to previously reported literature data. Figure 15E shows the Nyquist plot of a symmetric Li battery before and after 10 mV polarization. Figure 15F shows normal-state current measurements of a symmetric Li battery under 10 mV polarization for 10 hours. EIS was measured at an open-circuit voltage ranging from 10° to 10° Hz with an amplitude of 10 mV. [Figure 15C] Figures 15A-15F show the electrochemical characteristics of a symmetric Li battery with an integrated PCEE. Figure 15C shows the time-dependent Nyquist plot of a symmetric Li battery with an integrated PCEE. Figure 15B shows the Nyquist plot of a symmetric Li battery with an integrated PCEE after 25, 75, and 100 cycles. Figure 15C shows the cycling performance of a symmetric Li battery with an integrated PCEE at different current densities. Figure 15D shows the Li plating / stripping voltage hysteresis for an integrated PCEE compared to previously reported literature data. Figure 15E shows the Nyquist plot of a symmetric Li battery before and after 10 mV polarization. Figure 15F shows normal-state current measurements of a symmetric Li battery under 10 mV polarization for 10 hours. EIS was measured at an open-circuit voltage ranging from 10° to 10° Hz with an amplitude of 10 mV. [Figure 15D]Figures 15A-15F show the electrochemical characteristics of a symmetric Li battery with an integrated PCEE. Figure 15C shows the time-dependent Nyquist plot of a symmetric Li battery with an integrated PCEE. Figure 15B shows the Nyquist plot of a symmetric Li battery with an integrated PCEE after 25, 75, and 100 cycles. Figure 15C shows the cycling performance of a symmetric Li battery with an integrated PCEE at different current densities. Figure 15D shows the Li plating / stripping voltage hysteresis for an integrated PCEE compared to previously reported literature data. Figure 15E shows the Nyquist plot of a symmetric Li battery before and after 10 mV polarization. Figure 15F shows normal-state current measurements of a symmetric Li battery under 10 mV polarization for 10 hours. EIS was measured at an open-circuit voltage ranging from 10° to 10° Hz with an amplitude of 10 mV. [Figure 15E] Figures 15A-15F show the electrochemical characteristics of a symmetric Li battery with an integrated PCEE. Figure 15C shows the time-dependent Nyquist plot of a symmetric Li battery with an integrated PCEE. Figure 15B shows the Nyquist plot of a symmetric Li battery with an integrated PCEE after 25, 75, and 100 cycles. Figure 15C shows the cycling performance of a symmetric Li battery with an integrated PCEE at different current densities. Figure 15D shows the Li plating / stripping voltage hysteresis for an integrated PCEE compared to previously reported literature data. Figure 15E shows the Nyquist plot of a symmetric Li battery before and after 10 mV polarization. Figure 15F shows normal-state current measurements of a symmetric Li battery under 10 mV polarization for 10 hours. EIS was measured at an open-circuit voltage ranging from 10° to 10° Hz with an amplitude of 10 mV. [Figure 15F]Figures 15A-15F show the electrochemical characteristics of a symmetric Li battery with an integrated PCEE. Figure 15C shows the time-dependent Nyquist plot of a symmetric Li battery with an integrated PCEE. Figure 15B shows the Nyquist plot of a symmetric Li battery with an integrated PCEE after 25, 75, and 100 cycles. Figure 15C shows the cycling performance of a symmetric Li battery with an integrated PCEE at different current densities. Figure 15D shows the Li plating / stripping voltage hysteresis for an integrated PCEE compared to previously reported literature data. Figure 15E shows the Nyquist plot of a symmetric Li battery before and after 10 mV polarization. Figure 15F shows normal-state current measurements of a symmetric Li battery under 10 mV polarization for 10 hours. EIS was measured at an open-circuit voltage ranging from 10° to 10° Hz with an amplitude of 10 mV. [Figure 16] FIG. 16 shows an equivalent circuit for modeling the Nyquist plots of a symmetric Li cell. [Figure 17] Figure 17 shows the characterization of the SEI components of the cycled Li metal anode phase with built-in PCEE and SN100 by XPS. High-resolution Li 1s, C 1s, O 1s, N 1s, and F 1s XPS spectra of the Li metal anode were measured after 100 cycles of a symmetric Li cell with built-in PCEE and SN100 at a capacity of 1 mAhcm-2 and a current density of 1 mAcm-2. [Figure 18A] Figures 18A-18B show the cycling performance of asymmetric Li||Cu cells constructed with SN100. Figure 18A shows the coulombic efficiency as a function of cycle number at 0.5 mA cm-2 as well as 1 mA cm-2. Figure 18B shows the corresponding Li stripping and plating profiles. [Figure 18B] Figures 18A-18B show the cycling performance of asymmetric Li||Cu cells constructed with SN100. Figure 18A shows the coulombic efficiency as a function of cycle number at 0.5 mA cm-2 as well as 1 mA cm-2. Figure 18B shows the corresponding Li stripping and plating profiles. [Figure 19A]Figures 19A-19C show the Li plating and stripping behavior of the trace-Cu (on bare Cu) embedded PCEE. Figure 19A shows the cycling performance of the asymmetric Li||Cu battery at current densities of 0.5 and 1 mA cm, respectively. Figures 19B-19C show the Li stripping and plating profiles for the embedded PCEE at a capacity of 1 mAh cm and a current density of 0.5 mA cm (Figure 19B) and a capacity of 2 mAh cm and a current density of 1 mA cm (Figure 19C). [Figure 19B] Figures 19A-19C show the Li plating and stripping behavior of the trace-Cu (on bare Cu) embedded PCEE. Figure 19A shows the cycling performance of the asymmetric Li||Cu battery at current densities of 0.5 and 1 mA cm, respectively. Figures 19B-19C show the Li stripping and plating profiles for the embedded PCEE at a capacity of 1 mAh cm and a current density of 0.5 mA cm (Figure 19B) and a capacity of 2 mAh cm and a current density of 1 mA cm (Figure 19C). [Figure 19C] Figures 19A-19C show the Li plating and stripping behavior of the trace-Cu (on bare Cu) embedded PCEE. Figure 19A shows the cycling performance of the asymmetric Li||Cu battery at current densities of 0.5 and 1 mA cm, respectively. Figures 19B-19C show the Li stripping and plating profiles for the embedded PCEE at a capacity of 1 mAh cm and a current density of 0.5 mA cm (Figure 19B) and a capacity of 2 mAh cm and a current density of 1 mA cm (Figure 19C). [Figure 20A]Figures 20A-20C show the electrochemical stability of an integrated PCEE paired with a high-voltage NMC-622 cathode. Figure 20A shows an electrochemical flotation experiment conducted using a LiNMC-622 with an integrated PCEE. The cell was charged to 4.2 V at 0.2 C (1 C = 180 mAg-1) and then maintained at progressively higher voltages up to 4.7 V over 10 h. Figure 20B shows the rate performance of a full cell (35 μm-thick Li anode, 25 μm-thick integrated PCEE, and highly loaded NMC-622 (9.7 mg cm-2)) at the same current density in the voltage range of 2.7 to 4.5 V. (Inset: capacity utilization at various areal current densities). Figure 20C shows the cycling performance of a full cell (excess Li; 25 μm thick embedded PCEE, NMC-622 (2.1 mg cm-2)) as a function of cycle number in the voltage range of 2.7 to 4.5 V. The cell maintained a high capacity of ~140 mAh g-1 (82% capacity retention) with a high CE of 99.5% for 100 cycles, confirming stable operation at high voltages. The cell was run at 20°C. [Figure 20B] Figures 20A-20C show the electrochemical stability of an integrated PCEE paired with a high-voltage NMC-622 cathode. Figure 20A shows an electrochemical flotation experiment conducted using a LiNMC-622 with an integrated PCEE. The cell was charged to 4.2 V at 0.2 C (1 C = 180 mAg-1) and then maintained at progressively higher voltages up to 4.7 V over 10 h. Figure 20B shows the rate performance of a full cell (35 μm-thick Li anode, 25 μm-thick integrated PCEE, and highly loaded NMC-622 (9.7 mg cm-2)) at the same current density in the voltage range of 2.7 to 4.5 V. (Inset: capacity utilization at various areal current densities). Figure 20C shows the cycling performance of a full cell (excess Li; 25 μm thick embedded PCEE, NMC-622 (2.1 mg cm-2)) as a function of cycle number in the voltage range of 2.7 to 4.5 V. The cell maintained a high capacity of ~140 mAh g-1 (82% capacity retention) with a high CE of 99.5% for 100 cycles, confirming stable operation at high voltages. The cell was run at 20°C. [Figure 20C]Figures 20A-20C show the electrochemical stability of an integrated PCEE paired with a high-voltage NMC-622 cathode. Figure 20A shows an electrochemical flotation experiment conducted using a LiNMC-622 with an integrated PCEE. The cell was charged to 4.2 V at 0.2 C (1 C = 180 mAg-1) and then maintained at progressively higher voltages up to 4.7 V over 10 h. Figure 20B shows the rate performance of a full cell (35 μm-thick Li anode, 25 μm-thick integrated PCEE, and highly loaded NMC-622 (9.7 mg cm-2)) at the same current density in the voltage range of 2.7 to 4.5 V. (Inset: capacity utilization at various areal current densities). Figure 20C shows the cycling performance of a full cell (excess Li; 25 μm thick embedded PCEE, NMC-622 (2.1 mg cm-2)) as a function of cycle number in the voltage range of 2.7 to 4.5 V. The cell maintained a high capacity of ~140 mAh g-1 (82% capacity retention) with a high CE of 99.5% for 100 cycles, confirming stable operation at high voltages. The cell was run at 20°C. [Figure 21] Figure 21 illustrates the electrochemical oxidation stability. Linear sweep voltammetry (LSV) profiles of BA100, SN100, and Li|| stainless steel battery-integrated PCEE at a scan rate of 1 mVS (inset: LSV profile expanded in the potential range of 4 to 5.5 V). [Figure 22A] 22A-22B show the cycling performance of a Li||LiFePO4 battery at 1C without voltage hold. FIG. 22A shows the capacity and coulombic efficiency as a function of cycle number. FIG. 22B shows the corresponding voltage profile. 1C = 170 mAg-1. [Figure 22B] 22A-22B show the cycling performance of a Li||LiFePO4 battery at 1C without voltage hold. FIG. 22A shows the capacity and coulombic efficiency as a function of cycle number. FIG. 22B shows the corresponding voltage profile. 1C = 170 mAg-1. [Figure 23A]Figures 23A-23B show the electrochemical performance of full cells with high-voltage NMC-83 cathodes. Figure 23A shows the charge and discharge profiles of full cells in the voltage range of 2.7 to 4.3 V at 0.1 mA cm-2. Figure 23B shows the temperature-dependent voltage profiles of full cells charged / discharged at the same temperatures (60 to 0 °C) in the voltage range of 2.7 to 4.5 V. (Inset: Capacity utilization at various temperatures). All full cells were constructed with a 35 μm-thick Li anode; a 25 μm-thick embedded PCEE; and a high loading of NMC-83 (>10 mg cm-2). [Figure 23B] Figures 23A-23B show the electrochemical performance of full cells with high-voltage NMC-83 cathodes. Figure 23A shows the charge and discharge profiles of full cells in the voltage range of 2.7 to 4.3 V at 0.1 mA cm-2. Figure 23B shows the temperature-dependent voltage profiles of full cells charged / discharged at the same temperatures (60 to 0 °C) in the voltage range of 2.7 to 4.5 V. (Inset: Capacity utilization at various temperatures). All full cells were constructed with a 35 μm-thick Li anode; a 25 μm-thick embedded PCEE; and a high loading of NMC-83 (>10 mg cm-2). [Figure 24A]Figures 24A-24D show the results for a high-energy all-solid-state LMB with an elastic electrolyte. Figure 24A shows the cycling performance of a full cell as a function of cycle number in the voltage range of 2.7-4.3 V. The cell was cycled at a current density of 0.1 mA cm-2 for three cycles before initially cycling at 0.5 mA cm-2. Figure 24B shows the rate performance of the full cell in the voltage range of 2.7-4.5 V at the same current density. The inset shows the capacity utilization at various areal current densities. Figure 24C shows a Ragone plot for the full cell at ambient temperature (20-30 °C). The specific energy and power of each reference are displayed within the light-shaded area (blue, polymer / composite electrolyte; gray, inorganic electrolyte). The specific energy and power are normalized by the mass of the cell (anode, solid electrolyte, and cathode), excluding the weight of the cell casing and current collector. Figure 24D shows a schematic diagram of an all-solid-state LMB containing a thin Li metal anode, a thin built-in PCEE, and a highly loaded NMC-83. The full cells with built-in PCEE exhibit even higher specific energy than the typical full cells listed in Figure 25. All full cells were constructed with a 35 μm thick Li anode, a 25 μm thick built-in PCEE, and a highly loaded NMC-83 (>10 mg cm). [Figure 24B]Figures 24A-24D show the results for a high-energy all-solid-state LMB with an elastic electrolyte. Figure 24A shows the cycling performance of a full cell as a function of cycle number in the voltage range of 2.7-4.3 V. The cell was cycled at a current density of 0.1 mA cm-2 for three cycles before initially cycling at 0.5 mA cm-2. Figure 24B shows the rate performance of the full cell in the voltage range of 2.7-4.5 V at the same current density. The inset shows the capacity utilization at various areal current densities. Figure 24C shows a Ragone plot for the full cell at ambient temperature (20-30 °C). The specific energy and power of each reference are displayed within the light-shaded area (blue, polymer / composite electrolyte; gray, inorganic electrolyte). The specific energy and power are normalized by the mass of the cell (anode, solid electrolyte, and cathode), excluding the weight of the cell casing and current collector. Figure 24D shows a schematic diagram of an all-solid-state LMB containing a thin Li metal anode, a thin built-in PCEE, and a highly loaded NMC-83. The full cells with built-in PCEE exhibit even higher specific energy than the typical full cells listed in Figure 25. All full cells were constructed with a 35 μm thick Li anode, a 25 μm thick built-in PCEE, and a highly loaded NMC-83 (>10 mg cm). [Figure 24C]Figures 24A-24D show the results for a high-energy all-solid-state LMB with an elastic electrolyte. Figure 24A shows the cycling performance of a full cell as a function of cycle number in the voltage range of 2.7-4.3 V. The cell was cycled at a current density of 0.1 mA cm-2 for three cycles before initially cycling at 0.5 mA cm-2. Figure 24B shows the rate performance of the full cell in the voltage range of 2.7-4.5 V at the same current density. The inset shows the capacity utilization at various areal current densities. Figure 24C shows a Ragone plot for the full cell at ambient temperature (20-30 °C). The specific energy and power of each reference are displayed within the light-shaded area (blue, polymer / composite electrolyte; gray, inorganic electrolyte). The specific energy and power are normalized by the mass of the cell (anode, solid electrolyte, and cathode), excluding the weight of the cell casing and current collector. Figure 24D shows a schematic diagram of an all-solid-state LMB containing a thin Li metal anode, a thin built-in PCEE, and a highly loaded NMC-83. The full cells with built-in PCEE exhibit even higher specific energy than the typical full cells listed in Figure 25. All full cells were constructed with a 35 μm thick Li anode, a 25 μm thick built-in PCEE, and a highly loaded NMC-83 (>10 mg cm). [Figure 24D]Figures 24A-24D show the results for a high-energy all-solid-state LMB with an elastic electrolyte. Figure 24A shows the cycling performance of a full cell as a function of cycle number in the voltage range of 2.7-4.3 V. The cell was cycled at a current density of 0.1 mA cm-2 for three cycles before initially cycling at 0.5 mA cm-2. Figure 24B shows the rate performance of the full cell in the voltage range of 2.7-4.5 V at the same current density. The inset shows the capacity utilization at various areal current densities. Figure 24C shows a Ragone plot for the full cell at ambient temperature (20-30 °C). The specific energy and power of each reference are displayed within the light-shaded area (blue, polymer / composite electrolyte; gray, inorganic electrolyte). The specific energy and power are normalized by the mass of the cell (anode, solid electrolyte, and cathode), excluding the weight of the cell casing and current collector. Figure 24D shows a schematic diagram of an all-solid-state LMB containing a thin Li metal anode, a thin built-in PCEE, and a highly loaded NMC-83. The full cells with built-in PCEE exhibit even higher specific energy than the typical full cells listed in Figure 25. All full cells were constructed with a 35 μm thick Li anode, a 25 μm thick built-in PCEE, and a highly loaded NMC-83 (>10 mg cm). [Figure 25] Figure 25 shows a comparison of battery performance with previously reported solid-state LMB. [Figure 26A]Figures 26A-26D show a schematic procedure for preparing PCEEs using digital photographic images. PCEEs were prepared in four steps. First, a BA100 solution was prepared, consisting of BA (monomer), PEGDA (crosslinker), AIBN (thermal initiator), and LiTFSI (salt). PEGDA, AIBN, and LiTFSI were dissolved in BA (liquid state) and stirred at room temperature for 1 hour to achieve uniform mixing. Second, an SN100 solution was prepared, consisting of SN (plastic crystal) and LiTFSI (salt). SN was in a crystalline state at room temperature, and then LiTFSI was mixed with SN. 5 vol% fluoroethylene carbonate was also added to prevent side reactions of SN with Li metal. These components were then stirred at 50 °C for 1 hour to produce a homogeneous solution. In the third step, the BA100 and SN100 solutions were combined by adjusting the volume ratio. For BA50SN50, the volume ratio of BA100 to SN100 solution was 1: 1. Finally, the solution was stirred at 50°C for 1 hour and then polymerized at 70°C for 2 hours to form PCEE. [Figure 26B] Figures 26A-26D show a schematic procedure for preparing PCEEs using digital photographic images. PCEEs were prepared in four steps. First, a BA100 solution was prepared, consisting of BA (monomer), PEGDA (crosslinker), AIBN (thermal initiator), and LiTFSI (salt). PEGDA, AIBN, and LiTFSI were dissolved in BA (liquid state) and stirred at room temperature for 1 hour to achieve uniform mixing. Second, an SN100 solution was prepared, consisting of SN (plastic crystal) and LiTFSI (salt). SN was in a crystalline state at room temperature, and then LiTFSI was mixed with SN. 5 vol% fluoroethylene carbonate was also added to prevent side reactions of SN with Li metal. These components were then stirred at 50 °C for 1 hour to produce a homogeneous solution. In the third step, the BA100 and SN100 solutions were combined by adjusting the volume ratio. For BA50SN50, the volume ratio of BA100 to SN100 solution was 1: 1. Finally, the solution was stirred at 50°C for 1 hour and then polymerized at 70°C for 2 hours to form PCEE. [Figure 26C]Figures 26A-26D show a schematic procedure for preparing PCEEs using digital photographic images. PCEEs were prepared in four steps. First, a BA100 solution was prepared, consisting of BA (monomer), PEGDA (crosslinker), AIBN (thermal initiator), and LiTFSI (salt). PEGDA, AIBN, and LiTFSI were dissolved in BA (liquid state) and stirred at room temperature for 1 hour to achieve uniform mixing. Second, an SN100 solution was prepared, consisting of SN (plastic crystal) and LiTFSI (salt). SN was in a crystalline state at room temperature, and then LiTFSI was mixed with SN. 5 vol% fluoroethylene carbonate was also added to prevent side reactions of SN with Li metal. These components were then stirred at 50 °C for 1 hour to produce a homogeneous solution. In the third step, the BA100 and SN100 solutions were combined by adjusting the volume ratio. For BA50SN50, the volume ratio of BA100 to SN100 solution was 1: 1. Finally, the solution was stirred at 50°C for 1 hour and then polymerized at 70°C for 2 hours to form PCEE. [Figure 26D] Figures 26A-26D show a schematic procedure for preparing PCEEs using digital photographic images. PCEEs were prepared in four steps. First, a BA100 solution was prepared, consisting of BA (monomer), PEGDA (crosslinker), AIBN (thermal initiator), and LiTFSI (salt). PEGDA, AIBN, and LiTFSI were dissolved in BA (liquid state) and stirred at room temperature for 1 hour to achieve uniform mixing. Second, an SN100 solution was prepared, consisting of SN (plastic crystal) and LiTFSI (salt). SN was in a crystalline state at room temperature, and then LiTFSI was mixed with SN. 5 vol% fluoroethylene carbonate was also added to prevent side reactions of SN with Li metal. These components were then stirred at 50 °C for 1 hour to produce a homogeneous solution. In the third step, the BA100 and SN100 solutions were combined by adjusting the volume ratio. For BA50SN50, the volume ratio of BA100 to SN100 solution was 1: 1. Finally, the solution was stirred at 50°C for 1 hour and then polymerized at 70°C for 2 hours to form PCEE. [Figure 27A]Figures 27A-B show the galvanostatic charge / discharge profile of LiNi0.88Co0.09Al0.03O2 (NCA-88) at 0.2 C (Figure 27A) and the cycling performance of the full battery (Li / / integrated PCEE / / NCA-88) as a function of cycle number at 0.2 C in the voltage range of 2.7 to 4.3 V (1 C = 190 mA g-1) (Figure 27B). [Figure 27B] Figures 27A-B show the galvanostatic charge / discharge profile of LiNi0.88Co0.09Al0.03O2 (NCA-88) at 0.2 C (Figure 27A) and the cycling performance of the full battery (Li / / integrated PCEE / / NCA-88) as a function of cycle number at 0.2 C in the voltage range of 2.7 to 4.3 V (1 C = 190 mA g-1) (Figure 27B). [Figure 28] FIG. 28 shows the conductivity as a function of temperature for PCEE systems with single -(Li, Na, and K), di(di)-(Mg and Zn), and trivalent cations (Al).

[0017] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate many aspects described below. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention may be more readily understood by reference to the following detailed description, examples, figures, and claims, as well as their preceding and following descriptions. However, before the articles, systems, and / or methods of the present invention are disclosed and described, it is to be understood that the invention is not limited to the specific or exemplary embodiments of the disclosed articles, systems, and / or methods, which may, of course, vary, unless otherwise specified. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0019] The following description of the present invention is provided as an enabling teaching of the present invention in its best, currently known mode. To this end, those skilled in the art will recognize and appreciate that many variations on the various aspects of the present invention described herein are possible while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired advantages of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Thus, those of ordinary skill in the art will recognize that many modifications and adaptations to the present invention are possible and may even be preferred in certain circumstances and are a part of the present invention. Thus, the following description is offered to illustrate the principles of the present invention and not to limit it.

[0020] As used herein, the terms "optionally" or "optionally" mean that a hereinafter described event or circumstance may or may not occur, and that the description includes cases where the event or circumstance occurs and cases where it does not occur.

[0021] Certain features of the present disclosure that are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the present disclosure that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

[0022] As used in the detailed description and the appended claims, the singular forms "a," "an," and "said" include the plural forms unless the context clearly dictates otherwise. Thus, for example, reference to a "monomer" includes two or more monomers, reference to a "battery" includes two or more batteries, and so on.

[0023] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. The term "comprising" as used in the specification and claims can include the embodiments "consisting of" and "consisting essentially of." Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and the following claims, reference will be made to various terms defined herein.

[0024] The terms "for example" and "such as," and their grammatical equivalents, unless expressly stated otherwise, are understood to be followed by the phrase "without limitation." It is also understood that these phrases are used for descriptive purposes only. It is further understood that the term "exemplary," as used herein, means "an example of," and is not intended to convey an indication of a preferred or ideal embodiment.

[0025] The term "or" means "and / or." References to ranges of values ​​are used as a shorthand method of referring individually to each individual value falling within the range, unless otherwise stated herein, and each individual value is included in the specification as if it were individually recited herein. All range endpoints are included within the range and independently combinable. All methods described herein can be performed in any suitable order unless expressly stated otherwise herein or clearly contradicted by context.

[0026] Reference herein to a range of values ​​is intended to serve as a shorthand method of referring individually to each individual value recited or falling within the range, unless otherwise stated, and each individual value is included in the specification as if it were individually recited. Ranges provided herein are understood to be shorthand expressions for all values ​​within the range. For example, the range 1 to 50 is understood to include any number or combination of numbers from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, or subranges from the group consisting of 10-40, 20-50, 5-35, etc. Similarly, numerical ranges recited herein by endpoints include subranges subsumed within those ranges (e.g., 1 to 5 includes 1 to 1.5, 1.5 to 2, 2 to 2.75, 2.75 to 3, 3 to 3.90, 3.90 to 4, 4 to 4.24, 4.24 to 5, 2 to 5, 3 to 5, 1 to 4, and 2 to 4).

[0027] The organic moieties referred to in defining variable positions within the general formulae described herein (e.g., the term "halogen") are collective terms for the individual substituents contained within the organic moiety. The prefix C before the group or moiety n-m indicates in each case the number of carbon atoms possible in the group or moiety that follows.

[0028] As used herein, the term "ion" refers to any molecule, molecular portion, molecular cluster, molecular complex, moiety, or atom that contains or can be made to contain a charge (positive, negative, or both simultaneously in a single molecule, molecular cluster, molecular complex, or moiety (e.g., zwitterions)). Methods for generating charge on molecules, molecular portions, molecular clusters, molecular complexes, moieties, or atoms are disclosed herein and can be accomplished by methods known in the art, such as, for example, protonation, deprotonation, oxidation, reduction, alkylation, acetylation, esterification, deesterification, hydrolysis, and the like.

[0029] The term "anion" is a type of ion and is included within the meaning of the term "ion." An "anion" is any molecule, portion of a molecule (e.g., a zwitterion), cluster of molecules, molecular complex, moiety, or atom that contains or can be made to contain a net negative charge. The term "anion precursor" is used herein specifically to refer to a molecule that can be converted to an anion through a chemical reaction (e.g., deprotonation).

[0030] The term "cation" is a type of ion and is included within the meaning of the term "ion." A "cation" is any molecule, portion of a molecule (e.g., a zwitterion), cluster of molecules, molecular complex, moiety, or atom that contains or can be made to contain a net positive charge. The term "cation precursor" is used herein specifically to refer to a molecule that can be converted to a cation through a chemical reaction (e.g., protonation or alkylation).

[0031] As used herein, the term "substituted" means that a hydrogen atom has been removed and replaced with a substituent. All permissible substituents of organic compounds are intended to be inclusive. As used herein, "optionally substituted" means unsubstituted or substituted. It is understood that substitution at a given atom is limited by valence. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. Permissible substituents can be one or more and can be the same or different for appropriate organic compounds. For purposes of this disclosure, heteroatoms, such as nitrogen, can have hydrogen substitution and / or any permissible substituent of organic compounds described herein that satisfies the valence of the heteroatom. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. The terms "substituted" or "substituted" also include the implicit meaning that such substitution is in accordance with the allowed valences of the substituted atom and substituents, and that the substitution results in a stable compound, e.g., a compound that is not spontaneously transformed by rearrangement, cyclization, elimination, etc.

[0032] "Z 1 "," "Z 2 "," "Z 3 " and "Z 4 " is used herein as a generic symbol to denote various specific substituents. In certain embodiments, the generic symbol to denote various specific substituents is "R 1 "," "R 2 "," "R 3 " or "R 4 " where n is the number of substituents that follow. These symbols are not limited to those disclosed herein and may be any substituent, and in some cases may be defined as a specific substituent and in other cases may be defined as another substituent.

[0033] The expressions "ambient temperature" and "room temperature" as used herein are understood in the art and generally refer to a temperature, e.g., a temperature near the reaction temperature, i.e., the temperature of the space in which the reaction is carried out, e.g., about 20°C to about 30°C.

[0034] A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -(C=O)NH2 is attached through the carbon of the keto (C=O) group.

[0035] The term "aliphatic" as used herein means a non-aromatic hydrocarbon group (radical) and includes branched and unbranched alkyl, alkenyl, or alkynyl groups. n -C m alkyl" (or "C n-m "), used alone or in combination with other terms, refers to a saturated hydrocarbon group having n to m carbon atoms, which may be linear or branched. n-m and C n -C m It is understood that the terms C1-C are interchangeable and are used simply to indicate that a particular compound has between n and m carbon atoms. 24 (e.g., C1-C 22 , C1-C 20 , C1-C 18 , C1-C 16 , C1-C 14 , C1-C 12 , C1-C 10, C1-C8, C1-C6, or C1-C4) alkyl groups are contemplated. Examples of alkyl moieties include, but are not limited to, chemical groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, teri-butyl, isobutyl, sec-butyl; higher homologs such as 2-methyl-1-butyl, n-pentyl, 3-pentyl, n-hexyl, 1,2,2-trimethylpropyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Alkyl groups can be substituted or unsubstituted. Throughout the specification, "alkyl" is used generally to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are specifically referred to herein by identifying the particular substitutions on the alkyl group. The alkyl group may be substituted with one or more groups, including but not limited to alkyl, alkyl halide, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, provided that the substitutions are sterically compatible and satisfy the chemical bonding and deformation energy rules, as described below.

[0036] The term "heteroaliphatic" refers to an aliphatic moiety containing one or more heteroatoms in the chain, such as amine, carbonyl, carboxy, oxo, thio, phosphate, phosphonate, nitrogen, phosphorus, silicon, or boron atoms in place of carbon atoms. In certain embodiments, the only heteroatom is nitrogen. In certain embodiments, the only heteroatom is oxygen. In certain embodiments, the only heteroatom is sulfur. Herein, "heteroaliphatic" is intended to include, but is not limited to, heteroalkyl, heteroalkenyl, heteroalkynyl, heterocycloalkyl, heterocycloalkenyl, and heterocycloalkynyl moieties. In certain embodiments, "heteroaliphatic" is used to refer to heteroaliphatic groups (cyclic, acyclic, substituted, unsubstituted, branched, or unbranched) having 1 to 20 carbon atoms. In certain embodiments, heteroaliphatic groups are optionally substituted in a manner to form stable moieties. Non-limiting examples of heteroaliphatic moieties are polyethylene glycol, polyalkylene glycol, amides, polyamides, polylactic acid, polyglycolic acid, thioethers and ethers, alkyl-heterocycle-alkyl, -O-alkyl-O-alkyl, alkyl-O-haloalkyl, and the like.

[0037] Throughout the specification, "alkyl" is used generically to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are specifically referred to herein by identifying particular substitutions on the alkyl group.

[0038] For example, the term "halogenated alkyl" specifically refers to an alkyl group substituted with one or more halides, such as fluorine, chlorine, bromine, or iodine. "Haloalkyl" refers to a branched or straight-chain alkyl group substituted with one or more halo atoms, up to the maximum allowable number of halogen atoms, as described above. Examples of haloalkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl, and dichloropropyl. "Perhaloalkyl" refers to an alkyl group in which all hydrogen atoms have been replaced with halogen atoms. Examples include, but are not limited to, trifluoromethyl and pentafluoroethyl.

[0039] The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below. When "alkyl" is used in some instances and specific terms such as "alkylalcohol" are used in other instances, this does not mean that the term "alkyl" does not also refer to "alkylalcohol" and similar specific terms.

[0040] The "C" used here n -C m "Alkenyl" refers to an alkyl group having one or more carbon-carbon double bonds and having n to m carbons. Alkenyl may be straight or branched. Unless otherwise specified, C2-C 24 (For example, C2-C 22 , C2-C 20 , C2-C 18 , C2-C 16 , C2-C 14 , C2-C 12 , C2-C 10Alkenyl groups of C2-C8, C2-C6, or C2-C4 are contemplated. The alkenyl group may contain one or more unsaturated bonds.For example, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl thenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and 1-ethyl-2-methyl-2-propenyl.The term "vinyl" refers to a group having the structure -CH=CH; 1-propenyl refers to a group having the structure -CH=CH-CH, and 2-propenyl refers to a group having the structure -CH-CH=CH. (Z. 1 Z 2 )C=C(Z 3 Z 4 Asymmetric structures, such as alkene, are intended to include both the E and Z isomers. This can be assumed in the structural formulas herein where an asymmetric alkene is present, or can be shown explicitly with the bond symbol C=C. Examples of alkenyl groups include, but are not limited to, ethenyl, n-propenyl, isopropenyl, n-butenyl, sobutenyl, and the like. In various embodiments, the alkenyl moiety contains 2 to 6, 2 to 4, or 2 to 3 carbon atoms. Alkenyl groups can be substituted with one or more groups, including, but not limited to, alkyl, alkyl halide, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, thiol, or phosphonyl.

[0041] The "C" used here n -C m "Alkynyl" refers to an alkyl group having n to m carbons and having one or more carbon-carbon triple bonds. The alkynyl may be a straight or branched chain hydrocarbon moiety containing a triple bond. Unless otherwise specified, C2-C 24 (For example, C2-C 24 , C2-C 20 , C2-C 18 , C2-C 16 , C2-C 14 , C2-C 12 , C2-C 10Alkynyl groups of C2-C8, C2-C6, or C2-C4 are contemplated. The alkynyl group may contain one or more unsaturated bonds. Examples include C2-C6 alkynyls such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, and 2-butynyl. Pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2 and C2-C6-alkynyl, such as 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2-propynyl. In various embodiments, the alkynyl moiety contains 2 to 6, 2 to 4, or 2 to 3 carbon atoms. Alkynyl groups may be substituted with one or more groups including, but not limited to, alkyl, alkyl halide, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, as described below.

[0042] As used herein, alone or in combination with other terms, "C n -C mThe term "alkylene" refers to, but is not limited to, a divalent alkyl linking group having n to m carbons. Examples of alkylene groups include ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, 2-methyl-propane-1,3-diyl, and the like. In various embodiments, the alkylene moiety contains 2 to 6, 2 to 4, 2 to 3, 1 to 6, 1 to 4, or 1 to 2 carbon atoms.

[0043] As used herein, alone or in combination with other terms, "C n -C m The term "alkoxy" refers to a group of the formula -O-alkyl, where the alkyl group has n to m carbon atoms. In other words, the term alkoxy as used herein refers to an alkyl group attached through a single, terminal ether linkage; i.e., an "alkoxy" group is a group of the formula Z 1 -O- group, where Z 1 is unsubstituted or substituted alkyl as defined above. Unless otherwise specified, Z 1 is C1-C 24 (e.g., C1-C 22 , C1-C 20 , C1-C 18 , C1-C 16 , C1-C 14 , C1-C 12 , C1-C 10, C1-C8, C1-C6, or C1-C4) alkyl groups are contemplated, for example, methoxy, ethoxy, propoxy, 1-methyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1-dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy, 2,2-dimethyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy, 3- Examples of alkoxy groups include methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy. In other embodiments, exemplary alkoxy groups include methoxy, ethoxy, propoxy (e.g., w-propoxy and isopropoxy), tert-butoxy, and the like. In various embodiments, alkyl groups have 1 to 6, 1 to 4, or 1 to 3 carbon atoms.

[0044] The term "cyclic group" is used herein to refer to aryl groups, or non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both. Cyclic groups have one or more ring systems that may be substituted or unsubstituted. Cyclic groups can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups.

[0045] As used herein, "aryl" refers to an aromatic ring system ("C 6-14"C6 aryl" refers to a radical of a monocyclic or dodecapolycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 electrons shared in the cyclic arrangement) having 6 to 14 cyclic carbon atoms and 0 heteroatoms. In certain embodiments, an aryl group has 6 cyclic carbon atoms ("C6 aryl," e.g., phenyl). In certain embodiments, an aryl group has 10 cyclic carbon atoms ("C6 aryl," e.g., phenyl). 10 aryl" e.g., naphthyl such as 1-naphthyl and 2-naphthyl). In certain embodiments, the aryl group has 14 ring carbon atoms ("C 14 "Aryl" includes ring systems in which an aryl ring, as defined above, is fused to one or more cycloalkyl or heterocyclic groups, where the radical or point of attachment is on the aryl ring, and in this case the number of carbon atoms is designated subsequently by the number of carbon atoms in the aryl ring system. One or more of the fused cycloalkyl or heterocyclic groups may be 4 to 7-membered saturated or partially unsaturated cycloalkyl or heterocyclic groups.

[0046] "Arylalkyl" refers to an alkyl group, as defined herein, substituted with an aryl group, as defined herein, or an aryl group, as defined herein, substituted with an alkyl group, as defined herein.

[0047] The term "heterocycle" refers to saturated and partially saturated heteroatom-containing ring radicals containing one, two, three, or four heteroatoms independently selected from nitrogen, sulfur, boron, silicon, and oxygen. Heterocyclic rings include monocyclic 3- to 10-membered rings as well as 5- to 16-membered bicyclic ring systems, which can include bridged, fused, and spiro-fused bicyclic ring systems. Rings containing -OO-, -OS-, or -SS- moieties are not included. Examples of saturated heterocyclic groups include saturated 3- to 6-membered heteromonocyclic groups containing one to four nitrogen atoms (e.g., pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, piperazinyl); saturated 3- to 6-membered heteromonocyclic groups containing one to two oxygen atoms and one to three nitrogen atoms (e.g., morpholinyl); and saturated 3- to 6-membered heteromonocyclic groups containing one to two sulfur atoms and one to three nitrogen atoms (e.g., thiazolidinyl). Examples of partially saturated heterocyclic radicals include, but are not limited to, dihydrothienyl, dihydropyranyl, dihydrofuryl, and dihydrothiazolyl. Examples of partially saturated and saturated heterocyclic groups include pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, pyrazolidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, thiazolidinyl, dihydrothienyl, 2,3-dihydro-benzo[1,4]dioxanyl, indolinyl, isoindolinyl, dihydrobenzothienyl, dihydrobenzofuryl, isochromanyl, chromanyl, 1,2 1,2,3,4-Trihydroquinolyl, 1,2,3,4-tetrahydro-isoquinolyl, 1,2,3,4-tetrahydro-quinolyl, 2,3,4,4a,9,9a-hexahydro-1H-3-aza-fluorenyl, 5,6,7-trihydro-1,2,4-triazolo[3,4-a]isoquinolyl, 3,4-dihydro-2H-benzo[1,4]oxazinyl, benzo[1,4]dioxanyl, 2,3-dihydro-1H-1 l'-benzo[d]isothiazol-6-yl, dihydropyranyl, dihydrofuryl and dihydrothiazolyl.

[0048] "Heterocycle" also includes groups in which a heterocyclic radical is fused / condensed with an aryl or carbocycle radical, where the point of attachment is the heterocycle ring. "Heterocycle" also includes groups in which a heterocyclic radical is fused / condensed with an oxo group (i.e., [ka] ) is also included. For example, partially unsaturated fused heterocyclic groups containing 1 to 5 nitrogen atoms, such as indoline or isoindoline; partially unsaturated fused heterocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms; partially unsaturated fused heterocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms; and saturated fused heterocyclic groups containing 1 to 2 oxygen or sulfur atoms.

[0049] The term "heterocycle" also includes "bicyclic heterocycles." The term "bicyclic heterocycle" means a heterocycle as defined herein in which one bridged, fused, or spirocyclic portion of the heterocycle is present. The bridged, fused, or spirocyclic portion of the heterocycle may be a carbocycle, heterocycle, or aryl group resulting in a stable molecule. Unless excluded by context, the term "heterocycle" includes bicyclic heterocycles. Bicyclic heterocycles include groups in which the fused heterocycle is replaced with an oxo group. Non-limiting examples of bicyclic heterocycles are: [ka]

[0050] "Heterocyclealkyl" refers to an alkyl group, as defined herein, substituted with a heterocycle group, as defined herein, or a heterocycle group, as defined herein, substituted with an alkyl group, as defined herein.

[0051] The term "heteroaryl" refers to a stable aromatic ring system containing 1, 2, 3, or 4 heteroatoms independently selected from O, N, and S, wherein the ring nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom is optionally quaternized. For example, unsaturated 5- to 6-membered heteromonocyclyl groups containing 1 to 4 nitrogen atoms, such as pyrrolyl, imidazolyl, pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, and triazolyl [e.g., 4H-1,2,4-triazolyl, H-1,2,3-triazolyl, and 2H-1,2,3-triazolyl]; unsaturated 5- to 6-membered heteromonocyclic groups containing an oxygen atom, such as pyranyl, 2-furyl, and 3-furyl; and unsaturated 5- to 6-membered heteromonocyclic groups containing a sulfur atom, such as 2-thienyl and 3-thienyl. and the like; unsaturated 5- to 6-membered heteromonocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as oxazolyl, isoxazolyl, oxadiazolyl [e.g., 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl]; unsaturated 5- to 6-membered heteromonocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms, such as thiazolyl, thiadiazolyl [e.g., 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl]. In certain embodiments, the "heteroaryl" group is an 8-, 9-, or 10-membered bicyclic ring system. Examples of 8-, 9- or 10-membered bicyclic heteroaryl groups include benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, quinolinyl, isoquinolinyl, benzofuranyl, indolyl, indazolyl, and benzotriazolyl.

[0052] "Heteroarylalkyl" refers to an alkyl group, as defined herein, substituted with a heteroaryl group, as defined herein, or a heteroaryl group, as defined herein, substituted with an alkyl group, as defined herein.

[0053] As used herein, "carbocyclic," "carbocycle," or "cycloalkyl" includes saturated or partially unsaturated (i.e., non-aromatic) groups containing all carbon ring atoms and 3 to 14 ring carbon atoms and, in non-aromatic ring systems, 0 heteroatoms ("C3-14 cycloalkyl"). In certain embodiments, a cycloalkyl group has 3 to 10 ring carbon atoms ("C3-10 cycloalkyl"). In certain embodiments, a cycloalkyl group has 3 to 9 ring carbon atoms ("C3-9 cycloalkyl"). In certain embodiments, a cycloalkyl group has 3 to 8 ring carbon atoms ("C3-8 cycloalkyl"). In certain embodiments, a cycloalkyl group has 3 to 7 ring carbon atoms ("C3-7 cycloalkyl"). In certain embodiments, a cycloalkyl group has 3 to 6 ring carbon atoms ("C3-6 cycloalkyl"). In certain embodiments, a cycloalkyl group has 4 to 6 ring carbon atoms ("C4-6 cycloalkyl"). In certain embodiments, a cycloalkyl group has 5 to 6 ring carbon atoms ("C cycloalkyl"). In certain embodiments, a cycloalkyl group has 5 to 10 ring carbon atoms ("C cycloalkyl"). Exemplary C cycloalkyl groups include, but are not limited to, cyclopropyl (C), cyclopropenyl (C), cyclobutyl (C), cyclobutenyl (C), cyclopentyl (C), cyclopentenyl (C), cyclohexyl (C), cyclohexenyl (C), cyclohexadienyl (C), and the like. Exemplary C cycloalkyl groups include, but are not limited to, the aforementioned C cycloalkyl groups as well as cycloheptyl (C), cycloheptenyl (C), cycloheptadienyl (C), cycloheptatrienyl (C), cyclooctyl (C), cyclooctenyl (C), and the like. Exemplary C3-10 cycloalkyl groups include, but are not limited to, the aforementioned C3-8 cycloalkyl groups as well as cyclononyl (C9) and cyclononenyl (C9), cyclodecyl (C10), cyclodecenyl (C10), and the like.As noted in the examples above, in certain embodiments, a cycloalkyl group may be saturated or contain one or more carbon-carbon double bonds. The term "cycloalkyl" further includes ring systems in which a cycloalkyl ring is fused to a heterocycle, aryl, or heteroaryl ring, as defined above, and the point of attachment is on the cycloalkyl ring; in such cases, the carbon number is followed by the number of carbons in the carbocyclo ring system. The term "cycloalkyl" further includes ring systems in which a cycloalkyl ring has a spirocyclic heterocycle, aryl, or heteroaryl ring, as defined above, and the point of attachment is on the cycloalkyl ring; in such cases, the carbon number is followed by the number of carbons in the carbocyclo ring system. The term "cycloalkyl" also includes bicyclic or polycyclic fused, bridged, or spiro ring systems containing 5 to 14 carbon atoms and zero heteroatoms in the non-aromatic ring system. Representative examples of "cycloalkyl" include, but are not limited to, the following: [ka]

[0054] The term "bicyclic" refers to a ring system in which two rings are fused together, each ring being independently selected from carbocycle, heterocycle, aryl, and heteroaryl. Non-limiting examples of bicyclic groups are: [ka]

[0055] The term "amine" or "amino" as used herein refers to a group of the formula -NR 1 R 2 where R 1 and R 2 may each be a substituent as described herein, for example, hydrogen, alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above. An "amide" is -C(O)NR1 R 2 is.

[0056] The term "anhydride" as used herein refers to a compound of formula Z 1 C(O)OC(O)Z 2 where Z 1 and Z 2 may independently be an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group, as described above.

[0057] The term "cyclic anhydride" as used herein is represented by the following chemical formula: [ka] where Z 1 may be an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above.

[0058] The term "azide" as used herein refers to the formula -N=N=N.

[0059] The term "aldehyde" as used herein has the chemical formula -C(O)H. Throughout this specification, "C(O)" or "CO" is a shorthand notation for C=O, which is also referred to herein as "carbonyl."

[0060] As used herein, the term "carboxylic acid" has the formula -C(O)OH. As used herein, a "carboxylate" or "carboxyl" group has the formula -C(O)O-.

[0061] As used herein, the term "ester" refers to an ester of the formula -OC(O)R 1 or -C(O)OR 1 where R 1may be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above.

[0062] The term "ether" as used herein refers to a compound of the formula R 1 OR 2 where R 1 and R 2 may independently be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above.

[0063] The term "epoxy" or "epoxide" as used herein refers to a cyclic ether having a three-atom ring and can be represented by the following chemical formula: [ka] where Z 1 , Z 2 , Z 3 and Z 4 may independently be an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group, as described above.

[0064] The term "ketone" as used herein refers to a ketone having the formula R 1 C(O)R 2 where R 1 and R 2 may independently be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above.

[0065] The terms "halide," "halogen," or "halo" as used herein refer to fluorine, chlorine, bromine, and iodine.

[0066] The term "hydroxyl" as used herein is represented by the chemical formula --OH.

[0067] The term "nitro" as used herein has the chemical formula -NO2.

[0068] The term "phosphonyl" refers to a group having the chemical formula -P(O)(OZ 1 )2, where Z 1 may be hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above.

[0069] As used herein, the term "silyl" refers to a group of the formula -SiZ 1 Z 2 Z 3 where Z 1 , Z 2 , and Z 3 may independently be hydrogen, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groups as described above.

[0070] The term "sulfonyl" or "sulfone" refers to a group having the chemical formula -S(O)Z 1 is used herein to refer to a sulfo-oxo group represented by the formula: 1 may be hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group as described above.

[0071] As used herein, the term "sulfide" includes compounds of the formula -S-.

[0072] The term "thio" as used herein refers to a group of formula --SH.

[0073] The "C" used here n -C m The term "alkylthio" refers to a group of the formula -S-alkyl, where the alkyl group has n to m carbon atoms. In various embodiments, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.

[0074] The "C" used here n -C m The term "alkylsulfonyl" refers to a group of formula -S(O)-alkyl, where the alkyl group has n to m carbon atoms. In various embodiments, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.

[0075] The "C" used here n -C m The term "alkylsulfonyl" refers to a group of formula -S(O)-alkyl, where the alkyl group has n to m carbon atoms. In various embodiments, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.

[0076] The term "carbamyl" as used herein refers to a group of formula -C(O)NH2.

[0077] The term "carbonyl" as used herein, alone or in combination with other terms, refers to a -C(=O)- group, which can also be written as C(O).

[0078] The term "carboxy" as used herein refers to a group of formula -C(O)OH.

[0079] As used herein, "halogen" refers to F, Cl, Br, or I.

[0080] The term "sulfonylamino" or "sulfonamide" as used herein is represented by the formula -S(O)2NH-.

[0081] The "R" used here 1 "," "R 2 "," "R 3 "," "R n " etc. (where n is an integer) can independently have one or more of the groups listed above. For example, R 1 When is a linear alkyl group, one of the hydrogen atoms of the alkyl group can optionally be replaced with a hydroxyl group, an alkoxy group, an amine group, an alkyl group, a halide, etc. Depending on the group selected, the first group can be contained within the second group, or the first group can be pendant (i.e., attached) to the second group. For example, in the phrase "an alkyl group comprising an amino group," the amino group can be contained within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The properties of the selected group will determine whether the first group is embedded in or attached to the second group.

[0082] Unless otherwise specified, chemical formulas having chemical bonds shown only with solid lines, and not with wedges or dashed lines, contemplate each possible stereoisomer or mixture of stereoisomers (e.g., each enantiomer, each diastereomer, each meso compound, racemic mixture, or scalenic mixture).

[0083] As used herein, "phase" refers to a region of material having a substantially uniform composition that is generally a distinct and physically separate part of a heterogeneous system. The term "phase" does not imply that the materials comprising the phase are chemically pure, but merely that the chemical and / or physical properties of the materials comprising the phase are essentially uniform throughout the material, and that such chemical and / or physical properties are significantly different from the chemical and / or physical properties of other phases within the material. Examples of physical properties include density, thickness, aspect ratio, specific surface area, porosity, dimensions, elasticity, modulus, and ionic conductivity. Examples of chemical properties include chemical composition.

[0084] The terms "olefinically unsaturated group" or "ethylenically unsaturated group" are used broadly herein and are intended to encompass any group containing a carbon-carbon double bond group (>C=C< group). Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acrylate, (meth)acrylamide, (meth)acryloyl, allyl, vinyl, styrenyl, or other >C=C< containing groups.

[0085] "Polymer" means a substance formed by the polymerization of one or more monomers.

[0086] The term "(co)polymer" includes homopolymers, copolymers or mixtures thereof.

[0087] The term "(meth)acrylic..." includes "acrylic...", "methacrylic..." or mixtures thereof.

[0088] The term "prepolymer" is used herein to refer to a polymer having reactive groups available for bond-forming reactions that are crosslinked (inter- and / or intramolecular crosslinking). This does not mean that the prepolymer is not already a polymer (e.g., a monomer or polymer precursor). Rather, a "prepolymer" contains multiple crosslinkable groups and can be cured (e.g., crosslinked) to obtain a crosslinked polymer having an even higher molecular weight than the starting polymer.

[0089] As used herein, the "molecular weight" of a polymeric material (including monomeric or macromonomeric materials) is used unless otherwise specifically mentioned or test conditions are otherwise indicated. 1 It refers to the number average molecular weight as determined by H NMR spectroscopy.

[0090] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the present disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, all numerical values ​​inherently contain certain errors necessarily resulting from the standard deviation found in such testing measurements. Furthermore, when numerical ranges of varying scope are set forth herein, it is contemplated that any combination of these values, inclusive of the recited values, may be used. Ranges may also be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value.

[0091] Similarly, when values ​​are expressed as approximations by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each range are significant both in relation to the other endpoint, and independently of the other endpoint. Unless otherwise expressly stated, the term "about" means within 5% (e.g., within 2% or 1%) of the particular value modified by the term "about."

[0092] The term "composition," as used herein, is intended to encompass not only a product containing specified ingredients in specified amounts, but also any product that is produced, directly or indirectly, by combining specified ingredients in specified amounts.

[0093] References in the specification and final claims to parts by weight of a particular element or component in a composition indicate the weight relationship between the element or component and any other element or component in the composition or article to which the parts by weight are expressed. Thus, in a mixture containing 2 parts by weight of component X and 5 parts by weight of component Y, components X and Y are present in a weight ratio of 2:5, whether or not they contain additional components.

[0094] Weight percent (wt.%) of an ingredient is based on the total weight of the formulation or composition in which it is included, unless otherwise specified.

[0095] When an element is referred to as being "connected" or "coupled" to another element, it should be understood that this means that the element can be directly connected or coupled to the other element, or that there can be intervening elements. Conversely, when an element is referred to as being "directly connected" or "directly coupled" to another element, it means that there are no intervening elements between them. Other words used to describe the relationship between elements or layers should be interpreted in a similar manner (e.g., "between" and "immediately between," "adjacent" and "directly adjacent," "on" and "directly above"). As used herein, the term "and / or" includes one or more, any and all combinations of the associated listed items.

[0096] It will be understood that terms such as "first," "second," and the like can be used herein to describe various elements, components, regions, layers, and / or sections. Such elements, components, regions, layers, and / or sections are not limited to such terms. Such terms are used only to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be referred to as a second element, component, region, layer, or section without departing from the teachings of the exemplary embodiments.

[0097] As used herein, the term "substantially" means that the events or circumstances hereinafter described occur completely, or that the events or circumstances hereinafter described generally, typically, or roughly occur.

[0098] Additionally, the term "substantially" can refer, in certain embodiments, to at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% of a referenced property, ingredient, composition, or other term used to characterize or quantify the amount.

[0099] In other embodiments, the term "substantially free" as used herein, when used in connection with a composition or a component of a composition that is substantially absent, is intended to refer to an amount of about 1% by weight, e.g., less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.05% by weight, or less than about 0.01% by weight of the referenced substance, based on the total weight of the composition.

[0100] In other embodiments, the term "substantially free" as used herein, when used in connection with a surface that is substantially free of defects or substantially free of dendrites, is intended to refer to a surface having, for example, less than about 5% defects or dendrites, less than about 4.5% defects or dendrites, less than about 4% defects or dendrites, less than about 3.5% defects or dendrites, less than about 3% defects or dendrites, less than about 2.5% defects or dendrites, less than about 2% defects or dendrites, less than about 1.5% defects or dendrites, less than about 1% defects or dendrites, less than about 0.5% defects or dendrites, less than about 0.1% defects or dendrites, less than about 0.05% defects, or less than about 0.01% defects or dendrites of the entire surface.

[0101] Although aspects of the invention may be described and claimed in particular statutory classifications, such as systems statutory classifications, this is merely for convenience, and one of ordinary skill in the art will understand that each aspect of the invention may be described and claimed in any classification. Unless expressly stated otherwise, methods and aspects described herein should not be construed as requiring that their steps be performed in a particular order. Thus, if a method claim does not specifically recite in the claim or description that the steps are limited to a particular order, no order should be inferred in any respect. This applies to all possible implicit bases of interpretation, including questions of logic related to the sequence of steps or operational flow, the ordinary meaning ascribed to grammatical structure or punctuation, and the number or type of aspects described in the specification.

[0102] The present invention may be understood more readily by reference to the following detailed description of various aspects of the invention and the examples contained therein, as well as the drawings and their preceding and subsequent descriptions.

[0103] As noted above, in one embodiment, a polymer composition is disclosed that comprises: a) a matrix comprising an elastomeric polymer; and b) a plurality of plastic crystals dispersed within the matrix to form a three-dimensionally interconnected phase of plastic crystals, wherein the polymer composition exhibits an ionic conductivity of about 1.1 mS / cm or greater at about 20°C.

[0104] In certain embodiments, the polymer compositions disclosed herein may exhibit an ionic conductivity of from about 1.0 mS / cm to about 10 mS / cm, including exemplary values ​​of about 1.5 mS / cm, about 2.0 mS / cm, about 2.5 mS / cm, about 3.0 mS / cm, about 3.5 mS / cm, about 4.0 mS / cm, about 4.5 mS / cm, about 5.0 mS / cm, about 5.5 mS / cm, about 6.0 mS / cm, about 6.5 mS / cm, about 7.0 mS / cm, about 7.5 mS / cm, about 8.0 mS / cm, about 8.5 mS / cm, about 9.0 mS / cm, and about 9.5 mS / cm. In other embodiments, the polymer compositions disclosed herein have a viscosity of greater than about 1 mS / cm, greater than about 1.1 mS / cm, greater than about 1.2 mS / cm, greater than about 1.3 mS / cm, greater than about 1.4 mS / cm, greater than about 1.5 mS / cm, greater than about 1.6 mS / cm, greater than about 1.6 mS / cm, greater than about 1.7 mS / cm, greater than about 1.8 mS / cm, greater than about 1.9 mS / cm, greater than about 2.0 mS / cm, greater than about 2.1 mS / cm, greater than about 2.2 mS / cm, greater than about 2.3 mS / cm, greater than about 2.4 mS / cm. In other embodiments, the polymers disclosed herein may exhibit an ionic conductivity of greater than about 2.5 mS / cm, greater than about 2.6 mS / cm, greater than about 2.7 mS / cm, greater than about 2.8 mS / cm, greater than about 2.9 mS / cm, greater than about 3.0 mS / cm, greater than about 3.1 mS / cm, greater than about 3.2 mS / cm, greater than about 3.3 mS / cm, greater than about 3.4 mS / cm, greater than about 3.5 mS / cm, greater than about 3.6 mS / cm, greater than about 3.7 mS / cm, greater than about 3.8 mS / cm, greater than about 3.9 mS / cm, or even greater than about 4.0 mS / cm. In other embodiments, the ionic conductivity of the polymers disclosed herein may be greater than about 5.0 mS / cm.

[0105] In yet another embodiment, the elastomeric polymer may be derived from at least one monomer comprising formula (I): [ka] where R1, R2 and R3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently selected from C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10wherein X is C(O), O, or null; and wherein Y is OR, R, R'OR'', C(O)R, N(R)(R'''), or CN; wherein R is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R4 is independently and optionally selected from one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4' is (-O-CH2-CH2-)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; wherein R4′ is independently and optionally one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4'' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10wherein R is independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 or wherein R is P(O)(OR'''); substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; or wherein R is P(O)(OR'''); where R4''' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, and wherein n is 1 to 200.

[0106] In yet other embodiments, n can be between 1 and 200, with exemplary values ​​of 2, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, and 190. Any value between any two of the above disclosed values ​​is understood to be disclosed as well.

[0107] In yet another embodiment, R1, R2, and R3 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, C 1-5 Heteroalkyl, C 6-14 Aryl, C 1-13 Heteroaryl, C 6-14 Aryloxy, C 3-10 Cycloalkyl, C 3-10 Heterocycloalkyl, C 3-10 Cycloalkenyl, C 3-10 In another embodiment, R1, R2, and R3 are each selected from heterocycloalkenyl, halide, or amine. In another embodiment, R1, R2, and R3 are each hydrogen. In another embodiment, at least one of R1, R2, and R3 is hydrogen. In yet another embodiment, at least one of R1, R2, and R3 is a halide. In yet another embodiment, at least one of R1, R2, and R3 is an amine. In yet another embodiment, any, all, or at least one of R1, R2, and R3 can be substituted with any of the functional groups disclosed above.

[0108] In another embodiment, when X is C(O), it may be selected from YOR, R'OR, or N(R)(R'). In yet another embodiment, when X is O, it may be YC(O)R. In yet another embodiment, when X is null, Y may be CN. It is understood that R, R, R, and R' may be independently selected from any of the operative groups disclosed above.

[0109] In yet another exemplary and non-limiting embodiment, the monomer of Formula (I) may be selected from one or more of the following: [ka]

[0110] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0111] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0112] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0113] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0114] In another embodiment, the monomer (I) comprises: [ka]

[0115] In another embodiment, the polymer composition comprises a plurality of plastic crystals. The term plastic crystal is understood to refer to crystals composed of weakly interacting molecules that possess certain orientational and structural degrees of freedom. Plastic crystals can be considered soft materials. Without wishing to be bound by any theory, it is understood that the plastic crystals exhibit strong long-range order.

[0116] In certain embodiments, plastic crystals known in the art suitable for the desired application can be used. In yet another embodiment, the plastic crystals are [ka] can be selected from:

[0117] In yet another embodiment, the polymer compositions disclosed herein can include a metal salt. It is understood that any metal salt suitable for the desired application can be used. For example, in one embodiment, the metal salt is an alkali metal salt. However, in another embodiment, the metal salt is an alkaline earth metal salt. However, in yet another embodiment, the metal salt can include a post-transition metal salt. However, in yet another embodiment, the metal salt can include a transition metal salt. In yet another embodiment, the metal salt can include any combination of any of the disclosed metal salts.

[0118] In yet another embodiment, the polymer composition can include a metal salt, wherein the cation of the metal salt includes one or more of Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof.

[0119] In yet another embodiment, the anion of the metal salts disclosed herein can comprise any ion suitable for the desired application. For example, the anion can be a halide. In such an embodiment, the halide can be I- , Cl - , Br - , or F - In another embodiment, the anion of the metal salt can include bistriflimide (TFSI). - ), bis(fluorosulfonyl)imide (FSI - ), triflate (OTf - ), hexafluorophosphate (PF6 - ), hexafluoroarsenate (AsF6 - ), aluminum tetrachloride (AlCl4 - ), boron tetrachloride (BCl4 - ), boron tetrafluoride (BF4 - ), iodide (I - ), chlorate (ClO3 - ), bromate (BrO3 - ), iodate (IO3 - ), difluoro(oxalato)borate (DFOB - ), bis(oxalato)borate (BOB -- ), difluorophosphate (DFP), or a combination thereof.

[0120] In yet another embodiment, the metal salt can be present in an amount of 0% to about 70% by weight of the polymer, with exemplary values ​​of about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, and about 66.9% by weight.

[0121] In yet another embodiment, the polymer compositions disclosed herein are crosslinked. It is understood that the crosslinking can be covalent, ionic, or both. In yet another embodiment, the crosslinking can be achieved by any method known in the art, as discussed in more detail below. In some embodiments, crosslinking of the polymers disclosed herein can be achieved by adding a crosslinking agent during the polymerization process. In another embodiment, crosslinking can be achieved by irradiation. In such embodiments, irradiation can include IR, UV, or e-beam polymerization. In yet another embodiment, the crosslinking can be achieved by irradiating the polymer formed with the addition of a crosslinking agent. In yet another embodiment, crosslinking can be achieved by thermal initiation.

[0122] In yet another embodiment, the polymer compositions disclosed herein exhibit elastomeric properties. For example, without limitation, the polymer compositions can have a tensile strength of about 150% to about 500%, including exemplary values ​​of about 175%, about 200%, about 225%, about 250%, about 275%, about 300%, about 325%, about 350%, about 375%, about 400%, about 425%, about 450%, and about 475%.

[0123] In yet another aspect, the polymer compositions described herein can exhibit flame retardant properties.

[0124] In another embodiment, the polymer composition is stable over a temperature range of about -30°C to about 100°C, including exemplary values ​​of about -25°C, about -20°C, about -15°C, about -10°C, about -5°C, about 0°C, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, and about 95°C. The term "stable" as used herein is understood to indicate that the polymer composition maintains its properties over the disclosed temperature range. For example, the disclosed electrical and mechanical properties are not degraded or altered. The term "stable" is understood to mean that the polymer composition can be used for its intended purpose with electrical or mechanical properties in the disclosed range without any limitations or substantial changes in performance.

[0125] In yet another embodiment, the polymer compositions disclosed herein exhibit an ion transport number for any of the disclosed metal salt cations greater than about 0.4, or greater than about 0.45, or greater than about 0.5, or greater than about 0.6, or greater than about 0.7, or greater than about 0.8. For example, the ion transport number for a cation can be between about 0.4 and about 0.8, with exemplary values ​​of about 0.42, about 0.45, about 0.47, about 0.5, about 0.52, about 0.55, about 0.57, about 0.6, about 0.62, about 0.65, about 0.67, about 0.7, about 0.72, about 0.75, and about 0.77. It is understood that the specific ion transport number will vary depending on the specific cation. For example, and without limitation, the polymer compositions disclosed herein exhibit Li-ion transport numbers of about 0.7 to about 0.75, with exemplary numbers being about 0.71, about 0.72, about 0.73, and about 0.74.

[0126] In another embodiment, the polymer compositions disclosed herein can be used as a solid electrolyte, an ionic conductor, an actuator, a sensor, a capacitor, or a combination thereof. In another embodiment, the polymer compositions disclosed herein can be used in a solar cell, a supercapacitor, a fuel cell, a Li-S battery, a Na-S battery, a Li-air battery, a Na-air battery, a Zn-air battery, or any battery disclosed herein.

[0127] Also disclosed herein is a polymer composition formed by polymerizing a mixture comprising: a) one or more monomers of Formula (I); b) a plurality of plastic crystals; and c) a salt AB; [ka] where R1, R2 and R3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently selected from C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 optionally substituted with one or more of: heterocycloalkenyl, aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or null, wherein Y is OR, R, R'OR'', C(O)R, N(R)(R'"), or CN; where R4 is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10wherein R4 is independently and optionally selected from one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4' is (-O-CH2-CH2-)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 is a heteroalkynyl of the formula -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; wherein R4′ is independently and optionally one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4'' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R is independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; or where R4'' is P(O)(OR4''')2; where R4''' is hydrogen, C1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, where n is 1 to 200; wherein A is selected from Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof; and B is bistriflimide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), triflate (OTf - ), hexafluorophosphate (PF6 - ), hexafluoroarsenate (AsF6 - ), aluminum tetrachloride (AlCl4 - ), boron tetrachloride (BCl4 - ), boron tetrafluoride (BF4 - ), iodide (I - ), chlorate (ClO3 - ), bromate (BrO3 - ), iodate (IO3 - ), difluoro(oxalato)borate (DFOB - ), bis(oxalato)borate (BOB -- ), difluorophosphate (DFP), or a combination thereof.

[0128] In yet other embodiments, n can be between 1 and 200, with exemplary values ​​of 2, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, and 190. It is understood that any value between any two of the above disclosed values ​​is also disclosed.

[0129] In yet another embodiment, R1, R2, and R3 are each independently hydrogen, C 1-5 Alkyl, C 1-5 Alkoxy, C 1-5 Heteroalkyl, C 6-14 Aryl, C1-13 Heteroaryl, C 6-14 Aryloxy, C 3-10 Cycloalkyl, C 3-10 Heterocycloalkyl, C 3-10 Cycloalkenyl, C 3-10 In another embodiment, R1, R2, and R3 are each selected from heterocycloalkenyl, halide, or amine. In another embodiment, R1, R2, and R3 are each hydrogen. In another embodiment, at least one of R1, R2, and R3 is hydrogen. In yet another embodiment, at least one of R1, R2, and R3 is a halide. In yet another embodiment, at least one of R1, R2, and R3 is an amine. In yet another embodiment, any, all, or at least one of R1, R2, and R3 can be substituted with any of the functional groups disclosed above.

[0130] In another embodiment, when X is C(O), it may be selected from YOR, R'OR, or N(R)(R'). In yet another embodiment, when X is O, it may be YC(O)R. In yet another embodiment, when X is null, Y may be CN. It is understood that R, R, R, and R' may be independently selected from any of the operative groups disclosed above.

[0131] In yet another embodiment, the polymer composition formed from the polymerization of the disclosed mixtures may further exhibit an ionic conductivity of from about 1.0 mS / cm to about 10 mS / cm, with exemplary values ​​of about 1.5 mS / cm, about 2.0 mS / cm, about 2.5 mS / cm, about 3.0 mS / cm, about 3.5 mS / cm, about 4.0 mS / cm, about 4.5 mS / cm, about 5.0 mS / cm, about 5.5 mS / cm, about 6.0 mS / cm, about 6.5 mS / cm, about 7.0 mS / cm, about 7.5 mS / cm, about 8.0 mS / cm, about 8.5 mS / cm, about 9.0 mS / cm, and about 9.5 mS / cm. In yet another embodiment, the polymer compositions disclosed herein have a viscosity of greater than about 1 mS / cm, greater than about 1.1 mS / cm, greater than about 1.2 mS / cm, greater than about 1.3 mS / cm, greater than about 1.4 mS / cm, greater than about 1.5 mS / cm, greater than about 1.6 mS / cm, greater than about 1.6 mS / cm, greater than about 1.7 mS / cm, greater than about 1.8 mS / cm, greater than about 1.9 mS / cm, greater than about 2.0 mS / cm, greater than about 2.1 mS / cm, greater than about 2.2 mS / cm, greater than about 2.3 mS / cm, greater than about 2.4 mS / cm The polymers may exhibit an ionic conductivity of greater than about 2.5 mS / cm, greater than about 2.6 mS / cm, greater than about 2.7 mS / cm, greater than about 2.8 mS / cm, greater than about 2.9 mS / cm, greater than about 3.0 mS / cm, greater than about 3.1 mS / cm, greater than about 3.2 mS / cm, greater than about 3.3 mS / cm, greater than about 3.4 mS / cm, greater than about 3.5 mS / cm, greater than about 3.6 mS / cm, greater than about 3.7 mS / cm, greater than about 3.8 mS / cm, greater than about 3.9 mS / cm, or even greater than about 4.0 mS / cm. In yet another embodiment, the ionic conductivity of the polymers disclosed herein may be greater than about 5.0 mS / cm.

[0132] In other embodiments, the mixture can further include a cross-linking agent. In such embodiments, the cross-linking agent can include one or more of the following: [ka] Exemplary values ​​include 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, and 29.

[0133] However, it is understood that the polymer composition can be further crosslinked by irradiating the polymerizable mixture. Any known radiation exposure time can be used to form a crosslinked polymer. For example, without limitation, the polymer composition can be crosslinked with UV, IR, or e-beam radiation.

[0134] The plurality of plastic crystals can be any of those disclosed above. For example, without limitation, the plurality of plastic crystals can be derived from one or more of the following: [ka]

[0135] In yet another exemplary and non-limiting embodiment, the monomer of Formula (I) may be selected from one or more of the following: [ka]

[0136] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0137] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0138] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0139] In yet another embodiment, the monomer (I) is selected from one or more of the following: [ka]

[0140] In another embodiment, the monomer (I) comprises: [ka]

[0141] It is understood that the step of polymerizing the polymer composition can be carried out by any method known in the art. For example, the polymerization can be free radical polymerization, ionic polymerization, or coordination polymerization. In some embodiments, the mixture used to form the polymer composition disclosed herein can further include an initiator. In such embodiments, the initiator is a polymerization initiator. In other embodiments, the initiator can include a thermal initiator, a photoinitiator, or a combination thereof.

[0142] In some embodiments, the initiator is a thermal initiator. Any thermal initiator known in the art can be utilized as long as it produces the desired polymer composition. In this exemplary, non-limiting embodiment, the thermal initiator can include azobisisobutyronitrile, benzoyl peroxide, or a combination thereof. When any of these thermal initiators is used to form the polymer composition, the polymerization is thermal polymerization.

[0143] However, in other embodiments, the initiator is a photoinitiator. Any photoinitiator known in the art can be utilized as long as it produces the desired polymer composition. In this exemplary, non-limiting embodiment, the photoinitiator can include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2-hydroxyl-2-methyl-1-phenyl-1-propanone, methylbenzoyl formate, hydroxycyclohexyl phenyl ketone (Irgacure 184), or a combination thereof. When any of these photoinitiators is used to form the polymer composition, the polymerization is photopolymerization.

[0144] In one exemplary but non-limiting embodiment, the polymer composition can be synthesized by polymerizing a homogeneous solution comprising butyl acrylate (BA), poly(ethylene glycol) diacrylate (PEGDA), succinonitrile (SN), and LiTFSI.

[0145] In yet another embodiment, the mixture can include a ratio of one or more monomers of formula (I) below to a plurality of plastic crystals of from about 70:30 to about 30:70, with exemplary values ​​of about 60:40, 50:50, and about 40:60.

[0146] In yet another embodiment, the salt AB can be present in the mixture in an amount of 0% to about 70% by weight of the polymer composition, with exemplary values ​​being about 0.01%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, and about 66.9% by weight. In yet another embodiment, the salt AB can be added, for example, as a powder. In such embodiments, the salt is substantially dry and substantially free of water.

[0147] In another embodiment, the mixture is substantially free of water.

[0148] In another embodiment, the mixture can further include various additives. In one embodiment, the additive can include functional groups that protect the polymerization reaction from side reactions that could result in undesirable compositions. For example, without limitation, the mixture can include fluoroethylene carbonate (FEC), lithium nitrate (LiNO), or any combination thereof. It is understood that the compounds listed here are merely exemplary, and any other compounds that can achieve the desired application can be utilized. It is understood that all compounds present in the mixture are substantially free of water.

[0149] In another embodiment, the mixture is homogeneous prior to polymerization.

[0150] In yet another embodiment, a plurality of plastic crystals dispersed in the polymer composition can form a three-dimensional interconnected phase of plastic crystals.

[0151] In yet another embodiment, the polymer compositions disclosed herein exhibit elastic properties. For example, without limitation, the polymer compositions can have a tensile strength of about 150% to about 500%, including exemplary values ​​of about 175%, about 200%, about 225%, about 250%, about 275%, about 300%, about 325%, about 350%, about 375%, about 400%, about 425%, about 450%, and about 475%.

[0152] In yet another aspect, the polymer compositions described herein can exhibit flame retardant properties.

[0153] In yet another embodiment, the polymer composition is stable over a temperature range of about -30°C to about 100°C, with exemplary values ​​being about -25°C, about -20°C, about -15°C, about -10°C, about -5°C, about 0°C, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, and about 95°C. The term "stable" as disclosed herein is understood to indicate that the polymer composition maintains its properties over the disclosed temperature range. For example, the disclosed electrical and mechanical properties are not degraded or altered. The term "stable" is understood to mean that the polymer composition can be used for its intended purpose without any limitations or substantial changes in performance, with electrical or mechanical properties in the disclosed range.

[0154] In yet another embodiment, the polymer compositions disclosed herein exhibit an ion transport number for any of the disclosed metal salt cations greater than about 0.4, or greater than about 0.45, or greater than about 0.5, or greater than about 0.6, or greater than about 0.7, or greater than about 0.8. For example, the ion transport number for a cation can be between about 0.4 and about 0.8, with exemplary values ​​of about 0.42, about 0.45, about 0.47, about 0.5, about 0.52, about 0.55, about 0.57, about 0.6, about 0.62, about 0.65, about 0.67, about 0.7, about 0.72, about 0.75, and about 0.77. It is understood that the specific ion transport number will vary depending on the specific cation. For example, and without limitation, the polymer compositions disclosed herein exhibit Li-ion transport numbers of about 0.7 to about 0.75, with exemplary numbers being about 0.71, about 0.72, about 0.73, and about 0.74.

[0155] electrochemical battery Also disclosed herein are electrochemical cells. In such embodiments, the electrochemical cell can include a solid electrolyte comprising any of the polymer compositions disclosed herein, an anode electrode, and a cathode electrode, wherein the anode electrode and the cathode electrode are in electrical communication with the solid electrolyte.

[0156] In certain embodiments, the anode electrode can comprise a metallic material. It is understood that the metallic material can be a material containing the metal or a cation of a disclosed metal. In certain embodiments, the metallic material can comprise Li, Ca, Na, K, Mg, Zn, or Al, an alloy thereof, or a combination thereof. However, in other embodiments, the anode can comprise a material capable of intercalating any of the metallic materials disclosed herein. In other embodiments, the anode material can comprise ions of Li, Ca, Na, K, Mg, Zn, or Al, an alloy thereof, or a combination thereof. In certain embodiments, the anode is a Li-based material. In other embodiments, the anode is Li metal. In other embodiments, the anode is a K-based material. In other embodiments, the anode is K metal. In other embodiments, the anode is a Na-based material. In other embodiments, the anode is Na metal. In other embodiments, the anode is a Zn-based material. In other embodiments, the anode is Zn metal. In other embodiments, the anode is a Ca-based material. In other embodiments, the anode is Ca metal. In another embodiment, the anode is an Mg-based material. In another embodiment, the anode is Mg metal. In another embodiment, the anode is an Al-based material. In another embodiment, the anode is Al metal. In another embodiment, the anode is an alloy of any of the disclosed metallic materials.

[0157] In yet another embodiment, the anode material can also include a host material configured to accommodate and intercalate any of the metal materials disclosed above. Such host materials can include any material known in the art. For example, the host material can include a copper- or graphite-based material. In certain exemplary embodiments, the host material includes copper. In such exemplary embodiments, it can be presented as a foil, foam, grid, wire, filament, or any combination thereof. In yet another exemplary embodiment, the host material includes a carbon-based material. The carbon-based material can include hard carbon, carbon black, graphene, reduced graphene oxide, graphene oxide, graphite, or any combination thereof. In yet another embodiment, the additional host material can include silicon or a graphite / silicon composite.

[0158] In another embodiment, the cathode electrode may be a metal cathode or a composite cathode. It is understood that any cathode material known in the art that may be effective for the desired purpose may be utilized. In some embodiments, the cathode may be a metal cathode or a composite cathode.

[0159] In yet another embodiment, the cathode material can include copper, carbon, graphite, sodium, potassium, lithium, magnesium, calcium, aluminum, layered oxides, vanadium-based cathodes, sulfur-based cathodes, manganese-based cathodes, rock salt cathodes, disordered rock salt cathodes, lithium-rich cathodes, high voltage ceramics, low voltage ceramics, NMC (nickel-manganese-cobalt oxide) cathodes, NCA (nickel-cobalt-aluminum oxide) cathodes, LCO (lithium cobalt oxide) cathodes, lithium-nickel-cobalt-aluminum oxide materials (LNCAO), lithium-nickel-manganese-cobalt oxide (LNMCO), LFP (lithium iron phosphate) cathodes, fluoride-based cathodes, sulfur selenium cathodes, sulfur selenium tellurium cathodes, spinel, olivine, or combinations thereof.

[0160] When the metal cathode is similar to the metal anode, such an electrochemical cell may be a symmetric electrochemical cell, for example, without limitation, a symmetric cell may include a Li or K anode material and a Li or K cathode material, respectively.

[0161] In yet another embodiment, the cathode electrode comprises Na3V2(PO4)3(NVP), LNMCO, Na3V2(PO4)2F3(NVPF), KMnFe(CN)6, MnO2, V2O5, graphite, LiFePO4, LiCoO2, LiMnO2, derivatives thereof, or combinations thereof.

[0162] In yet another embodiment, the cathode material is Li metal, LiNi 1-x-y- Mn x Co y O2, or LiNi 1-a-b Co a Al b02, where 1≧x≧0, 1≧y≧0, 1≧a≧0, and 1≧b≧0. In such exemplary embodiments, x can have any value between 0 and 1, with exemplary values ​​of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0. In yet other embodiments, y can have any value between 0 and 1, with exemplary values ​​of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0. In yet another embodiment, a can have any value between 0 and 1, including exemplary values ​​of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0. In yet another embodiment, b can have any value between 0 and 1, including exemplary values ​​of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0.

[0163] In yet another exemplary and non-limiting embodiment, the cathode material is LiCoO2, LiNi 0.9 Mn 0.05 Co 0.05 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2, LiNi 0.83 Mn 0.06 Co 0.11 O2, or LiNi 0.88 Co 0.09 Al 0.03 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0.4 Mn 0.3 Co 0.3O2, LiNi 0.5 Mn 0.3 Co 0.2 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2, or LiNi 0.8 Mn 0.1 Co 0.1 It may contain a composite cathode of O2.

[0164] In yet another embodiment, the cathode material can further include an additive, such as, but not limited to, poly(ethylene oxide), cellulose, carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), or polyvinylidene fluoride binder (PVDF).

[0165] In yet another embodiment, the electrochemical cell of the present disclosure provides a current of about 0.25 mAcm for about 500 cycles, about 600 cycles, about 700 cycles, about 800 cycles, about 900 cycles, about 1,000 cycles, about 1,250 cycles, about 1,500 cycles, about 1,750 cycles, about 2,000 cycles, about 5,000 cycles, or about 10,000 cycles. -2 , about 0.5mAcm -2 , about 0.75mAcm -2 , about 1mAcm -2 , about 0.1mAcm -2 ~about 10mAcm -2 , about 1.5mAcm -2 , about 2mAcm -2 , about 2.5mAcm -2 , about 3mAcm -2 , about 3.5mAcm -2 , about 4mAcm -2 , about 4.5mAcm -2 , about 5mAcm -2 , about 5.5 mAcm -2 , about 6mAcm -2 , about 6.5mAcm -2 , about 7mAcm -2 , about 7.5mAcm -2 , approximately 8 mA cm -2 , about 8.5mAcm -2 , approximately 9 mAcm-2 , about 9.5mAcm -2 and an exemplary value of about 0.1 mAcm -2 ~about 10mAcm -2 at a current density of greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, greater than about 99.1%, greater than about 99.2%, greater than about 99.3%, greater than about 99.4%, greater than about 99.5%, greater than about 99.6%, greater than about 99.7%, greater than about 99.8%, or greater than about 99.9%.

[0166] In yet another embodiment, the battery is substantially stable for about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, or about 1,000 plating / stripping (de-stripping) cycles in a temperature range of about -30°C to about 100°C, with exemplary values ​​being about -25°C, about -20°C, about -15°C, about -10°C, about -5°C, about 0°C, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, and about 95°C.

[0167] In yet another embodiment, the electrochemical cells disclosed herein are configured to provide a specific energy of about 350 to about 520 watt-hours per kilogram of the anode, cathode, and solid electrolyte after 500 cycles at a specific energy of about 150 to about 500 W / kg. In such embodiments, the specific energy of the cell may be about 350 to about 600 watt-hours per kilogram of anode, cathode, and solid electrolyte after about 500 cycles at a specific energy of about 150 to about 500 W / kg, with exemplary values ​​of about 400, about 425, about 450, about 475, about 500, about 520, about 550, and about 575 watt-hours per kilogram of anode, cathode, and solid electrolyte, including exemplary values ​​of about 200, about 250, about 300, about 350, about 40 ...25, about 450, about 475, about 500, about 520, about 550, and about 575 watt-hours per kilogram of anode, cathode, and solid electrolyte, including exemplary values ​​of about 400, about 425, about 450, about 475, about 500, about 520, about 550, and about 575 watt-hours per kilogram of anode, cathode, and solid electrolyte, including exemplary values ​​of about 350 to about 600 watt-hours per kilogram of anode, cathode, and solid electrolyte after about 500 cycles at a specific energy of about

[0168] In yet another embodiment, the electrochemical cell has a current of about 0.25 mAcm-2 , about 0.5mAcm -2 , about 0.75mAcm -2 , about 1mAcm -2 , about 0.1mAcm -2 ~about 10mAcm -2 , about 1.5mAcm -2 , about 2mAcm -2 , about 2.5mAcm -2 , about 3mAcm -2 , about 3.5mAcm -2 , about 4mAcm -2 , about 4.5mAcm -2 , about 5mAcm -2 , about 5.5 mAcm -2 , about 6mAcm -2 , about 6.5mAcm -2 , about 7mAcm -2 , about 7.5mAcm -2 , approximately 8 mA cm -2 , about 8.5mAcm -2 , approximately 9 mAcm -2 , about 9.5mAcm -2 and an exemplary value of about 0.1 mAcm -2 ~about 10mAcm -2 at least about 500 hours, at least about 600 hours, at least about 700 hours, at least about 800 hours, at least about 900 hours, at least about 1,000 hours, at least about 1,250 hours, at least about 1,500 hours, at least about 1,750 hours, at least about 2,000 hours, at least about 5,000 hours, or at least about 10,000 hours at a current density of

[0169] In yet another embodiment, the battery has a current of about 0.25 mAcm -2 , about 0.5mAcm -2 , about 0.75mAcm -2 , about 1mAcm -2 , about 0.1mAcm -2 ~about 10mAcm -2 , about 1.5mAcm -2 , about 2mAcm -2 , about 2.5mAcm -2 , about 3mAcm -2, about 3.5mAcm -2 , about 4mAcm -2 , about 4.5mAcm -2 , about 5mAcm -2 , about 5.5 mAcm -2 , about 6mAcm -2 , about 6.5mAcm -2 , about 7mAcm -2 , about 7.5mAcm -2 , approximately 8 mA cm -2 , about 8.5mAcm -2 , approximately 9 mAcm -2 , about 9.5mAcm -2 and an exemplary value of about 0.1 mAcm -2 ~about 10mAcm -2 at a current density of up to about 500 hours, up to about 600 hours, up to about 700 hours, up to about 800 hours, up to about 900 hours, up to about 1,000 hours, up to about 1,100 hours, up to about 1,200 hours, up to about 1,300 hours, up to about 1,400 hours, and up to about 1,500 hours.

[0170] In yet another embodiment, the electrochemical cell can exhibit a reversible capacity of about 100 mAh / g or less, about 110 mAh / g or less, about 120 mAh / g or less, about 130 mAh / g or less, about 130 mAh / g or less, about 140 mAh / g or less, about 150 mAh / g or less, about 160 mAh / g or less, about 170 mAh / g or less, about 180 mAh / g or less, about 190 mAh / g or less, and about 200 mAh / g or less.

[0171] In yet another embodiment, the solid electrolyte composition does not undergo any substantial change during about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 900, or about 1,000 plating / stripping cycles in a temperature range of about -30°C to about 100°C, including exemplary values ​​of about -25°C, about -20°C, about -15°C, about -10°C, about -5°C, about 0°C, about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, and about 95°C.

[0172] In yet another embodiment, the solid electrolyte can have a thickness of about 10 nm to about 1 mm, with exemplary values ​​being about 15 nm, about 20 nm, about 50 nm, about 100 nm, about 250 nm, about 500 nm, about 750 nm, about 1 μm, about 5 μm, about 10 μm, about 25 μm, about 50 μm, about 75 μm, about 100 μm, about 250 μm, about 500 μm, about 750 μm, and about 990 μm.

[0173] In yet another embodiment, the electrochemical cells disclosed herein exhibit a high capacity retention of greater than about 80%, greater than about 81%, greater than about 82%, greater than about 83%, greater than about 84%, greater than about 80%, 85% or greater, greater than about 86%, greater than about 87%, greater than about 88%, greater than about 89%, greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, or greater than about 99% for at least about 50 cycles, at least about 80 cycles, at least about 100 cycles, at least about 200 cycles, at least about 300 cycles, at least about 400 cycles, at least about 500 cycles, at least about 600 cycles, at least about 700 cycles, at least about 800 cycles, at least about 900 cycles, or at least about 1000 cycles.

[0174] In another embodiment, the battery has a rechargeability of about 99.9% or greater, about 99% or greater, about 98% or greater, or about 97% or greater, or about 96% or greater, or about 95% or greater for at least about 50 cycles, at least about 80 cycles, at least about 100 cycles, at least about 200 cycles, at least about 300 cycles, at least about 400 cycles, at least about 500 cycles, at least about 600 cycles, at least about 700 cycles, at least about 800 cycles, at least about 900 cycles, or at least about 1000 cycles. , about 94 or more, or about 93 or more, or about 92 or more, or about 91 or more, or about 90% or more, about 89 or more, or about 88 or more, or about 87 or more, or about 86 or more, or about 85% or more, about 84 or more, or about 83 or more, or about 82 or more, or about 81 or more, or about 80% or more, about 79 or more, or about 78 or more, or about 77 or more, or about 76 or more, or about 75% or more, or about 74 or more, or about 73 or more, or about 72 or more, or about 71 or more, or about 70% or more.

[0175] In yet another embodiment, the solid electrolyte can be formed in situ. In such an embodiment, the mixture described above can be inserted into the electrochemical cell during cell construction, and the polymerization process can be accomplished within the cell. In such an exemplary, non-limiting embodiment, polymerization can be heat-activated.

[0176] In another embodiment, the solid electrolyte can be formed separately and added as a separate component in the battery construction.

[0177] In yet another aspect, the electrochemical cells disclosed herein operate such that the anode material is substantially dendrite free during plating cycles.

[0178] In another embodiment, the electrochemical cell disclosed herein is a battery. In another embodiment, the battery is a secondary battery.

[0179] For example, electrochemical cells of the present disclosure include portable batteries, including batteries in portable and / or wearable electronic devices such as cell phones, watches, or laptop computers; stationary electronic devices such as desktop and mainframe computers; power tools such as power drills; electric or hybrid land, water, or air-based vehicles such as boats, submarines, buses, trains, trucks, automobiles, motorcycles, mopeds, electric bicycles, airplanes, drones, other flying vehicles, or toy versions thereof; other toys; and stationary power storage for energy storage, such as power storage from wind, solar, wave, hydro, or nuclear energy and / or grid storage, or for small-scale use in homes, businesses, or hospitals.

[0180] A battery according to the present disclosure may also be a multi-cell battery including at least about 10, at least about 100, at least about 500, 10-10,000, 100-10,000, 1,000-10,000, 10-1,000, 100-1,000, or 500-1,000 electrochemical cells of the present disclosure. The cells of the multi-cell battery can be arranged in parallel or in series.

[0181] method Also disclosed herein are methods for making the polymer compositions disclosed herein. In some embodiments, the methods include: a) forming a mixture including: i) one or more monomers of Formula (I) as disclosed above; ii) any of the disclosed plastic crystals; and iii) any of the disclosed salts AB; and polymerizing the mixture to form the polymer composition described above.

[0182] In another embodiment, the mixture can further include a crosslinking agent. Any of the disclosed cross-liners can be used. In another embodiment, the mixture can further include an initiator. Any of the initiators described above can be used.

[0183] In one exemplary, non-limiting embodiment, the polymer composition can be synthesized by polymerizing a homogeneous solution comprising butyl acrylate (BA), poly(ethylene glycol) diacrylate (PEGDA), succinonitrile (SN), and LiTFSI.

[0184] In yet another aspect, the disclosed method produces the polymer composition, wherein a plurality of plastic crystals are dispersed in the polymer composition to form a three-dimensionally interconnected phase of plastic crystals, and the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20°C.

[0185] In another aspect, the method produces any of the disclosed polymer compositions.

[0186] Also disclosed herein is a method of manufacturing an electrochemical cell comprising the steps of: a) providing an anode material; b) providing a cathode material; and c) providing a solid electrolyte formed by the disclosed method.

[0187] In yet another aspect, there is further disclosed a method of making an electrochemical cell, comprising the steps of: a) providing an anode material; b) providing a cathode material; and c) providing a mixture of any of the compounds disclosed herein and polymerizing the mixture in situ during operation of the electrochemical cell to form the disclosed solid electrolyte.

[0188] By way of non-limiting illustration, examples of particular aspects of the present disclosure are provided below.

[0189] Example The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and / or methods claimed herein are made, evaluated, and contemplated, and are merely illustrative and are not intended to limit the disclosure. While efforts are made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), some errors and deviations should be accounted for. Unless otherwise specified, parts are parts by weight, temperature is at or near degrees Celsius, and pressure is at or near atmospheric.

[0190] Without being bound by any theory, it is hypothesized that superior ionic and mechanical properties can be achieved if ion-conducting materials can form three-dimensional (3D) interconnected phases within a mechanically robust elastomeric matrix through PIPS. In this disclosure, another class of SPEs for high-energy LMBs is reported. The materials are based on in-situ formed elastomers with 3D interconnected phases of ion-conducting plastic crystals. Co-continuous structures of plastic crystal-embedded elastomeric electrolytes (PCEEs) are developed through PIPS between the polymer and plastic crystals within the cell. PCEEs exhibit high ionic conductivity (1.1 mS cm at 20°C) along with excellent mechanical properties and a high lithium-ion transfer number (t+) of 0.75. -1 ) are shown. In addition, due to its mechanical elasticity, the PCEE formed in-situ in the battery (hereinafter referred to as "built-in PCEE") effectively accommodates the substantial volume change of Li during fast charge-discharge cycles. Using the built-in PCEE, LiNi 0.83 Mn 0.06 Co 0.11 Stable operation of the SPE-based solid-state LMB with an O2 (NMC-83) cathode was demonstrated. This elastic electrolyte system presents a promising strategy for achieving high-performance and stable solid-state LMB.

[0191] Example 1 Electrolyte preparation For the fabrication of PCEEs, electrolyte preparation and cell assembly were performed in an argon-filled glovebox with O2 and water (HO) concentrations below 0.1 ppm. A butyl acrylate (BA)-based solution was prepared by dissolving 1 mol% poly(ethylene glycol) diacrylate (PEGDA) (Sigma-Aldrich), 0.5 mol% AIBN (Sigma-Aldrich), and 1 M LiTFSI powder (≥99%; Sigma-Aldrich) in BA liquid (Sigma-Aldrich). To compare the BA-based elastomer (BA100) with PCEEs, the BA-based solution was polymerized at 70 °C for 2 h. A succinonitrile (SN)-based solution (SN100) was prepared by mixing SN (Sigma-Aldrich) with 1 M LiTFSI powder and 5 vol% fluoroethylene carbonate additive (Sigma-Aldrich) to prevent side reactions between SN and Li metal at 50 °C. The prepared liquid solutions were homogeneously mixed at a volume ratio of 1:1 at 50 °C to fabricate the embedded PCEE (Figures 26A-26D). The prepared solution was then injected into a cell (e.g., a 2032-type coin cell), and the assembled cell was heated at 70 °C for 2 h to generate the embedded PCEE (Figures 2A-2C). A handmade mold was used to prepare a free-standing ex-situ PCEE.

[0192] PCEEs can also be produced through a photopolymerization process. By replacing thermal initiators (e.g., azobisisobutyronitrile) with photoinitiators (e.g., photoinitiators bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2-hydroxyl-2-methyl-1-phenyl-1-propanone, and methylbenzoyl formate), the polymerization time for PCEEs can be reduced from 2 hours to 5–20 minutes.

[0193] material characterization Fourier transform infrared spectroscopy spectra were measured using a Bruker ALPHA-P spectrometer in the attenuated total reflectance setting. Thermogravimetric analysis tests (TA Instruments Q500) were performed at 10°C min under a nitrogen atmosphere.-1 The differential scanning calorimetry curves were measured from room temperature to 700 °C at a heating rate of 10 °C min under nitrogen atmosphere using a TA Instruments Q200. -1 The heating and cooling rates were 100 s. The morphology of the built-in PCEE was observed using a SEM (Hitachi SU-5000) and a TEM (Talos F200X). Cross-sectional TEM samples were prepared by micro-sectioning using a diamond knife (RMC PowerTomeX). Elemental mapping by electron energy loss spectroscopy was performed using a TEM equipped with high-angle annular dark-field imaging. 3D tomographic images were obtained using an X-ray microscope (Zeiss Xradia 520 versa). Mechanical tensile stress and interfacial adhesion strength measurements were performed using a universal tester (Lloyd Instruments LR5K). The adhesion energy was calculated using a previously reported method. X-ray photoelectron spectroscopy (XPS; Thermal Scientific K-alpha XPS instrument) was used to investigate the composition of the SEI formed on the Li metal anode after 100 cycles in a symmetric Li cell containing built-in PCEE and SN100 (Figure 17). The cycled cells were disassembled in an argon-filled glove box. The cycled Li metal anode was then transferred to the XPS using a vacuum transfer vessel to prevent contamination and side reactions with ambient oxygen and moisture. For comparison, the top surface of the cycled Li metal anode was etched using argon ion sputtering until the ratio of Li atoms in the SEI component of the built-in PCEE was approximately 30%. High-resolution XPS Li 1s, C 1s, O 1s, N 1s, and F 1s spectra were deconvoluted using XPSPEAKS4.1.

[0194] Electrode preparation NMC-622, NMC-83, and LFP cathodes were fabricated using a slurry casting technique. To fabricate the slurry, the active material, conductive additive SuperP carbon, SN-LiTFSI with a molar ratio of 20:1, and polyvinylidene fluoride were dissolved in N-methyl-2-pyrrolidone in a weight ratio of 7:1:1:1 and then coated onto an aluminum foil current collector. The cathodes were dried in a vacuum oven at 55 °C for 24 hours. The active loading density of the LFP cathode was 1.5 mg cm. -2 The active loading density of the NMC-622 cathode was 2.1 mg cm -2 and 9.8 mg cm -2 The active loading density of the NMC-83 cathode was 10.3–10.6 mg cm -2 The range was.

[0195] Electrochemical measurements The electrochemical performance of all cells was tested using 2032-type coin cells assembled with Li foil as the anode in an argon-filled glove box (M. Braun, O2 and HO < 0.1 ppm). Linear sweep voltammetry was performed using a stainless steel (SS) asymmetric cell with a Li || 1 mV s -1 At a scan rate of Li / Li + The cycles were performed from 1.5 V to 6 V vs. . EIS (Bio-Logic VMP3) of the PCEE was performed from 100 Hz to 105 Hz using a peak voltage of 10 mV at open circuit voltage. The ionic conductivity of the electrolyte was measured using EIS with a symmetric cell of SS||electrolyte||SS in an environmental chamber (MC-812R, Espec) at the desired temperature. In this study, polypropylene and glass fiber were applied as separators to prevent short-circuiting of the PCEE liquid precursor for the full battery, considering compatibility with current roll-to-roll Li-ion battery manufacturing. Cycling tests of a 35 μm-thick Li|| and 25 μm-thick built-in PCEE|| high-load NMC-83 cell were performed at 0.5 mA cm without voltage hold. -2 before cycling at a current density of 0.1 mA cm 2The constant current charge / discharge tests of the 35 μm thick Li|| 25 μm thick embedded PCEE|| high load NMC-83 cells were carried out in the voltage range of 2.7–4.3 V with three initialization cycles at a current density of 0.1–3 mA cm -2 The tests were carried out in the voltage range of 2.7 to 4.5 V at the same current density (0.1 mA cm) using an Arbin battery tester. For the temperature dependence test, a 35 μm thick Li|| and a 25 μm thick embedded PCEE|| high-load NMC-83 cell were tested at the same current density (0.1 mA cm). -2 The electrodes were charged and discharged in an environmental chamber at various temperatures (0°C to 60°C). All specific capacitances and areal volumes were normalized using the weight of the active material in the electrode and the area of ​​the electrode, respectively.

[0196] Example 2 Design of elastic electrolytes The embedded PCEE was synthesized by polymerizing a homogeneous solution composed primarily of butyl acrylate (BA), succinonitrile (SN), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) at 70 °C in an assembled electrochemical cell (Figure 1A, Figure 2A, 2C). SN, a typical plastic crystal, was selected as the ion-conducting material because of its high ionic conductivity when complexed with Li salts. For the polymerization, azobisisobutyronitrile (AIBN; 0.5 mol%) and poly(ethylene glycol) diacrylate (PEGDA; 1 mol%) were used as the thermal initiator and crosslinker, respectively. During this polymerization, the BA / PEGDA polymer formed an in-situ polymer that was chemically crosslinked by PEGDA to eventually form an elastomeric network, while the SN-LiTFSI phase partitioned into nanoscale domains.

[0197] The synthesized PCEEs exhibited high mechanical resilience due to the elastomeric matrix (Figure 2B). Three-dimensional tomography and scanning electron microscopy (SEM) images revealed that the PCEEs possessed an interconnected network structure in which wormlike polymer ducts were connected three-dimensionally (Figures 1B, 1C, and 3). Specifically, the SN phase was well surrounded by a crosslinked polymer phase, and the interface between the SN phase and the elastomeric matrix was smoothly connected, as revealed by transmission electron microscopy (TEM) (Figure 1D). Elemental mapping images using electron energy loss spectroscopy confirmed that the nitrogen (N) of the SN phase was embedded in the oxygen (O) of the BA-based elastomeric matrix (Figure 1E). Without wishing to be bound by any theory, this unique structure is attributed to nanoscale phase separation between PIPS, driven by the increase in the molecular weight of the polymerized BA / PEGDA and the enthalpy interaction between the SN and the resulting polymer. Importantly, the coarsening of the resulting SN phase was effectively suppressed by the elastomer matrix, allowing the formation of 3D interconnected SN phases as effective ion-conducting pathways within the BA-based elastomer. Furthermore, differential scanning calorimetry, thermogravimetry, and Fourier transform infrared spectroscopy (FTIR) demonstrated that the PCEE exhibited both plastic crystalline and rubbery polymer phase properties (Figures 4–6).

[0198] It should be noted that the unique structure of PCEE is completely different from that of conventional blends (Figures 7A-7D). Simple blending of SN with a BA-based polymer (BA100) without PIPS showed a macroscopically separated morphology. The ionic conductivity and tensile roughness of the blend were substantially 32 and 47 times worse than those of PCEE, respectively (Figures 7C, 7D). The interconnected nature of the SN phase in PCEE was further investigated through measurements of ionic conductivity with temperature. The low ionic conductivity of BA100 (approximately 10 at 20 °C) -6 mScm -1 ), the PCEE is 1.1 mScm at 20°C. -1 The composite (SN100; 4.1 mS cm at 20 °C) exhibits a high ionic conductivity, which is slightly lower than that of SN-LiTFSI.-1 (Fig. 8A, Fig. 9). The activation energy (Ea) of the incorporated PCEE is estimated to be 0.13 eV, which is similar to that of SN100 (0.11 eV) but much smaller than that of BA100 (0.69 eV).

[0199] Considering the volume fraction of the SN conductive phase in PCEE, the tortuosity of the continuous conductive phase was determined to be very low (1.9). This result suggests that the ionic conductivity pathways of highly connected continuous SN domains were successfully developed within the elastomeric matrix of PCEE. Furthermore, X-ray diffraction results indicated that the crystallinity of the SN phase within the elastomeric phase was well maintained, contributing to the high ionic conductivity of PCEE (Figure 10). The excellent mechanical resilience of PCEE was demonstrated through tensile tests. PCEE showed that SN100 could not be measured due to its extreme brittleness (Figure 7B). Overall, these results indicate that the SN network embedded in PCEE did not impair the mechanical robustness of the elastomeric matrix.

[0200] The PCEE also exhibited excellent flame retardancy (Figure 11). A photograph of the embedded PCEE formed on Li metal was compared with that of ex-situ synthesized PCEE (hereafter referred to as "ex-situ PCEE") (Figure 7C). The embedded PCEE made perfect contact with the electrode, forming a more stable interface than the ex-situ PCEE. SEM cross-sectional images show that the embedded PCEE was smoothly bonded to the Li metal anode (Figure 7D). Here, the solution that initially wetted the rough electrode was polymerized in situ along the surface. The interfacial adhesion test showed that the embedded PCEE exhibited strong adhesion to the electrode, significantly exceeding that of the ex-situ PCEE (2.7 J m). -2 ) has a higher adhesive energy of 21.5 Jm -2 (Fig. 7E, Fig. 12). -2This adhesion energy is considered a key requirement for creating a stable interface that can withstand mechanical stress during cell fabrication and operation. Electrochemical Impedance Spectroscopy (EIS) measurements also revealed that the overall resistance of the built-in PCEE was 122 Ω cm. -2 and ex-situ PCEE (304 Ω cm -2 ) was shown to be lower than that of the control (Figure 7F).

[0201] Investigation of Li reversibility The built-in PCEE exhibited excellent mechanical and electrochemical properties, so we decided to use it as a solid electrolyte. Li plating and stripping tests were conducted in a symmetric Li cell using the disclosed PCEE (Figure 14A). 10 mA cm -2 At high current densities, the SN100 battery lasted only a few cycles. In contrast, the PCEE-embedded cell showed excellent cycling performance with low polarization for over 1,500 hours, achieving an accumulated capacity of 7.5 Ahcm. -2 (Figure 13) In particular, in the case of the built-in PCEE, the -2 A very low polarization of 13 mV was observed at 1000 s.c., which is significantly lower than that of ex situ PCEE (63–111 mV). This low polarization can be attributed to the conformal coating of PCEE built into the lithium metal, which can substantially reduce the interfacial resistance and generate uniform lithium ion flux. It can be seen that the "arched" shape at the edge of the voltage profile, commonly observed with resinous and dead Li accumulation, did not appear even after repeated plating and stripping of Li metal for 1,500 h (inset in Figure 14A). These results far exceed the ARPA-E (Advanced Research Projects Agency-Energy) IONICS (New Ion-Conducting Solids) integration and optimization goals based on current density, cumulative capacity, and areal capacity per cycle. The compatibility of Li metal and PCEE was confirmed by a stable interfacial resistance (175 Ω m) at the Li-PCEE (solid-solid) interface for 30 days.-2 ) was further supported by the results (Fig. 15A). Furthermore, with increasing cycles, the overall resistance of the built-in PCEE decreased significantly (Fig. 15B). These results indicate that the in-situ polymerized PCEE effectively reduces the interfacial resistance at the solid-solid interface, enabling highly stable Li plating and stripping cycles. The morphology of the Li metal anode using various electrolytes was investigated using a 10 mA cm -2 The results were compared after 100 cycles at 100 mA / cm². In the case of SN100, the Li metal exhibited a porous structure containing mossy dead Li after only a few cycles (Figure 14B), which explains the sudden failure of the Li cell (Figure 14A). In contrast, the Li anodes with both ex-situ and embedded PCEE exhibited a dense and uniform Li structure without dendritic Li after 100 cycles (200 h) (Figures 14C and 14D). However, after removing the attached PCEE film, the Li metal with embedded PCEE exhibited a much smoother surface (Figure 14D) compared to the ex-situ PCEE, which showed a wrinkled surface with cracks (Figure 14C). The stability of the Li cell with embedded PCEE was significantly improved at 20 mA / cm². -2 and 20mAhcm -2 This was further investigated under higher current conditions (Figure 15C). After voltage fluctuations during the initial cycles (<50 h), the Li cells showed a stable polarization of 25–29 mV over 500 h. The voltage hysteresis of the PCEE-integrated Li cells at various current densities was much lower than that of previously reported polymer-based electrolytes (Figure 15D). The Bruce-Vincent method was then used to determine the integrated PCEE values ​​(Figures 15E, 15F, and 16).

[0202] In particular, the embedded PCEE exhibited a high t+ value of 0.75, which is significantly higher than the t+ values ​​of conventional organic liquid electrolytes (t+ ≈ 0.4) and PEO-based polymer electrolytes (t+ < 0.5). The excellent stability and high t+ value during high-rate Li plating and stripping cycles are important for enabling high-rate charging of LMB. Furthermore, an inorganic-organic hybrid SEI layer was found in the embedded PCEE, which favors interfacial stability, while the SEI layer derived from SN100 is primarily composed of organic compounds (Figure 17). The embedded PCEE also exhibited excellent stability and cycling capability in an asymmetric Li||Cu cell (Figure 14E). 1 mAh cm -2 with 0.5mAcm -2 In the present study, the coulombic efficiency (CE) of the Li||Cu battery with SN100 fluctuated and faded out after 35 cycles (Fig. 18).

[0203] In contrast, the cell with built-in PCEE showed 100.0% CE with a small polarization of less than 8 mV after 500 cycles (Figure 19). The Li||Cu cell with PCEE showed 4 mA cm for 430 and 200 cycles, respectively. -2 and 10mAhcm -2 with a capacity of 2mAcm -2 and 5 mAcm -2 The CE of 100.0% was maintained at even higher current densities of 1 mAh cm (Figures 14E and 14F). To better understand the cycling behavior, the morphological changes of the Li||Cu cell incorporating the PCEE during the Li plating and stripping process were investigated. SEM cross-sectional images showed that the PCEE was conformally coated on the copper (Cu) foil before electroplating (Figure 14G). -2 at 0.5mAcm -2After the first Li plating, dense and uniformly deposited Li was observed on the Cu foil (Figure 14H). After subsequent Li stripping, the Li deposited on the Cu foil completely disappeared (Figure 14I). These results indicate that the PCEE, with its high elasticity and strong adhesive strength, successfully accommodated the large volume change during Li plating (Figure 14J). Furthermore, due to the resilience of the built-in PCEE, the system was not deformed and was able to return to its original state even after the stripping process. Therefore, the highly stable cycling process of cells using PCEE begins with its excellent mechanical and interfacial properties.

[0204] High-energy lithium battery demonstration For solid-state LMB applications, LiFePO4 (LFP), LiNi 0.6 Mn 0.2 Co 0.2 We investigated PCEEs with various built-in cathodes, including O2 (NMC-622) and NMC-83 cathodes. Prior to battery performance testing, electrochemical float experiments of the PCEEs were performed to rigorously define the feasible electrochemical window (Figure 19A). The measured leakage current was less than 20 μA up to 4.6 V, consistent with the linear sweep voltammetry results showing an oxidation wave at 4.75 V (Figure 21). Thus, the excellent oxidation stability of PCEEs allows for more stable operation (rate performance and cycling) with the NMC-622 cathode at a high voltage of 4.5 V (Figures 20B and 20C). The use of SPEs with high-voltage cathodes was limited to a voltage of 4.3 V. Therefore, this study demonstrates stable operation of SPE-based all-solid-state LMBs at a high voltage of 4.5 V at ambient temperature. Additionally, a full battery with an LFP cathode delivered 93 mAhg at 1 C without appreciable capacity loss (0.005% per cycle) over 1,000 cycles at 20°C. -1 (Figure 22) Toward high-energy LMB, there is a strong demand for full batteries with limited Li metal anode sources, highly loaded cathodes, and thin solid electrolytes.

[0205] Furthermore, a low negative / positive capacitance (N / P) ratio of 3.4 (35 μm thick Li anode, 25 μm thick built-in PCEE), and high loading of NMC-83 (>10 mg cm -2 )) electrochemical testing of the full cell was performed at 0.1 mAcm -2 2.1mAhcm during the initialization cycle -2 The battery then delivered a high capacity of 0.5 mA cm after 100 cycles at 30 °C (Figure 23A). -2 1.1mAhcm with 99.4% CE -2 The capacity of the ion exchanger was maintained at 0.1 mAcm (88% capacity retention) (Fig. 24A). -2 to 3mAcm -2 The rate capability of the cell was evaluated at various current densities up to 1 mAcm (Figure 24B). -2 at a rate as high as 1.3mAhcm -2 Capacity (0.1mAcm -2 The full cell showed negligible capacity loss (99%) from 60 to 40 °C, and maintained 92% of its capacity at 20 °C and 57% at 0 °C (inset in Figure 23B).

[0206] The excellent rate and low-temperature performance are attributed to the extremely high ionic conductivity and t+ of PCEE. The specific energy and power output of the all-solid-state LMB at ambient temperature were calculated based on the weights of the anode, cathode, and solid electrolyte using a Ragawne-type plot (Figure 24C, Figure 25). A full cell using an NMC-83 cathode produced 410 Wh kg -1 (791Whkg NMC-83 -1 ) at ambient temperature, exhibiting a high specific energy of over 184 Wkg -1 235Whkg -1 This performance of the full battery with a thin PCEE is much higher than any previously reported battery using ceramic, polymer, or composite electrolytes tested at ambient temperature (Figures 23C and 23D).

[0207] Furthermore, as shown in Figures 27A-27B, PCC is LiNi x Co y Al z It was confirmed that O2 (NCA) can be used as a cathode.

[0208] Example 3 In addition to Li-ions, PCEE has high ionic conductivity for various metal cations, including Na, K, Mg, Zn, and Al (Figure 28). Therefore, PCEE can be used in various metal batteries.

[0209] Without being bound by any theory, we hypothesize that the specific energy of the cell can be further increased by modifying the cathode structure or stacking several cells (batteries). In summary, we report a class of SPEs based on the in-situ formation of an elastomeric electrolyte containing a 3D interconnected plastic crystalline phase. This class successfully combines the advantages of elastomers and plastic crystalline electrolytes, including high ionic conductivity, excellent mechanical properties, electrochemical stability, low interfacial resistance, and high lithium ion mobility. The built-in PCEE enabled excellent cycling performance in symmetric Li and asymmetric Li||Cu cells with a low voltage hysteresis of less than 26 mV and a CE of 100.0%. Finally, we demonstrated stable operation of a PCEE-based solid-state LMB with high specific energy and power output at ambient temperature under the restrictive conditions of a limited Li source and a heavily loaded NMC cathode (N / P ratio <3.4). Without being bound by any theory, it is believed that the elastic electrolyte system disclosed herein is broadly applicable to the operation of a variety of post-metal (e.g., sodium, potassium, zinc, magnesium, and aluminum) batteries, including metal-metal, air, and metal-sulfur batteries due to its excellent mechanical properties and high ionic conductivity.

[0210] The apparatus, systems, and methods in the appended claims are intended to exemplify certain aspects of the claims and are not limited in scope by the specific apparatus, systems, and methods described herein. All functionally equivalent apparatus, systems, and methods are intended to be within the scope of the claims. Various modifications of the apparatus, systems, and methods in addition to those shown and described herein are intended to be within the scope of the appended claims. Also, although only certain representative apparatus, system, and method steps disclosed herein have been specifically described, other combinations of apparatus, system, and method steps are also intended to be within the scope of the appended claims even if not specifically recited. Thus, although steps, elements, components, or combinations of components may be explicitly referred to herein or below, other combinations of steps, elements, components, and components are included even if not explicitly recited.

[0211] While several embodiments of the present invention have been disclosed in the foregoing specification, it will be understood that many variations and other embodiments of the invention pertaining to this invention will come to mind to one skilled in the art having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. It is understood, therefore, that the invention is not limited to the specific embodiments disclosed above, and that many modifications and other embodiments are intended to be included within the scope of the appended claims. Moreover, although specific terms are employed in this specification and in the following claims, they are used in a generic and descriptive sense only and not for the purpose of limiting the invention described or the scope of the claims that follow.

[0212] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. Publications cited herein and the material for which they are cited are specifically incorporated by reference.

[0213] The claims are not intended to, and should not be construed as including, means-plus- or step-plus-function limitations, unless the claims are expressly recited in a particular claim using the phrase "means for" or "step for," respectively.

[0214] In view of the described processes and compositions, more specifically described particular embodiments of the invention are set forth below. However, such specifically mentioned embodiments should not be construed as having a limiting effect on any other claims that may include different or more general teachings set forth herein, nor should the "particular" embodiments be construed as limited in any manner other than the inherent meaning and formula of the language literally used therein.

[0215] Aspects In view of the described electrodes, batteries, methods, and variations thereof, more specifically described particular embodiments of the present invention are set forth below. However, such specifically mentioned embodiments should not be construed as having a limiting effect on any other claims that may include different or more general teachings set forth herein, nor should the "particular" embodiments be construed as limited in any manner other than by the inherent meaning and formula of the language literally used therein.

[0216] Aspect 1: A polymer composition comprising: a) a matrix comprising an elastic polymer; b) a plurality of plastic crystals dispersed within the matrix to form a three-dimensionally interconnected phase of plastic crystals; and wherein the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20°C.

[0217] Embodiment 2: The polymer composition of embodiment 1, wherein the elastomeric polymer is derived from at least one monomer comprising: [ka] where R1, R2 and R3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently selected from C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10wherein X is C(O), O, or null, and Y is OR, R, R'OR'', C(O)R, N(R)(R'''), or CN; where R4 is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R4 is independently and optionally selected from one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4' is (-O-CH2-CH2-)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; wherein R4′ is independently and optionally one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4'' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10wherein R is independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4''' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, and wherein n is 1 to 200.

[0218] Embodiment 3: The polymer composition of embodiment 2, wherein X is C(O) and Y is OR4, R4'OR4'', or N(R4)(R4''').

[0219] Embodiment 4: The polymer composition of embodiment 2, wherein X is O and Y is C(O)R4.

[0220] Embodiment 5: The polymer composition of embodiment 2, wherein X is none and Y is CN.

[0221] Aspect 6: The polymer composition of any of Aspects 2-5, wherein (I) is selected from one or more of the following: [ka]

[0222] Aspect 7: The polymer composition of any of Aspects 2-6, wherein (I) is selected from one or more of the following: [ka]

[0223] Embodiment 8: The polymer composition of any of embodiments 2-7, wherein (I) is selected from one or more of the following: [ka]

[0224] Embodiment 9: The polymer composition of any of embodiments 2 to 8, wherein (I) is selected from one or more of the following: [ka]

[0225] Embodiment 10: The polymer composition of any of embodiments 2 to 9, wherein (I) is selected from one or more of the following: [ka]

[0226] Embodiment 11: The polymer composition of any of embodiments 2 to 10, wherein (I) comprises: [ka]

[0227] Embodiment 12: The polymer composition of any of embodiments 1-11, wherein the plurality of plastic crystals is derived from one or more of the following: [ka]

[0228] Embodiment 13: The polymer composition of any of embodiments 1 to 12, further comprising a metal salt, wherein the cation of the metal salt comprises one or more of Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof.

[0229] Aspect 14: The anion of the metal salt is bistriflimide (TFSI - ), bis(fluorosulfonyl)imide (FSI - ), triflate (OTf - ), hexafluorophosphate (PF6 - ), hexafluoroarsenate (AsF6 - ), aluminum tetrachloride (AlCl4 - ), boron tetrachloride (BCl4 - ), boron tetrafluoride (BF4 - ), iodide (I - ), chlorate (ClO3 - ), bromate (BrO3 - ), iodate (IO3 - ), difluoro(oxalato)borate (DFOB - ), bis(oxalato)borate (BOB -- 14. The polymer composition of embodiment 13, comprising: a fluorocarbon polymer; a difluorophosphate (DFP); or a combination thereof.

[0230] Embodiment 15: The polymer composition of any of embodiments 1 to 14, wherein the polymer composition is crosslinked.

[0231] Embodiment 16: The polymer composition of any of embodiments 1 to 15, wherein the polymer composition has a tensile strain of about 150% to about 500%.

[0232] Embodiment 17: The polymer composition of any of embodiments 1 to 16, wherein the polymer composition is flame retardant.

[0233] Embodiment 18: The polymer composition of any of embodiments 1 to 17, wherein the polymer composition is stable in a temperature range of about -30°C to about 100°C.

[0234] Embodiment 19: The polymer composition of any of embodiments 13 to 18, wherein the ion transference number for cations is greater than about 0.4.

[0235] Embodiment 20: A solid electrolyte comprising the polymer composition of any of embodiments 1 to 19.

[0236] Aspect 21: A battery comprising the solid electrolyte of aspect 20.

[0237] Embodiment 22: A polymer composition formed by polymerizing a mixture comprising: a) one or more monomers of Formula (I); b) a plurality of plastic crystals; and c) a salt AB. [ka] where R1, R2 and R3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C3-10 wherein R and R are each independently selected from C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 optionally substituted with one or more of: heterocycloalkenyl, aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or null, wherein Y is OR, R, R'OR, C(O)R, N(R)(R'"), or CN; where R4 is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R4 is independently and optionally selected from one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4' is (-O-CH2-CH2-)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; wherein R4′ is independently and optionally one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4'' is hydrogen, C 1-20 Alkyl, C2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R is independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Or, where R4'' is P(O)(OR4''')2; where R4''' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, where n is 1 to 200; wherein A is selected from Li, K, Na, Ca, Mg, Zn, Al, or combinations thereof; and B is bistriflurimide (TFSI) - ), bis(fluorosulfonyl)imide (FSI - ), triflate (OTf - ), hexafluorophosphate (PF6 - ), hexafluoroarsenate (AsF6 - ), aluminum tetrachloride (AlCl4 - ), boron tetrachloride (BCl4 - ), boron tetrafluoride (BF4 - ), iodide (I - ), chlorate (ClO3 - ), bromate (BrO3 - ), iodate (IO3 - ), difluoro(oxalato)borate (DFOB - ), bis(oxalato)borate (BOB -- ), difluorophosphate (DFP), or a combination thereof.

[0238] Embodiment 23: The polymer composition of embodiment 22, wherein the mixture further comprises a crosslinker.

[0239] Embodiment 24: The polymer composition of embodiment 23, wherein the crosslinker comprises one or more of the following: [ka]

[0240] Embodiment 25: The polymer composition of any of Embodiments 22-24, wherein the plurality of plastic crystals originates from one or more of the following: [ka]

[0241] Embodiment 26: The polymer composition of any of Embodiments 22 to 25, wherein X is C(O) and Y is OR4, R4'OR4'', or N(R4)(R4''').

[0242] Embodiment 27: The polymer composition of any of embodiments 22 to 25, wherein X is O and Y is C(O)R4.

[0243] Embodiment 28: The polymer composition of any of embodiments 22 to 25, wherein X is none and Y is CN.

[0244] Embodiment 29: The polymer composition of any of Embodiments 22 to 28, wherein (I) is selected from one or more of the following: [ka]

[0245] Embodiment 30: The polymer composition of any of Embodiments 22 to 29, wherein (I) is selected from one or more of the following: [ka]

[0246] Embodiment 31: The polymer composition of any of Embodiments 22 to 30, wherein (I) is selected from one or more of the following: [ka]

[0247] Embodiment 32: The polymer composition of any of Embodiments 22 to 31, wherein (I) is selected from one or more of the following: [ka]

[0248] Embodiment 33: The polymer composition of any one of Embodiments 22 to 32, wherein (I) is selected from one or more of the following: [ka]

[0249] Embodiment 34: The polymer composition of any of Embodiments 22-23, wherein (I) comprises: [ka]

[0250] Embodiment 35: The polymer composition of any of embodiments 22 to 24, wherein the mixture further comprises an initiator.

[0251] Embodiment 36: The polymer composition of embodiment 35, wherein the initiator comprises a thermal initiator, a photoinitiator, or a combination thereof.

[0252]

[0041] Aspect 37: The polymer composition of aspect 36, wherein the initiator comprises azobisisobutyronitrile, benzoyl peroxide, or a combination thereof.

[0253] Embodiment 38: The polymer composition of embodiment 35, wherein the polymerization is thermal polymerization.

[0254] Example 39: The polymer composition of example 38, wherein the initiator comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2-hydroxyl-2-methyl-1-phenyl-1-propanone, methyl benzoyl formate, hydroxycyclohexyl phenyl ketone (Irgacure 184), or a combination thereof.

[0255] Embodiment 40: The polymer composition of embodiment 39, wherein the polymerization is photopolymerization.

[0256] Embodiment 41: The polymer composition of any of embodiments 23 to 40, wherein the polymer composition is obtained by polymerization of a homogeneous solution comprising butyl acrylate (BA), poly(ethylene glycol) diacrylate (PEGDA), succinonitrile (SN), and LiTFSI.

[0257] Embodiment 42: The polymer composition of any of embodiments 22 to 41, wherein the plurality of plastic crystals are dispersed in the polymer composition to form a three-dimensionally interconnected phase of plastic crystals, and wherein the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20°C.

[0258] Embodiment 43: The polymer composition of any of embodiments 22 to 41, wherein the polymer composition has a tensile strain of about 150% to about 500%.

[0259] Embodiment 44: The polymer composition of any of embodiments 22 to 43, wherein the polymer composition is flame retardant.

[0260] Embodiment 45: The polymer composition of any of embodiments 22 to 44, wherein the polymer composition is stable at a temperature range of about -30°C to about 100°C.

[0261] Embodiment 46: The polymer composition of any of embodiments 22 to 45, wherein A has an ion transference number greater than about 0.4.

[0262] Embodiment 47: A solid electrolyte comprising the polymer composition of any of embodiments 1 to 46.

[0263] Embodiment 48: A battery comprising the solid electrolyte of embodiment 47.

[0264] Embodiment 49: An electrochemical cell comprising the solid electrolyte of embodiment 20 or 47.

[0265] Embodiment 50: The electrochemical cell of Embodiment 49, comprising: an anode electrode; and a cathode electrode, wherein the anode electrode and the cathode electrode are in electrical communication with the solid electrolyte.

[0266] Embodiment 51: The electrochemical cell of embodiment 50, wherein the anode electrode comprises a metallic material.

[0267] Embodiment 52: The electrochemical cell of embodiment 51, wherein the metallic material comprises Li, Ca, Na, K, Mg, Zn, Al, alloys thereof, or combinations thereof.

[0268] Embodiment 53: The electrochemical cell of any of Embodiments 50 to 52, wherein the cathode electrode is a metal cathode or a composite cathode.

[0269]

[0044] Embodiment 54: The electrochemical cell of embodiment 53, wherein the cathode comprises copper, carbon, graphite, sodium, potassium, lithium, magnesium, calcium, aluminum, a layered oxide, a vanadium-based cathode, a sulfur-based cathode, a manganese-based cathode, a rock salt cathode, a disordered rock salt cathode, a lithium-rich cathode, a high voltage ceramic, a low voltage ceramic, an NMC (nickel-manganese-cobalt oxide) cathode, an NCA (nickel-cobalt-aluminum oxide) cathode, an LCO (lithium-cobalt oxide) cathode, a lithium-nickel-cobalt-aluminum oxide material (LNCAO), a lithium-nickel-manganese-cobalt oxide (LNMCO), an LFP (lithium iron phosphate) cathode, a fluoride-based cathode, a sulfur selenium cathode, a sulfur selenium tellurium cathode, a spinel, an olivine, or a combination thereof.

[0270] Embodiment 55: The electrochemical cell of embodiment 54, wherein the cathode electrode comprises Na3V2(PO4)3(NVP), LNMCO, Na3V2(PO4)2F3(NVPF), KMnFe(CN)6, MnO2, V2O5, graphite, LiFePO4, LiCoO2, LiMnO2, derivatives thereof, or combinations thereof.

[0271] Embodiment 56: The electrochemical cell of any of Embodiments 50 to 55, wherein the anode material comprises Li.

[0272] Embodiment 57: The electrochemical cell of embodiment 56, wherein the Li is metallic.

[0273] Embodiment 57: The electrochemical cell of embodiment 56, wherein the Li is metallic.

[0274] Aspect 58: The cathode material is Li metal, LiNi 1-x-y Mn x Co y O2, or LiNi 1-a-b Co a Al b58. The electrochemical cell of any of embodiments 54-57, comprising O2, wherein 1≧x≧0, 1≧y≧0, 1≧a≧0, and 1≧b≧0.

[0275] Aspect 59: The cathode material is LiCoO, LiNi 0.9 Mn 0.05 Co 0.05 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2, LiNi 0.83 Mn 0.06 Co 0.11 O2, or LiNi 0.88 Co 0.09 Al 0.03 O2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2, LiNi 0.4 Mn 0.3 Co 0.3 O2, LiNi 0.5 Mn 0.3 Co 0.2 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2, or LiNi 0.8 Mn 0.1 Co 0.1 59. The electrochemical cell of embodiment 58, comprising a composite cathode of O2.

[0276] Aspect 60: The battery has a current of about 0.1 mAcm -2 ~about 10mAcm -2 59. The electrochemical cell of any of embodiments 48-58, wherein the cell exhibits a cyclic Coulombic efficiency of greater than about 99.5% for about 1,000 cycles at a current density of

[0277] Embodiment 61: The electrochemical cell of any of Embodiments 58-59, wherein the cell is configured to provide about 350 to about 520 watt-hours of specific energy per kilogram of anode, cathode, and solid electrolyte after about 500 cycles with a specific energy of about 150 to about 500 W / kg.

[0278] Aspect 62: The battery has a current of about 0.1 mAcm -2 ~about 10mAcm -2 62. The electrochemical cell of any of embodiments 50-61, wherein the cell exhibits substantially stable plating and stripping cycles for at least about 500 hours at a current density of

[0279] Aspect 63: The battery has a current of about 0.1 mAcm -2 ~about 10mAcm -2 63. The electrochemical cell of any of embodiments 50-62, wherein the cell exhibits substantially stable plating and stripping cycles for up to about 1500 hours at a current density of

[0280] Embodiment 65: The electrochemical cell of any of Embodiments 49 to 64, wherein the solid electrolyte is formed in situ.

[0281] Embodiment 66: The electrochemical cell of any of Embodiments 49 to 65, wherein the anode is substantially dendrite-free.

[0282] Embodiment 67: A battery comprising the electrochemical cell of any of embodiments 49 to 66.

[0283] Aspect 68: The battery of Aspect 67, wherein the battery is a secondary battery.

[0284] Embodiment 69: A method for producing the polymer composition of any of embodiments 1-19 or 22-46.

[0285] Aspect 70: A method of making the polymer composition comprising: a) forming a mixture comprising: i) one or more monomers of formula (I); ii) a plurality of plastic crystals; iii) a salt AB; and b) polymerizing the mixture to form the polymer composition; wherein [ka] where R1, R2 and R3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently selected from C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10optionally substituted with one or more of: heterocycloalkenyl, aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or none; wherein Y is OR, R, R'OR, C(O)R, N(R)(R'"), or CN; where R4 is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R4 is independently and optionally selected from one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4' is (-O-CH2-CH2-)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 and heteroalkynyl of -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; wherein R4′ is independently and optionally one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R4'' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C3-10 wherein R is independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; or where R4'' is P(O)(OR4''')2; where R4''' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 wherein R and R are each independently and optionally selected from C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; wherein n is 1 to 200; wherein A is selected from Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof; and B is bistriflurimide (TFSI) - ), bis(fluorosulfonyl)imide (FSI -), triflate (OTf - ), hexafluorophosphate (PF6 - ), hexafluoroarsenate (AsF6 - ), aluminum tetrachloride (AlCl4 - ), boron tetrachloride (BCl4 - ), boron tetrafluoride (BF4 - ), iodide (I - ), chlorate (ClO3 - ), bromate (BrO3 - ), iodate (IO3 - ), difluoro(oxalato)borate (DFOB - ), bis(oxalato)borate (BOB -- ), difluorophosphate (DFP), or a combination thereof.

[0286] Embodiment 71: The method of embodiment 70, wherein the mixture further comprises a cross-linking agent.

[0287] Embodiment 72: The method of embodiment 71, wherein the crosslinker comprises one or more of the following: [ka]

[0288] Embodiment 73: The method of any of embodiments 70-72, wherein the plurality of plastic crystals originates from one or more of the following: [ka]

[0289] Embodiment 74: The method of any of embodiments 70 to 73, wherein (I) is selected from one or more of the following: [ka]

[0290] Embodiment 75: The method of any of embodiments 70 to 74, wherein (I) is selected from one or more of the following: [ka]

[0291] Embodiment 76: The method of any of embodiments 70 to 75, wherein (I) is selected from one or more of the following: [ka]

[0292] Embodiment 77: The method of any of embodiments 70 to 76, wherein (I) is selected from one or more of the following: [ka]

[0293] Embodiment 78: The method of any of embodiments 70 to 77, wherein (I) is selected from one or more of the following: [ka]

[0294] Embodiment 79: The method of any of embodiments 70 to 78, wherein (I) comprises: [ka]

[0295] Embodiment 80: The method of any of embodiments 70 to 79, wherein the mixture further comprises an initiator.

[0296] Embodiment 81: The method of embodiment 80, wherein the initiator comprises a thermal initiator, a photoinitiator, or a combination thereof.

[0297] Embodiment 82: The method of embodiment 81, wherein the initiator comprises azobisisobutyronitrile, benzoyl peroxide, or a combination thereof.

[0298] Embodiment 83: The method of embodiment 82, wherein said polymerization is thermal polymerization.

[0299] Example 84 The method of example 81, wherein the initiator comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2-hydroxyl-2-methyl-1-phenyl-1-propanone, methyl benzoyl formate, hydroxycyclohexyl phenyl ketone (Irgacure 184), or a combination thereof.

[0300] Embodiment 85: The method of embodiment 84, wherein said polymerization is photopolymerization.

[0301] Example 86: The method of any of Examples 71 to 85, wherein the polymer composition is synthesized by polymerization of a homogeneous solution comprising butyl acrylate (BA), poly(ethylene glycol) diacrylate (PEGDA), succinonitrile (SN), and LiTFSI.

[0302] Embodiment 87: The method of any of embodiments 70 to 86, wherein the plurality of plastic crystals are dispersed in the polymer composition to form a three-dimensional interconnected phase of plastic crystals, and wherein the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20°C.

[0303] Embodiment 88: The method of any of embodiments 70-87, wherein the polymer composition has a tensile strain of about 150% to about 500%.

[0304] Embodiment 89: The method of any of embodiments 70 to 88, wherein the polymer composition is flame retardant.

[0305] Embodiment 90: The method of any one of embodiments 70-89, wherein the polymer composition is stable at a temperature range of about -30°C to about 100°C.

[0306] Embodiment 91: The method of any of embodiments 70-89, wherein A has an ion transference number greater than about 0.4.

[0307] Embodiment 92: A method of making an electrochemical cell, comprising the steps of: a) providing an anode material; b) providing a cathode material; and c) providing a solid electrolyte formed by the method of any one of Embodiments 70-91.

[0308] Embodiment 93: A method of making an electrochemical cell, comprising: a) providing an anode material; b) providing a cathode material; and c) providing a mixture of any one of embodiments 70 through 92 and polymerizing the mixture in situ during operation of the electrochemical cell to form the solid electrolyte of embodiment 19 or 46. [Item 1] A polymer composition comprising: a) a matrix comprising an elastic polymer; b) a plurality of plastic crystals dispersed within the matrix so as to form a three-dimensionally interconnected phase of plastic crystals; and wherein the polymer composition exhibits an ionic conductivity of at least about 1.1 mS / cm at about 20°C. [Item 2] Item 1, wherein the elastomeric polymer is derived from at least one monomer comprising: [ka] where R 1 、R 2 and R 3 are each independently hydrogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; 1 and R 2 are each independently 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 heteroalkyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 optionally substituted with one or more of: heterocycloalkenyl, aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or null, where Y is OR 4 、R 4 、R 4 'OR 4 '', C(O)R 4 , N(R 4 )(R 4 ''') or CN; where R 4 is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; 4 may independently and optionally be one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R 4 ' is (-O-CH 2 -CH 2 -)n, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; 4 ' may independently and optionally be one or more C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where R 4 '' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; 4 '' may independently and optionally include C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; or where R4'' is P(O)(OR4'') 2 and; where R 4 ''' is hydrogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C 1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), halide, amine; 4 '' and R 4 '' each independently and optionally, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 1-20 Alkoxy, C1-20 Heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, -(C 0-5 alkyl)(C 6-14 aryl), -(C 0-5 alkyl)(C 1-13 heteroaryl), -(C 0-5 alkyl)(C 6-14 aryloxy), -(C 0-5 alkyl)(C 3-10 cycloalkyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkyl), -(C 0-5 alkyl)(C 3-10 cycloalkenyl), -(C 0-5 alkyl)(C 3-10 heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, and Here, n is an integer of 1 to 200. [Item 3] where X is C(O) and Y is OR 4 、R 4 'OR 4 '', or N(R 4 )(R 4 3. The polymer composition according to item 2, wherein [Item 4] where X is O and Y is C(O)R 4 3. The polymer composition according to item 2, wherein [Item 5] 3. The polymer composition according to item 2, wherein X is nothing and Y is CN. [Item 6] wherein (I) is selected from one or more of the following polymer compositions:

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Claims

1. A polymer composition comprising: a) a matrix comprising an elastomeric polymer; b) a plurality of plastic crystals dispersed within the matrix so as to form a three-dimensionally interconnected phase of plastic crystals; and wherein the polymer composition exhibits an ionic conductivity of at least 1.1 mS / cm at 20°C; The elastomeric polymer is derived from at least one monomer comprising: 【Chemical 1】 Here, R １ , R ２ and R ３ are each independently hydrogen, C １－１２ Alkyl, C １－１２ Alkoxy, C １－１２ heteroalkyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; １ and R ２ are each independently C １－１２ Alkyl, C １－１２ Alkoxy, C １－１２ heteroalkyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ optionally substituted with one or more of: aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or null; where Y is OR ４ , R ４ , R ４ 'OR ４ '', C(O)R ４ , N(R ４ ) (R ４ ''') or CN; Here, R ４ is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ independently and optionally, one or more C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Here, R ４ ' is (-O-CH ２ -CH ２ -)n, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ ' independently and optionally, one or more C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Here, R ４ '' is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ '' independently and optionally, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Or, where R4" is P(O)(OR4'") ２ and Here, R ４ ''' is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ '' and R ４ '' each independently and optionally, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, and where n is 1 to 200; (I) is Selected from one or more of the following: 【Chemistry 2】 ； Selected from one or more of the following: 【Chemistry 3】 ； Selected from one or more of the following: 【Chemistry 4】 ； Selected from one or more of the following: 【Chemistry 5】 ； is 【Chemistry 6】 ;or, Including: 【Chemistry 7】 、 The plurality of plastic crystals may be derived from one or more of the following: 【Chemistry 8】 。

2. 10. The polymer composition of claim 1, further comprising a metal salt, wherein the cation of the metal salt comprises one or more of Li, K, Na, Ca, Mg, Zn, Al, or combinations thereof.

3. Here, the anion of the metal salt is bistriflimide (TFSI － ), bis(fluorosulfonyl)imide) (FSI － ), triflate (OTf － ), hexafluorophosphate (PF ６ － ), hexafluoroarsenate (AsF ６ － ), aluminum tetrachloride (AlCl ４ － ), boron tetrachloride (BCl ４ － ), boron tetrafluoride (BF ４ － ), iodide (I － ), chlorate (ClO ３ － ), bromate (BrO ３ － ), iodate (IO ３ － ), difluoro(oxalato)borate (DFOB － ), bis(oxalato)borate (BOB －－ ), difluorophosphate (DFP), or a combination thereof.

4. 4. The polymer composition of claim 1, wherein the polymer composition is crosslinked.

5. A polymer composition formed by polymerizing a mixture comprising: a) one or more monomers of formula (I), b) a plurality of plastic crystals; and c) a salt AB, where: 【Chemistry 9】 Here, R １ , R ２ and R ３ are each independently hydrogen, C １－１２ Alkyl, C １－１２ Alkoxy, C １－１２ heteroalkyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halides, and amines; Here, R １ and R ２ are each independently C １－１２ Alkyl, C １－１２ Alkoxy, C １－１２ heteroalkyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ optionally substituted with one or more of: aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or none; where Y is OR ４ , R ４ , R ４ 'OR ４ '', C(O)R ４ , N(R ４ ) (R ４ ''') or CN; Here, R ４ is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ independently and optionally, one or more C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Here, R ４ ' is (-O-CH ２ -CH ２ -)n, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ ' independently and optionally, one or more C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Here, R ４ '' is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ '' independently and optionally, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Or, where R ４ '' is P(O)(OR ４ ''') ２ and Here, R ４ ''' is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ '' and R ４ '' each independently and optionally, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; wherein n is 1 to 200; wherein A is selected from Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof; and further, B is bistriflimide (TFSI － ), bis(fluorosulfonyl)imide) (FSI － ), triflate (OTf － ), hexafluorophosphate (PF ６ － ), hexafluoroarsenate (AsF ６ － ), aluminum tetrachloride (AlCl ４ － ), boron tetrachloride (BCl ４ － ), boron tetrafluoride (BF ４ － ), iodide (I － ), chlorate (ClO ３ － ), bromate (BrO ３ － ), iodate (IO ３ － ), difluoro(oxalato)borate (DFOB － ), bis(oxalato)borate (BOB －－ ), difluorophosphate (DFP), or a combination thereof; (I) is Selected from one or more of the following: 【Chemistry 10】 ； Selected from one or more of the following: 【Chemistry 11】 ； Selected from one or more of the following: 【Chemistry 12】 ； Selected from one or more of the following: 【Chemistry 13】 ； is 【Chemistry 14】 ;or, Including: 【Chemistry 15】 、 The plurality of plastic crystals may be derived from one or more of the following: 【Chemistry 16】 。

6. 6. The polymer composition of claim 5, wherein the mixture further comprises a crosslinker.

7. 7. The polymer composition of claim 6, wherein the crosslinker comprises one or more of the following: 【Chemistry 17】

8. 8. The polymer composition of claim 5, wherein the mixture further comprises an initiator.

9. 10. The polymer composition of claim 8, wherein the initiator comprises a thermal initiator, a photoinitiator, or a combination thereof.

10. 9. The polymer composition of claim 8, wherein the initiator comprises azobisisobutyronitrile, benzoyl peroxide, or a combination thereof.

11. The polymer composition of claim 10, wherein the polymerization is a thermal polymerization.

12. 9. The polymer composition of claim 8, wherein the initiator comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2-hydroxyl-2-methyl-1-phenyl-1-propanone, methyl benzoyl formate, hydroxycyclohexyl phenyl ketone (Irgacure 184), or a combination thereof.

13. The polymer composition of claim 12 , wherein the polymerization is photopolymerization.

14. 8. The polymer composition of claim 6 or 7, wherein the polymer composition is synthesized by polymerization of a homogeneous solution comprising butyl acrylate (BA), poly(ethylene glycol) diacrylate (PEGDA), succinonitrile (SN), and LiTFSI.

15. 8. The polymer composition of claim 5, wherein the plurality of plastic crystals are dispersed in the polymer composition to form a three-dimensionally interconnected phase of plastic crystals, and wherein the polymer composition exhibits an ionic conductivity of at least 1.1 mS / cm at 20°C.

16. 8. An electrochemical cell comprising the polymer composition of any one of claims 1 to 3 and claims 5 to 7.

17. 17. The electrochemical cell of claim 16 further comprising: a) an anode electrode; and b) a cathode electrode; Here, the anode electrode and the cathode electrode are in electrical communication with a solid electrolyte.

18. 20. The electrochemical cell of claim 17, wherein the anode electrode comprises a metallic material.

19. 20. The electrochemical cell of claim 18, wherein the metallic material comprises Li, Ca, Na, K, Mg, Zn, Al, alloys thereof, or combinations thereof.

20. 18. The electrochemical cell of claim 17, wherein the cathode electrode is a metal cathode or a composite cathode.

21. 21. The electrochemical cell of claim 20, wherein the cathode comprises copper, carbon, graphite, sodium, potassium, lithium, magnesium, calcium, aluminum, layered oxides, vanadium-based cathodes, sulfur-based cathodes, manganese-based cathodes, rock salt cathodes, irregular rock salt cathodes, lithium-rich cathodes, high-voltage ceramics, low-voltage ceramics, NMC (nickel-manganese-cobalt oxide) cathodes, NCA (nickel-cobalt-aluminum oxide) cathodes, LCO (lithium-cobalt oxide) cathodes, lithium-nickel-cobalt-aluminum oxide materials (LNCAO), lithium-nickel-manganese-cobalt oxide (LNMCO), LFP (lithium iron phosphate) cathodes, fluoride-based cathodes, sulfur selenium cathodes, sulfur selenium tellurium cathodes, spinel, olivine, or any combination thereof.

22. Here, the cathode electrode is Na ３ V ２ (P.O. ４ ) ３ (NVP), LNMCO, Na ３ V ２ (P.O. ４ ) ２ F ３ (NVPF), KMnFe (CN) ６ , MnO ２ , V ２ O ５ , graphite, LiFePO ４ , LiCoO ２ , LiMnO ２ 22. The electrochemical cell of claim 21 comprising:

23. 20. The electrochemical cell of claim 17 wherein the anode material comprises Li.

24. 24. The electrochemical cell of claim 23 wherein Li is metallic.

25. Here, the cathode material is Li metal, LiNi １－ｘ－ｙ Mn ｘ Co ｙ O ２ , or LiNi １－ａ－ｂ Co ａ Al ｂ O ２ 22. The electrochemical cell of claim 21, comprising:

26. Here, the cathode material is LiCoO ２ , LiNi ０．９ Mn ０．０５ Co ０．０５ O ２ , LiNi ０．６ Mn ０．２ Co ０．２ O ２ , LiNi ０．８３ Mn ０．０６ Co ０．１１ O ２ , or LiNi ０．８８Ｃ o ０．０９ Al ０．０３ O ２ , LiNi ０．８Ｃ o ０．１５ Al ０．０５ O ２ , LiNi １／３ Mn １／３ Co １／３ O ２ , LiNi ０．４ Mn ０．３ Co ０．３ O ２ , LiNi ０．５ Mn ０．３ Co ０．２ O ２ , LiNi ０．６ Mn ０．２ Co ０．２ O ２ , or LiNi ０．８ Mn ０．１ Co ０．１ O ２ 26. The electrochemical cell of claim 25 comprising a composite cathode of

27. Here, the battery has a current of 0.1 mA cm －２ ~10mAcm －２ 17. The electrochemical cell of claim 16, exhibiting a cyclic Coulombic efficiency of greater than 99.5% for 1,000 cycles at a current density of 1000 volts.

28. 26. The electrochemical cell of claim 25, wherein the cell is configured to provide a specific energy of 350 to 520 watt-hours per kilogram of anode, cathode, and solid electrolyte after 500 cycles with a specific energy of 150 to 500 W / kg.

29. 18. The electrochemical cell of claim 17, wherein the cell exhibits a reversible capacity of up to 200 mAh / g.

30. 17. The electrochemical cell of claim 16, wherein the polymer composition is an in-situ formed solid electrolyte.

31. 18. The electrochemical cell of claim 17, wherein the anode is substantially dendrite free during plating cycles.

32. A method of making a polymer composition comprising: a) forming a mixture comprising: i. one or more monomers of formula (I): ii. a plurality of plastic crystals; iii. Salt AB, and b) polymerizing the mixture to form the polymer composition; where: 【Chemistry 18】 Here, R １ , R ２ and R ３ are each independently hydrogen, C １－１２ Alkyl, C １－１２ Alkoxy, C １－１２ heteroalkyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; １ and R ２ are each independently C １－１２ Alkyl, C １－１２ Alkoxy, C １－１２ heteroalkyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ optionally substituted with one or more of: aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; where X is C(O), O or none; where Y is OR ４ , R ４ , R ４ 'OR ４ '', C(O)R ４ , N(R ４ ) (R ４ ''') or CN; Here, R ４ is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ independently and optionally, one or more C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Here, R ４ ' is (-O-CH ２ -CH ２ -)n, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ is a heteroalkynyl of the formula -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ ' independently and optionally, one or more C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Here, R ４ '' is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ '' independently and optionally, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; Or, where R ４ '' is P(O)(OR ４ ''') ２ and Here, R ４ ''' is hydrogen, C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), halide, amine; ４ '' and R ４ "'" each independently and optionally represents C １－２０ Alkyl, C ２－２０ Alkenyl of C ２－２０ Alkynyl of C １－２０ Alkoxy, C １－２０ Heteroalkyl of C ２－２０ heteroalkenyl of C ２－２０ heteroalkynyl of -(C ０－５ alkyl) (C ６－１４ aryl), -(C ０－５ alkyl) (C １－１３ heteroaryl), -(C ０－５ alkyl) (C ６－１４ aryloxy), -(C ０－５ alkyl) (C ３－１０ cycloalkyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkyl), -(C ０－５ alkyl) (C ３－１０ cycloalkenyl), -(C ０－５ alkyl) (C ３－１０ heterocycloalkenyl), substituted with aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; wherein n is 1 to 200; wherein A is selected from Li, K, Na, Ca, Mg, Zn, Al, or a combination thereof; and B is bistriflimide (TFSI － ), bis(fluorosulfonyl)imide) (FSI － ), triflate (OTf － ), hexafluorophosphate (PF ６ － ), hexafluoroarsenate (AsF ６ － ), aluminum tetrachloride (AlCl ４ － ), boron tetrachloride (BCl ４ － ), boron tetrafluoride (BF ４ － ), iodide (I － ), chlorate (ClO ３ － ), bromate (BrO ３ － ), iodate (IO ３ － ), difluoro(oxalato)borate (DFOB － ), bis(oxalato)borate (BOB －－ ), difluorophosphate (DFP), or a combination thereof; (I) is Selected from one or more of the following: 【Chemistry 19】 ； Selected from one or more of the following: 【Chemistry 20】 ； Selected from one or more of the following: 【Chemical 21】 ； Selected from one or more of the following: 【Chemical 22】 ； is 【Chemical 23】 ;or, Including: 【Chemistry 24】 、 The plurality of plastic crystals may be derived from one or more of the following: 【Chemistry 25】 。

33. 33. The method of claim 32, wherein the mixture further comprises a cross-linking agent.

34. 34. The method of claim 33, wherein the cross-linking agent comprises one or more of the following: 【Chemical 26】

35. 35. The method of any one of claims 32 to 34, wherein the mixture further comprises an initiator.

36. 36. The method of claim 35, wherein the initiator comprises a thermal initiator, a photoinitiator, or a combination thereof.

37. 36. The method of claim 35, wherein the initiator comprises azobisisobutyronitrile, benzoyl peroxide, or a combination thereof.

38. 38. The method of claim 37, wherein the polymerization is thermal polymerization.

39. 36. The method of claim 35, wherein the initiator comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2-hydroxyl-2-methyl-1-phenyl-1-propanone, methyl benzoyl formate, hydroxycyclohexyl phenyl ketone (Irgacure 184), or a combination thereof.

40. 40. The method of claim 39, wherein the polymerization is photopolymerization.

41. 35. The method of any one of claims 32 to 34, wherein the polymer composition is synthesized by polymerization of a homogeneous solution comprising butyl acrylate (BA), poly(ethylene glycol) diacrylate (PEGDA), succinonitrile (SN), and LiTFSI.

42. 35. The method of any one of claims 32 to 34, wherein the plurality of plastic crystals are dispersed in the polymer composition to form a three-dimensional interconnected phase of plastic crystals, and wherein the polymer composition exhibits an ionic conductivity of at least 1.1 mS / cm at 20°C.

43. A method of manufacturing an electrochemical cell comprising: a) providing an anode material; b) providing a cathode material; and c) providing a solid electrolyte formed by the method of any one of claims 32 to 34.

44. A method of manufacturing an electrochemical cell comprising: a) providing an anode material; b) providing a cathode material; c) providing a mixture according to any one of claims 32 to 34, and d) polymerizing the mixture in-situ during operation of the electrochemical cell to form a solid electrolyte comprising the polymer composition of any one of claims 1-3 and claims 5-7.

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