Gel electrolyte composition for batteries and packaging method

Abstract

The method can include receiving a gel electrolyte precursor solution including a polymer precursor (e.g., a monomer or oligomer), an initiator, and a plasticizer; adding the gel electrolyte precursor solution to the battery stack; thoroughly distributing the gel electrolyte precursor solution throughout the battery stack; and curing the gel electrolyte precursor to form a covalently bonded gel electrolyte network interspersed throughout the battery stack.

Description

[Technical Field]

[0001] The present invention relates generally to the field of ion-conducting compositions, and more particularly to novel and useful compositions and methods for the fabrication and packaging of robust polymer electrolytes.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 485,332, filed February 16, 2023, which is incorporated by reference in its entirety. [Background technology]

[0003] Batteries have become increasingly essential to society, permeating every aspect of our lives. They essentially power the functioning of nearly every automated device we have at hand, and too often, the limits of technological development are driven by the limitations of the battery itself. As the functionality desired from portable devices increases, users and the desire for increased portability demand more stable, environmentally resistant, and more powerful batteries.

[0004] Thus, there is a need in the battery field for new and useful battery compositions and methods for producing batteries with properties such as increased energy density, improved safety, flexibility, etc. The present invention provides such new and useful compositions and methods by incorporating a strong, ionically conductive polymer electrolyte into batteries. [Brief explanation of the drawings]

[0005] [Figure 1] FIG. 1 is an exemplary schematic diagram of a battery system including a robust polymer electrolyte. [Figure 2] FIG. 2 is a flowchart illustrating an exemplary method. [Figure 3] FIG. 3 is a schematic diagram of an embodiment of the method using a simple battery. [Figure 4]FIG. 4 is a comparative image of an interface formed using an exemplary method and a conventionally constructed interface. [Figure 5] Figure 5 is a table comparing the conductivity of polymer electrolytes with that of liquid electrolytes. [Figure 6] FIG. 6 is a graph showing the toughness and ionic conductivity of exemplary compositions. [Figure 7] FIG. 7 is a graph showing the capacity and coulombic efficiency of the polymer electrolyte after cell flexing. [Figure 8] FIG. 8 is a graph showing the 1C / 1C cycle life of lithium ion pouch batteries utilizing exemplary tough polymer electrolyte compositions. [Figure 9] FIG. 9 is a graph showing the rate capability in the range of C / 10 to 2C of a lithium ion pouch battery utilizing an exemplary tough polymer electrolyte composition. [Figure 10] FIG. 10 is a schematic diagram of various exemplary formulation types of the composition. [Figure 11] FIG. 11 is a schematic diagram of various exemplary formulation types of the composition. [Figure 12] FIG. 12 is a schematic diagram of various exemplary formulation types of the composition. [Figure 13] FIG. 13 is a schematic diagram of various exemplary formulation types of the composition. [Figure 14] FIG. 14 is a schematic diagram of various exemplary formulation types of the composition. [Figure 15] FIG. 15 is a flow chart illustrating an example of curing an electrolyte precursor to form a gel electrolyte. [Figure 16] FIG. 16 is a schematic diagram showing an example of a hardened gel electrolyte having a cross-linked structure. DETAILED DESCRIPTION OF THE INVENTION

[0006] The following description of embodiments of the invention is not intended to limit the invention to those embodiments, but rather to enable any person skilled in the art to make and use the invention.

[0007] 1. Overview Compositions and methods for manufacturing and implementing electrolytic polymers in batteries include preparing one or more polymer electrolyte precursor solutions, the electrolyte precursors comprising at least one polymeric monomer and / or oligomeric subunit; dispensing the one or more polymer electrolyte precursor solutions throughout a battery volume and thoroughly infiltrating the battery components with the one or more solutions; and activating (e.g., curing) the one or more polymer electrolyte precursor solutions to polymerize the at least one polymeric monomer and / or oligomeric subunit. The one or more polymer electrolyte solutions may comprise a gel and / or polymer, and may have an ion-conducting oligomeric subcomponent that may include and / or promote dynamic bonding interactions (e.g., hydrogen bonding, ion pairing, metal chelates, host-guest interactions, etc.) that are polymerized when the solution is cured, a plasticizer (e.g., a solvent, additive, salt such as a lithium-based salt for lithium-ion batteries or a sodium-based salt for sodium-ion batteries), a polymerization initiator, a polymerization inhibitor, and / or any other suitable ingredient. While the term plasticizer is used, it should be noted that examples of plasticizers may not function as plasticizers for all polymers, but may nonetheless be included (e.g., they may include salts, solvents, additives, etc. that do not soften and / or increase the flexibility of a cured polymer). The compositions and methods function to construct and incorporate polymer (e.g., gel)-based electrolytes within battery cells, which can function as the sole or supplemental battery electrolyte. As shown in FIG. 8, an exemplary electrolyte formulation allows batteries incorporating the electrolyte to retain 80% or more of their initial capacity after 1000 battery cycles. The compositions and methods can achieve battery flexibility and improve battery function in one or more ways as described herein.

[0008] The present compositions and methods provide stable ionically conductive media for use with a wide range of general-purpose and application-specific batteries. That is, the present compositions and methods can provide stable electrolytes that can be incorporated into any volume to function as the ionically conductive media. In this case, a robust polymer electrolyte is one that exhibits improved modulus, extensibility, and / or ultimate stress (e.g., compared to a comparable battery having the same electrolyte but without the polymer). This method allows the electrolyte to be incorporated and polymerized directly into the battery, which can provide improved stability, functionality, and structural integrity compared to electrolytes incorporated by more conventional means.

[0009] In one aspect, the present compositions and methods are particularly useful for fabricating form-fit batteries, enabling efficient integration of battery components in flexible form-fit batteries. This may make the present systems and methods useful for fabricating smart sensors, medical devices, flexible electronics, defense systems, and / or gadgets with unprecedented functionality that have increasingly stringent geometric limitations. The present compositions and methods can also provide highly stable electrolytes that are particularly useful for integration into structural batteries and high-energy-density cells.

[0010] The present compositions and methods can provide many potential advantages. The present compositions and methods are not limited to providing such advantages, but are presented merely to illustrate how the compositions and methods can be used. The list of advantages is not intended to be exhaustive, and other advantages may additionally or alternatively exist.

[0011] As part of the method of incorporating the electrolyte composition, the present compositions and methods offer the potential advantage of simplified and scalable battery construction, allowing more "complex" batteries to be produced using simpler existing manufacturing processes.

[0012] The present compositions and methods offer the potential advantage of producing stable electrolyte compositions that can have greater stability and tunability compared to conventional electrolytes (e.g., liquids and solids, such as ceramic, non-gelling polymer electrolytes). More specifically, the electrolyte compositions can offer the potential advantage of less flammable batteries with little or no leakage of solvent and / or other electrolyte components when punctured or cut.

[0013] One potential advantage of the present electrolyte composition (e.g., cured polymer electrolyte) is that it provides greater structural integrity compared to current batteries that use other conventional electrolytes. Due to the interfacial tension of the electrolyte composition, the electrolyte composition offers the potential advantage of eliminating the need for external pressure to prevent misalignment of the battery layers (although external pressure may still be desired or implemented for other reasons).

[0014] Additionally, the adhesive properties of the electrolyte composition offer the potential advantage of enabling flexibility within the battery: the adhesive properties eliminate the need for uniform external pressure on the battery cell, thereby enabling flexibility.

[0015] The electrolyte composition can further provide a continuous interface along the battery components (e.g., between electrodes, via a separator, etc.), which can offer the potential benefit of reducing the interfacial impedance between battery layers.

[0016] Polymer electrolytes also provide a more stable electrolyte compared to other (e.g., liquid) electrolytes. Furthermore, in situ incorporation of polymer electrolytes can lead to the formation of a superior solid electrolyte interface (SEI) within the battery, potentially providing greater stability and ionic conductivity.

[0017] Another potential advantage of the present systems and methods is their ability to stabilize volume. The combination of mechanical properties and ionic conductivity of the polymer electrolytes described herein, as well as high volume change anodes, can help reduce breakage and / or instability associated with battery applications involving flexing. Examples of such volume change anodes include Si and SiO. X The advantages of volume change anodes include reduced electrode cracking, reduced particle breakage, improved interfacial stability, and / or reduced interfacial resistance.

[0018] Another potential advantage of the compositions and methods of the present invention is the ability to enable flexible batteries. For example, by providing a tough, ionically conductive polymer electrolyte, the present systems and methods may enable the construction of flexible batteries with improved interfacial adhesion and enhanced electrode stability.

[0019] Additionally, flexible batteries offer the advantage of incorporating battery components into curved areas of a device that would normally be considered "dead space," thereby potentially increasing the device's battery capacity. Non-limiting examples of such areas can include vehicle roofs (e.g., automobile roofs, or more generally, vehicle roofs or other curved surfaces of a vehicle, including doors, hoods, trunks, etc.), watch bands, eyeglasses (e.g., temples, bridges, end pieces, hinges, etc.), and / or other suitable areas of electronic devices (e.g., wearables, vehicles, power tools, medical equipment, computers, mobile phones, cameras, micromobility, consumer electronics, IoT devices, etc.).

[0020] Another potential advantage of flexible batteries is that they can retain capacity even when folded, i.e., the present systems and methods can provide batteries that can be folded thousands of times (e.g., 1000, 1500, 2000, 3000, 4000, 5000, 7500, 8000, 9000, 10000, 20000, 50000, etc.) with little or no loss of battery capacity (e.g., less than 90% change in capacity between folded and intermediate folded states).

[0021] 2.Composition The polymer electrolyte composition (e.g., upon curing) includes a polymer component and one or more plasticizers (e.g., solvents, salts, additives, etc.). The polymer component (e.g., the cured polymer component) can include dynamic crosslinking groups, covalent bonds, and / or other suitable groups. The polymer components can enable dynamic crosslinking through hydrogen bonding, urethane domains, ionic chelates, ion-pair interactions, and / or other approaches (e.g., dynamic covalent bonds, mechanical bonds, etc.). The polymer component (e.g., oligomers) can also include additional covalent crosslinking functional groups, including acrylates, methacrylates, cyanoacrylates, epoxies, thiols, imides, etc. The composition functions as an ionically conductive medium or a conductive medium precursor (e.g., before curing), enabling ion flow, particularly for use in batteries (or other charge storage devices, such as capacitors, supercapacitors, etc.). More specifically, in some embodiments, the composition can function as a battery electrolyte or in combination with a battery electrolyte (i.e., as a complementary battery electrolyte). The electrolyte can be tunable so that it can be incorporated into a variety of batteries (eg, flexible batteries, structural batteries, high-energy batteries, etc.).

[0022] As used herein, the term "component" generally refers to at least one compound having the properties of that component. For example, a polymer component refers to at least one polymer compound in a composition. Each polymer compound in a polymer component may have a distinct molecular structure and may have a different concentration.

[0023] Unless otherwise stated herein, experimental data is measured at standard ambient temperature and pressure (SATP), i.e., a standard ambient temperature of about 25° C. and a standard ambient pressure of about 1 bar.

[0024] The composition can be in two forms: a precursor variation (also referred to as a precursor, precursor variant, precursor electrolyte, precursor composition, or uncured electrolyte) or an active variation (also referred to as an active variant, active composition, active electrolyte, cured polymer electrolyte, or cured electrolyte). The terms "composition" or "electrolyte" may be used herein to refer to either a precursor variant or an active variant. A precursor variant is an inactive (e.g., pre-cured, unpolymerized, etc.) variant of an electrolyte composition and may contain some and / or all of the components of the electrolyte composition. Depending on the embodiment, the precursor can be converted to an active composition by adding one or more compounds (e.g., initiator compounds) and / or performing an activation process (e.g., curing). The precursor serves as an inactive form of the electrolyte and can be more suitable for storage and transportation. For example, the precursor can be used for sale and / or distribution in combination with an "activating" component that can be used to convert the precursor composition to an active composition.

[0025] In some embodiments, the precursor can include a polymer component that is not fully polymerized (e.g., unpolymerized, partially polymerized, incompletely polymerized), and the precursor can be converted to an active composition by the addition of a polymerization initiator under appropriate thermodynamic conditions. In other embodiments, the precursor lacks one or more components (e.g., a salt component), which can be added (e.g., prior to curing). Note that the precursor electrolyte can have several electrolyte functions. That is, the precursor composition can function as an electrolyte, but conversion of the electrolyte precursor to an electrolyte (e.g., by introduction of a polymerization initiator, catalyst, curing mechanism, activation mechanism, etc.) can provide the electrolyte with altered or enhanced performance capabilities compared to the electrolyte precursor.

[0026] In some embodiments, the precursor composition can improve battery packaging prior to activation of the composition. That is, the precursor composition can serve as an aspect of improved dispersion in the battery. Examples of improved dispersion can include faster dispersion throughout the battery, improved electrolyte distribution (e.g., more uniform distribution throughout the battery), and / or improved penetration into battery components (e.g., improved penetration into the separator, improved penetration into the electrodes, etc.).

[0027] In some of these embodiments, the precursor electrolyte can have advantageous material properties that differ from those of the active electrolyte. A typical comparison between the precursor composition and the active composition is that the precursor composition has a lower viscosity and is in a liquid state, whereas the active composition is generally non-flammable, has a short self-extinguishing time, and behaves like a solid (e.g., a gel, a solid, etc.). For example, the precursor composition can have a low viscosity (e.g., less than 40 cP at 25° C.). In another example, the precursor composition can comprise a liquid composition compared to a free-standing (e.g., a gel, a solid) active composition. In some embodiments, the precursor composition and / or the active composition can have a short self-extinguishing time (SET<5 s / g) and be flame-retardant.

[0028] The composition can be converted or provided as an active composition. The active composition can be a functional electrolyte. In some embodiments, the active composition can have one or more additional components (e.g., polymerization initiator additives, polymerization inhibitor additives) that do not provide direct functional capabilities to the electrolyte but are introduced to enable the precursor composition to be converted into the active composition. However, activation-controlling additives (e.g., inhibitors, initiators) can have a direct functional impact on the operation of the battery. In many embodiments, the active composition can be free-standing. As used herein, the term free-standing can refer to a "relatively" solid state on the time scale of the battery's activity. That is, free-standing can refer to a solid state, a viscoelastic gel, and / or other similar "solid-like" state.

[0029] The active composition can have the same material state as the precursor composition, although it is usually different. For example, in some embodiments, the precursor and active electrolyte are both liquids. In other embodiments, the precursor is a liquid and the active electrolyte is a gel or gel-like. In other embodiments, the precursor is a liquid and the active electrolyte is a solid. The functional properties of the active electrolyte can vary depending on the desired implementation.

[0030] In some embodiments, the active composition provides improved toughness (>50,000 J / m 3), and can improve adhesion (>0.4 N / cm) between the active composition and battery components (e.g., electrodes, separators, current collectors, etc.). The active composition can also shorten the self-extinguishing time (<5 s / g) when combustion is induced and / or occurs. In some embodiments, the storage temperature range (e.g., -80°C to 85°C) and operating temperature range (e.g., -20°C to 60°C) of the active composition can be extended and / or the active composition can be tailored to exhibit higher performance within a specific range (e.g., for precursor compositions, for liquid electrolyte solutions, and for precursor solutions excluding polymer precursors such as monomers or oligomers). The active composition can have elastic properties such that the resulting material has a storage modulus higher than the loss modulus at room temperature. The elastic modulus of the active composition can be in the range of 0.1 MPa to 100 MPa. The active composition can also have ionic conductivity (e.g., >0.1 mS / cm). In one example, the active composition has an electrical conductivity of about 0.1 mS / cm to 100 mS / cm. However, the active composition can have any suitable ionic conductivity (eg, >100 mS / cm).

[0031] In one example, for implementation in a battery or other suitable incorporation, the composition can include a pre-cured electrolyte polymer, which is polymerized in situ. That is, the pre-cured electrolyte composition can include an unpolymerized or incompletely polymerized pre-cured state, which can be sufficiently polymerized to function as a battery electrolyte, a supplemental electrolyte to a battery electrolyte, and / or a substitute for a battery electrolyte after injection into a use system (e.g., a battery). In another embodiment, the electrolyte composition can include a fully active (e.g., strong and / or ionically conductive) polymer electrolyte. The electrolyte composition can also be prepared and polymerized ex situ before being incorporated into a battery. That is, the electrolytic polymer composition can be prepared to a fully functional state (e.g., a cured state) before injection into a use system. In another embodiment, the electrolytic polymer composition can be prepared during a battery cycle (e.g., a charge / discharge cycle), in which case the cure state can depend on the characteristics of the cycle (e.g., the depth of discharge, the voltage maintained during the cycle, the time the battery is held at a given voltage, the number of cycles, etc.).

[0032] The composition can include a polymer component, which includes at least one polymer compound and / or monomers and / or oligomers that can be polymerized to form the polymer compound. The polymer component can comprise 8% to 80% (by weight, mass, volume, stoichiometric, etc.) of the composition. An electrolyte containing the polymer compound can exhibit an elastic or partially elastic response to strain. Additionally or alternatively, it can exhibit a storage modulus at room temperature that is higher than the loss modulus.

[0033] As used herein, polymer compounds (e.g., activated polymers, activated polymer precursors, activated polymer electrolytes) preferably include compounds with crosslinking capabilities, including dynamic and covalent bonds (e.g., to provide greater toughness, improve ionic conductivity). For example, as shown in Figures 10-14, each polymer component can include subcomponents that allow for dynamic crosslinking (dynamic polymer subunits) and / or covalent crosslinking (covalently crosslinked subunits). In many embodiments, activated polymer electrolytes have a toughness of 50,000 J / m², as measured by tensile testing to break at 25°C and / or using other suitable measurement methods. 3 Examples of dynamic crosslinking subunits include urea, urethane, hydrogen-bonding groups (e.g., hydrogen-bond donors, hydrogen-bond acceptors), imine groups, boronic esters, ionic chelating domains, and / or other functional groups. Subunits can be toughened by additional mechanisms, including, but not limited to, steric entanglement (e.g., produced by crosslinking compounds such as polycyclic compounds, particularly isobornyl derivatives or spiro compounds). Examples of covalent crosslinking subunits (e.g., subunits, functional groups in monomers or oligomers that can result in covalent crosslinks in activated polymers) include acrylate, methacrylate, cyanoacrylate, epoxy, imide, and / or thiol (e.g., for thiol-ene reactions) functional groups.

[0034] As used herein, each polymeric compound (e.g., a polymer precursor) is a distinct molecule, which may or may not be composed of distinct monomeric subunits compared to a second polymeric compound. A distinct molecule may be a monomer, an oligomer (as used herein, an oligomer can refer to a material comprising 2 to 20 repeating monomeric subunits and / or a material in which one or more physical properties, such as the material's phase, melting point, glass transition temperature, or viscosity, change substantially after the addition or removal of a single monomeric unit), a polymer (e.g., a polymer electrolyte can be formed from a polymer that undergoes polymerization to form a crosslinked network containing both covalent and dynamic bonds), a molecule or atom that can interact with other molecules (e.g., a polymer electrolyte), and / or any suitable compound. That is, in the case of a polymer precursor comprising (e.g., derived from) two compounds, a first polymeric precursor and a second polymeric precursor, the first polymeric precursor can have distinct monomeric subcomponents compared to the second polymeric precursor. Additionally or alternatively, the two polymeric precursors can have the same monomeric subunits with one or more different functional groups.

[0035] In one example, the polymer component (e.g., the collection of all polymer precursors, the collection of molecular species that will become the polymer, etc.) includes one oligomeric compound (and / or its monomer, dimer, trimer, etc. components). In another example, the polymer component includes two oligomeric compounds (and / or their monomer, dimer, trimer, etc. components). In another example, the polymer component includes three oligomeric compounds (and / or their monomer, dimer, trimer, etc. components). In a fourth example, the polymer component includes four oligomeric compounds (and / or their monomer, dimer, trimer, etc. components). In another example, the polymer component includes five oligomeric compounds (and / or their monomer, dimer, trimer, etc. components). In another example, the polymer component includes six or more oligomeric compounds (and / or their monomer, dimer, trimer, etc. components).

[0036] As used herein, monomer and oligomer are generally used to refer to polymer subunits of compounds that are not polymerized (e.g., not "fully" polymerized, not activated, incompletely polymerized, uncured, curing, etc.). That is, compounds referred to as monomers and oligomers are considered not sufficiently polymerized to be in a so-called "fully" polymerized state. Also, because the polymerization process may include curing, this is sometimes referred to as the uncured state. As part of describing an electrolyte composition, a reference to a polymer component comprising primarily oligomers (or other subcomponents) suggests that the electrolyte is in a precursor / uncured / not fully polymerized state. Because a polymer component may generally include polymer subcomponents of any polymerization level, a cured "fully" polymerized polymer component refers to a polymer component that has been sufficiently polymerized to exhibit the desired functional properties of the polymer component. Functional properties that can be used to define / identify an active polymer component include compositional state (e.g., transition from a liquid to a free-standing state), toughness (>50,000 J / m at 25°C), and mechanical properties. 3), ionic conductivity (>0.1 mS / cm at 25°C), adhesion properties with electrolyte-electrode adhesion greater than 0.4 N / cm, wettability, etc. Additionally or alternatively, the polymerization state can be expressed in molecular terms (e.g., concentration of polymers with length greater than N). Depending on the particular implementation, the particular concentration can vary. Additionally or alternatively, the polymerization state can be expressed in terms of the absence of covalent crosslinks in the precursor state (e.g., only dynamic crosslinks, no crosslinks, crosslink density of about 1 mol / m 3 less than 10 mol / m ), whereas in the polymerized state there is crosslinking (e.g., sufficient crosslinking to result in a free-standing film, with a crosslink density of about 10 mol / m ). 3 This can be expressed in terms of the degree of crosslinking between the polymeric components (e.g., greater than 0.1 MPa, covalent crosslinking, etc.). In many embodiments, the polymeric components are considered to transition to a polymerized state when the composition's modulus of elasticity exceeds 0.1 MPa (e.g., 0.1 to 100 MPa, or any value or range of values ​​therebetween). In one example, the modulus of elasticity in the polymerized state can be 0.1 MPa to 1 MPa. In another example, the modulus of elasticity is 0.5 MPa to 2 MPa. In yet another example, the modulus of elasticity is 50 MPa to 100 MPa.

[0037] Like the polymeric component, depending on the state and embodiment of the electrolyte composition, each compound that is part of the polymeric component can be in a polymerized or unpolymerized state (e.g., the compounds that make up the polymeric component of the electrolyte can be monomers, oligomers, polymers, etc.). A polymerized / cured state refers to a state in which the polymeric component has been sufficiently polymerized so that either the electrolyte composition or the particular polymeric compound exhibits desired functional or molecular properties. For example, the polymeric component is sufficiently "tough" and / or the composition is sufficiently ionically conductive.

[0038] Like the polymer components, electrolyte compositions can have at least one active and / or inactive state. In many embodiments, their active / inactive state can be directly attributed to the state of the polymer components. That is, depending on the embodiment and stage, each polymer compound may be distinctly fully polymerized (e.g., as a fully functional electrolyte), not fully polymerized (e.g., as a monomer component), or partially polymerized (e.g., as a dimer, trimer, etc.). The stage of polymerization may depend on the desired use case (e.g., primary electrolyte or auxiliary electrolyte) and / or the stage of battery development (e.g., electrolyte storage, battery preparation, battery operation). Alternatively, other factors may affect the state of the composition. The active / inactive state of an electrolyte composition can be determined by any of the functional or molecular properties of the composition, such as the state of the composition (e.g., liquid, solid), ionic conductivity, wettability, adhesive properties, the polymerization level of the polymer components, and / or other suitable properties. An inactive state is when the composition is not sufficiently ionically conductive and / or when the polymer components are not sufficiently polymerized. For example, the state of the active polymer component and / or electrolyte composition can be set by the level of crosslinking. In one embodiment, the state of the active polymer, and therefore the active electrolyte composition, is set by the level of covalent crosslinking within the electrolyte composition.

[0039] Typically, once a polymer component and / or electrolyte composition is in an active state, it cannot be returned to an inactive state. However, in some embodiments, switching between the active and inactive states can be reversible. In other embodiments, an active polymer may be degraded to a degraded state (e.g., a state in which the polymer and / or electrolyte no longer achieves the target properties) by sequential depolymerization (to polymer precursors for subsequent polymerization), random chemical degradation (e.g., along the polymer backbone, along the backbone of a polymer precursor, e.g., along the backbone of an oligomer used to form the polymer, etc.), and / or other means.

[0040] Functional properties indicative of the inactive and active states of the electrolyte composition may further include the toughness and / or adhesion provided by the polymer component, the viscosity and / or wettability of the polymer component (and / or polymer precursor, inactive electrolyte composition, etc.), the transition temperature (e.g., melting point, glass transition temperature, etc.) of the polymer component, the ionic conductivity of the electrolyte (e.g., active electrolyte, inactive electrolyte, etc.), etc. Molecular properties indicative of the inactive and active states include the degree of crosslinking between polymer subunits, the molecular weight of the polymer component, etc. For example, in some embodiments, the active state is defined as a tensile strength of 50,000 J / m at room temperature. 3 and in some embodiments, the inactive state comprises a liquid having a viscosity of less than 40 cP at 25° C., while the active state comprises a free-standing film (e.g., the inactive state may be used to infiltrate battery components before solidifying as a film), and in some embodiments, the active state may not have a melting point.

[0041] In some embodiments, a composition may include multiple active and / or inactive states. Alternatively, a composition may have a "continuous" transition between an inactive state and an active state. For example, a composition may continuously improve in performance as an electrolyte as polymerization proceeds. In this example, a composition is considered active when it has been polymerized (or otherwise activated) sufficiently to reach a predetermined threshold of electrolyte activity. Depending on the embodiment, the threshold may be any varying property of the composition. Examples include ionic conductivity, adhesive properties, extensibility, Young's modulus (or other stress / strain properties), wettability, etc.

[0042] As noted above, the polymeric components may be in a polymerized state in which each polymeric compound is fully (or nearly fully) polymerized, or in a pre-cured state in which each polymeric compound is unpolymerized and includes "shorter" oligomeric pieces (i.e., oligomeric compounds or oligomeric subcomponents). Each polymeric compound may be composed of subcomponents, such as potential monomeric subcomponents, and / or shorter N-mer subcomponents, and / or crosslinkers in the pre-cured state.

[0043] Polymeric compounds can include crosslinking functional groups as individual monomer units or as subunits of an oligomer. Depending on the embodiment, the crosslinker can include any common type of crosslinker. Examples of covalent crosslinkers that can be included include acrylate domains, methacrylate domains, epoxy domains, thiol domains, and / or imide domains. However, other domains can also be used for covalent crosslinking. Examples of dynamic crosslinking domains include hydrogen-bonding crosslinkers (e.g., amide, carbamate, urea, carboxyl, hydroxyl, hydroperoxyl, hemiacetal, hemiketal, carboxamide, amidine, primary amine, secondary amine, tertiary amine, primary ketamine, primary aldimine, imide, azide, diimide, cyanate, isocyanate, nitrate, nitrile, nitrosoxy, nitro, nitroso, oxime, etc.), ionic chelating domains (e.g., amine, anionic pendant group, cationic pendant group, chelating group, zwitterionic pendant group, etc.), ion-pair bonding interactions, and / or steric interactions. However, other crosslinkers can also be used. In many embodiments, each polymer compound can have toughening domains (which are typically the result of, or arise as a result of, dynamic crosslinking). The toughness of the polymer components can be further adjusted by using different additive crosslinkers in the pre-cured state and by varying the crosslink density. In this case, additional crosslinkers can be used, including, but not limited to, N-N' methylenebisacrylamide, pentaerythritol tetraacrylate, diethylene glycol dimethacrylate, (2,2-bis(((4-azido-2,3,5,6-tetrafluorobenzoyl)oxy)methyl)propane-1,3-diylbis(4-azido-2,3,5,6-tetrafluorobenzoate)), or crosslinking via acid-amine condensation.

[0044] In many embodiments, the polymer (and / or its precursor) can include toughening domains (or toughening components) that can include dynamic bonds (e.g., hydrogen bonds, dynamic covalent bonds, ion pairing, steric entanglement, metal chelates, π-π interactions, π-cation interactions, π-anion interactions, and / or host-guest interactions such as interactions having an interaction strength of about 0.5 to 50 kJ / mol), and / or polar moieties (e.g., urethanes, carbamates, carbamides, O-thiocarbamates, S-thiocarbamates, dithiocarbamates, carboxyimidates, amidines, carbonates, carboxylates, carboxamides, imides, oximes, thioesters, didicarboxylic acids, and the like, optionally including steric interference effects; polycyclic rings; intermolecular interactions mediated by dipoles, quadrupoles, multipoles, induced multipoles, and the like). In the pre-cured state, the electrolyte composition can include dynamically bound resins and / or monomers, including, but not limited to, dynamically bound methacrylates (e.g., (2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate), guest-host interactions (e.g., alpha-cyclodextrin and polyethylene glycol), metal-ligand interactions (e.g., 2-2'-bipyridine-5-5'-dicarboxylic acid amide and Zn, Mg, or Fe-based ions), ion pair interactions (e.g., acrylic acid and 2-(diisopropylamino)ethyl methacrylate), and / or dynamic covalent bonds. Other examples of dynamic bonding resins and monomers include polyester urethane acrylate, polyester urethane methacrylate, polyether urethane acrylate, polycarbonate urethane acrylate, polycarbonate-polyether urethane acrylate, polycarbonate-polyester urethane acrylate, polyether-polyester urethane acrylate, polyimide urethane acrylate, polyester acrylate, epoxy acrylate, polycarbonate acrylate, polyester-polycarbonate acrylate, polyether acrylate, polyether-polyester acrylate, polyether-polycarbonate acrylate,Polyether-polyester-polycarbonate (or other sequences such as polyether-polycarbonate-polyester, polyester-polyether-polycarbonate, etc.) acrylates, aminated acrylates (e.g. aminated polyether acrylate, aminated urethane acrylate, aminated polyester urethane acrylate, aminated polycarbonate acrylate, combinations thereof, etc.), polycarbonate urethane methacrylate, polycarbonate-polyether urethane methacrylate, polycarbonate-polyester urethane methacrylate, polyether-polyester urethane methacrylate, polyimide urethane methacrylate, polyester methacrylate, epoxy methacrylate, polycarbonate methacrylate, polyester-polycarbonate methacrylate, polyether methacrylate, polyether-polyester methacrylate, polyether-polycarbonate methacrylate, polyether-polycarbonate-polycarbonate (or other sequences such as polyether-polycarbonate-polyester, polyester-polyether-polycarbonate) methacrylate, aminated methacrylate (e.g., aminated polyether methacrylate, amino aminated urethane methacrylate, aminated polyester methacrylate, aminated polycarbonate methacrylate, combinations thereof, etc.), polybutadiene urethane acrylate, polybutadiene urethane methacrylate, bisphenol A epoxy diacrylate, silicone urethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyether urethane acrylate, difunctional (e.g., diacrylate, diurethane, diurethane diacrylate) aromatic urethane acrylate, hydrophobic urethane acrylate (e.g., difunctional aliphatic hydrophobic urethane acrylate, aliphatic hydrophobic urethane acrylate, etc.), hydrophobic urethane acrylate (e.g., difunctional aliphatic hydrophobic urethane methacrylate, aliphatic hydrophobic urethane methacrylate, etc.), isobornyl acrylate (IBOA), poly(ethylene glycol) methacrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) diacrylate,trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), (hydroxyethyl) methacrylate (HEMA), urethane epoxy monomers and / or oligomers (e.g., monofunctionalized with epoxy head groups, difunctionalized with epoxy head groups, etc.), urea epoxy monomers and / or oligomers (e.g., monofunctionalized with epoxy head groups, difunctionalized with epoxy head groups, etc.), urea imide monomers and / or oligomers (e.g., mono-functionalized with an imide head group, di-functionalized with an imide head group, etc.), ureaimide monomers and / or oligomers (e.g., mono-functionalized with an imide head group, di-functionalized with an imide head group, etc.), thiolurethane monomers and / or oligomers (e.g., mono-functionalized with a thiol head group, di-functionalized with a thiol head group, etc.), thiolurea monomers and / or oligomers (e.g., mono-functionalized with a thiol head group, di-functionalized with a thiol head group, etc.), difunctionalized with an alkyl head group, etc.), polycarbonate epoxy oligomers, polyester epoxy oligomers, polyether epoxy oligomers, polycarbonate-polyester epoxy oligomers, polycarbonate-polyether epoxy oligomers, polyester-polyether epoxy oligomers, polycarbonate-polyether-polyester (or other similar sequence variations) epoxy oligomers, polycarbonate imide oligomers, polyester imide oligomers, polyether imide oligomers, polycarbonate-polyester imide oligomers, polycarbonate-polyether imide oligomers, polyester-polyether imide oligomers, polycarbonate-polyether-polyester (or other similar sequence variations) imide oligomers, polycarbonate thiol oligomers, polyester thiol oligomers, polyether thiol oligomers, polycarbonate-polyester thiol oligomers, polycarbonate-polyether thiol oligomers, polyester-polyether thiol oligomers,Polycarbonate-polyether-polyester (or other similarly ordered variations) thiol oligomers, and many more possible additional carbonates, esters, ethers, nitriles, and / or other species. The above examples (e.g., polyester-polycarbonate, but also applicable to any of the similarly referenced materials above) containing multiple polymer or oligomer subgroups can form block co-oligomers (also called copolymers), alternating co-oligomers, random co-oligomers, graft co-oligomers, and / or combinations thereof.

[0045] In addition to one or more toughening domains, the polymeric compound can also include an ion-conducting domain (e.g., a polar moiety such as those described above). Alternatively, the electrolyte composition may include an ion-conducting component. The ion-conducting component and / or the ion-conducting domain may function to improve the ionic conductivity of the electrolyte composition. In some embodiments, the ion-conducting component may include ion-conducting polyethylene glycol, poly(ethylene glycol) methyl ether methacrylate, carbonate, ester, ether, nitrile, and / or other suitable functional groups (e.g., polar functional groups as described above). In one example, the toughening component and the ion-conducting component are part of the same resin. In another example, the toughening component and the ion-conducting component are separate. In many embodiments, the ionic conductivity of the polymer electrolyte in the activated state (e.g., lithium ion conductivity, mobile ions in an energy storage system, etc.) is greater than 0.1 mS / cm at 25°C.

[0046] The composition may include a salt component. The salt component may include at least one salt compound. The electrolyte composition preferably includes 8% to 40% (mass, volume, stoichiometric, etc., ratio of one or more salt compounds to the polymer, based on the total electrolyte composition). The salt concentration is typically about 1 M to 10 M (e.g., 1.5 M, 2 M, 3 M, 4 M, 5 M, 6 M, 7.5 M, 8 M, 9 M, values ​​or ranges therebetween, etc.). For example, the salt concentration may be about 1 M to 2 M. In another example, the salt concentration may be about 2 M to 3 M. The salt component functions to provide ions to the electrolyte. Additionally or alternatively, the salt component may affect the solid electrolyte interface (SEI layer), battery conductivity, battery passivation, operating / stable temperature range, battery cyclability, polymer plasticity, and / or other suitable properties. The selection of the salt component depends on the use case of the polymer electrolyte. Without loss of generality, the salt component will be described herein in the context of a lithium battery use case. For example, in the case of a lithium battery, the salt component can include a lithium salt.More specifically, examples of lithium salt compounds include lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium tetracyanoborate (LiB(CN)4), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluorosulfonyl)imide (LiTFSI), lithium tris(trifluoromethanesulfonyl)methide (LiTFSM), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate LiDFOB, lithium fluoroalkylphosphates (LFAPs such as lithium tris(pentafluoroethyl)trifluorophosphate), lithium sulphite, ... Lithium salts include, but are not limited to, cyclo-difluoromethane-1,1-bis(sulfonyl)imide (LiDMSI), lithium-cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide (LiHPSI), lithium-cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide (LiBETI), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(monofluoromalonato)borate (LiBFMB), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), lithium 4,5-dicyano-2-(pentafluorylethyl)imidazole (LiPDI), and / or other suitable lithium salts.

[0047] In one embodiment, the salt component includes one salt. In a second embodiment, the salt component includes two salts. In a third embodiment, the salt component includes three salts. In a fourth embodiment, the salt component includes four salts. In another embodiment, the salt component includes five or more salts. In some embodiments, the salt component can be modified during use. The number of salts generally depends on the desired electrolyte properties and can be embodiment-specific. In one example of a lithium battery, the salt component can include at least LiPF6 and LiDFOB. In another example of a lithium battery, the salt component can include at least LiTFSI and LiBOB. In one low-temperature embodiment, the salt component can include at least LiBF4. For example, the pre-cured electrolyte composition can include a salt component with a set of salts that improves battery penetration. For battery performance, additional salts can be added to improve the ionic conductivity of the electrolyte, improve the stability of the electrode / electrolyte interface, or reduce cell impedance. In one embodiment of a high-energy density anode battery, the salt component can include at least LiTFSI and LiFSI.

[0048] The composition may include additive components. The additive components may include any number of additive compounds and function to provide specific properties for the electrolyte composition and / or battery functional implementation. The additive components may comprise approximately 1% to 80% by weight of the composition. The additive concentrations may vary widely depending on the specific compound. For example, the flame-retardant additive component may vary from approximately 0% to 20% of the composition, the plasticizing additive component may vary from approximately 10% to 80% of the composition, and other additive components may generally vary from approximately 1% to 10% of the composition. The additive components may be useful for improving battery stability (e.g., reducing flammability), improving interfacial stability between the electrodes and the electrolyte (e.g., promoting SEI formation), improving battery cycling, setting or modifying the temperature operating range of the battery, improving electrolyte implementation (e.g., hardening the electrolyte), reducing electrolyte decomposition, reducing battery component decomposition (e.g., reducing electrode decomposition), and / or imparting other properties or functionality to the battery and / or imparting properties for electrolyte formation or battery operation. In some embodiments, the additive component may include a secondary salt compound (e.g., an additional salt from the salt compounds described above). In some embodiments, the electrolytic polymer composition may be additive-free. The type, number, and / or concentration of the additive compound may depend on the desired function (e.g., high-temperature functionality, extreme stability, battery cyclability) and / or battery embodiment (e.g., battery type, battery separator characteristics, battery application, etc.).Examples of potential "functional" additive compounds include 1,3,2-dioxathiolane-2,2-dioxide (DTD), vinyl acetate (VA), 2-vinylpyridine (VP), fluoroethylene carbonate (FEC), trivinylcyclotriboroxane (tVCBO), VC, LiDFOB, LiBOB, sulfone, ethyl methyl sulfone, tetramethyl sulfone (TMS), prop-1-ene-1,3-sulfone (PES), 1,3-propane sultone (PS), cyclic sulfate, dioxolone, 5-methyl-4-((trifluoromethoxy)methyl)-1,3-dioxol-2-one, phenylboronic acid glycol ester (PBE), 5-methyl-4-((trimethylsilyloxy)methyl)-1,3-dioxol-2-one, trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphite, and the like. phosphate (TBP), triphenyl phosphate (TPP), tris(2,2,2-trifluoroethyl)phosphate (TFP), methyl P,P-bis(2,2,2-trifluoroethyl)phosphate (BMP), trimethyl phosphite (TMPi), tris(2,2,2-trifluoroethyl)phosphite (TTFPi), dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate (DEEP), bis(2,2,2-trifluoroethyl)methyl phosphate (TFMP), bis(2,2,2-trifluoroethyl)ethyl phosphate (TFEP), hexa(methoxy)cyclotriphosphazene (HMOCPN), (ethoxy)pentafluorocyclotriphosphazene (PFPN), (phenoxy)pentafluorocyclotriphosphazene (FPPN), and / or other suitable additives.

[0049] In some embodiments, the additive component can include at least one of FEC, VC, EC, and DEC. In some other embodiments, the additive component can include at least one of FEC, VC, EC, and DMC. In other embodiments, the additive component can additionally or alternatively include at least one of a flame retardant additive (e.g., phosphates, phosphites, phosphonates, phosphonites, phosphides such as TMP, TEP, TBP, TPP, TFP, BMP, TMPi, TTFPi, DMMP, DEEP, TFMP, TFEP, DMMP, DEEP, TFMP, TFEP, HMOCPN, PFPN, FPPN, etc.).

[0050] In some embodiments, the electrolyte can include a plasticizer. The plasticizer includes at least one plasticizer compound and functions to improve the flexibility of the electrolyte. Additionally or alternatively, the plasticizer can reduce the viscosity of the electrolyte composition before curing and / or perform other functions. Any typical plasticizer compound can be included as part of the plasticizer. Examples of plasticizer compounds include ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), propylene carbonate (PC), vinylene carbonate (VC), dimethoxyethane (DME), diethyl ether, tetrahydrofuran (THF), methyl formate (MF), ethyl formate (EF), methyl propionate (MP), methyl butanoate, ethyl formate (EF), ethyl acetate (EA), ethyl propionate (EP), propyl formate, propyl acetate (PA), propyl propionate (PP), glyme, diglyme, triglyme, tetraglyme, and / or other suitable plasticizers (e.g., electrolyte solvent, liquid electrolyte solvent), and the like. In one embodiment, a combination of DEC and EC (e.g., 1:1, 1:2, 2:1, 3:7, 7:3, etc. (v / v, w / w, w / v, v / w, etc.)) is included as the plasticizer component. In one aspect, the plasticizer can constitute a majority weight percent (e.g., greater than 50 wt%) of the electrolyte composition. Alternatively, the plasticizer can constitute a less than majority weight percent. In one aspect, the plasticizer can constitute approximately 40% to 50% of the electrolyte composition. In another aspect, the plasticizer can constitute approximately 30% to 40% of the electrolyte composition. In a third aspect, the plasticizer can constitute approximately 20% to 30% of the electrolyte solution. In a fourth aspect, the plasticizer can constitute less than 20% of the electrolyte solution. In one example of the fourth aspect, the plasticizer can constitute approximately 10% to 20% of the electrolyte solution. In another example of the fourth aspect, the plasticizer can constitute approximately 0.01% to 10% of the electrolyte solution. Any desired method can be used to select the plasticizer, for example, the plasticizer can be selected so that the salt is sufficiently soluble and has high conductivity.

[0051] In some embodiments (e.g., in the case of a pre-cured electrolyte), the electrolyte components can include an initiator (e.g., a polymerization initiator). The initiator functions to initiate polymerization of the polymeric components, thereby enabling polymerization of the polymeric compound, i.e., polymerization of the monomeric and / or oligomeric subunits (e.g., polymer precursors) of the polymeric compound. That is, the initiator can be added to an inactive electrolyte to activate or assist in activation of the electrolyte. Thus, the initiator can be added to the composition before and / or when electrolyte activation is desired. Alternatively, the initiator can be part of the initial composition, and the initiator can be activated by subjecting the composition to appropriate thermodynamic conditions. Decomposition products resulting from the generation of radicals by decomposition (e.g., thermal decomposition) of the initiator are preferably substantially inert to electrochemical reactions (e.g., within the voltage window of the battery, in the electrolyte, etc.). For example, nitrogen can be formed during radical formation using an initiator (in which case the nitrogen is vented from the cell).

[0052] The initiator is preferably a thermal initiator (e.g., an initiator that is heated to a threshold temperature to activate the initiator), however, the initiator may additionally or alternatively be mechanically activated (e.g., upon application of a threshold force), electromagnetically activated (e.g., by irradiation with electromagnetic radiation of sufficient wavelength, frequency, intensity, etc., such as gamma rays, X-rays, ultraviolet light, visible radiation, etc.), electrochemically activated (e.g., activated at a threshold potential), and / or otherwise activated. Examples of initiators include 1-1'-azobis(cyclohexanecarbonitrile), 2,2'-azobisisobutyronitrile (AIBN), 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2'-azobis[2-(2-imidazolin-2-yl)-propane]dihydrochloride, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peracetate, tert-butyl hydroperoxide (TBHP), cumene hydroperoxide, di-tert-butylperoxy Initiators such as tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1′-azobis(cyclohexanecarbonitrile) (ABCN or ACHN), ammonium persulfate, potassium persulfate (or other persulfates), lauroyl peroxide, tert-butyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide (BPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), 2,2-dimethoxy-2-phenylacetophenone (DMPA), and / or any suitable initiator may be used.The concentration of the initiator is typically about 0.1% to about 10% (e.g., 0.1%, 0.2%, 0.3%, 0.5%, 1%, 2%, 2.5%, 3%, 5%, 7%, 7.5%, 9%, 10%, any value or range therebetween, etc.) by weight relative to the polymer precursor.

[0053] In some embodiments (e.g., in the case of pre-cured electrolytes), the electrolyte can include an inhibitor (or polymerization inhibitor). The inhibitor can function to prevent or delay premature polymerization of the tough polymer component or other components, thereby delaying the initiation or polymerization of the tough polymer electrolyte until a desired time. The inhibitor can be part of the initial composition or can be added at a later step. Examples of polymerization inhibitors include phenothiazine (PTZ), butylated hydroxytoluene (BHT), hydroquinone (HQ), 4-methoxyphenol (MEHQ), monobenzone, hydroquinone, guaiacol, 2-hydroxy-5-methoxybenzaldehyde, 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, chloranil, quinone methide, p-phenylenediamine, diethylhydroxylamine, hydroxylhydroxylamine, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), 4-hydroxy-TEMPO (TEMPOL), and / or any other suitable inhibitor.

[0054] As noted above, compositions can be provided in various states, but with substantially the same overall (or relative) concentrations of components. These states can reflect the electrolyte being in an inactive (uncured) or active (cured) state. As shown in the examples of Formulations A-D in Figures 10-13, these states can relate to the relative polymerization levels of the polymeric compounds forming the polymeric components. As shown in Formulation A (Figure 10), the composition can exist (or be constructed) in a state where the polymeric compound (e.g., oligomer) includes the ion-conducting component and / or the toughening component, and a covalent crosslinker is indicated by "X." In many embodiments, the same compounds can also exist (or be constructed) in a state where the ion-conducting component and / or the toughening component are present both as part of the polymer precursor and as separate components, as shown in Formulation B (Figure 11). This can occur in a partially polymerized state of the electrolyte composition or when polymer precursor subunits are added to modify the properties of the electrolyte composition. The composition can also be present (or constructed) as shown in Formula C (FIG. 12) where all components are in separate monomeric states (note, however, that the Formula C example shows a different type of crosslinker than Formula A, but can use the same type of crosslinker). In many embodiments, Formula C can be the unpolymerized (e.g., inactive) form of the electrolyte. Similar to Formulas A-C, Formula D (FIG. 13) shows an example of a composition having monomer subunits for multiple (e.g., two) toughening polymer compounds. In this example, each polymer compound can incorporate the same ion-conducting component, and each polymer precursor can incorporate a different toughening component. In another embodiment, as shown in Formula E (FIG. 14), the composition can include a single polymer compound (Polymer 1), and upon polymerization, the polymer can incorporate two different toughening components (e.g., Components 1 and 2) and an ion-conducting component.

[0055] As noted above, electrolyte compositions can vary significantly depending on the intended use case (e.g., battery type) and operating conditions (e.g., operating temperature, battery size, cyclability, etc.). Furthermore, depending on how the electrolyte composition is initialized (i.e., in situ or ex situ), the composition can further include components that allow for polymerization and "activation" of the polymer compound within the battery volume. Sample battery formulations using the above specifications are provided herein. However, those skilled in the art will recognize that the formulations are not limited to these specific examples (e.g., other ratios can be used, and polymer precursors, salts, plasticizers, initiators, inhibitors, additives, and / or other species can be substituted with other materials from the relevant lists).

[0056] In a first exemplary lithium battery embodiment, the composition can include a tough polymer component containing a covalent crosslinker, the polymer component including a urethane acrylate and / or urethane methacrylate present in the range of 5-50 wt%, isobornyl acrylate (IBOA) present in the range of 1-15 wt%, a salt component including LiPF6 present in the range of 5-20 wt% and LiDFOB present in the range of 0.1-8 wt%, an additive component including TMP present in the range of 0.5-20 wt%, FEC present in the range of 0.1-5 wt%, VC present in the range of 0.1-5 wt%, and a plasticizer including DEC present in the range of 10-40 wt% and EC present in the range of 10-40 wt%. In one embodiment of this exemplary composition, the composition can further include an initiator, benzoyl peroxide, present in the range of 0.01-3 wt%, and an inhibitor, MEHQ, present in the range of 0.005-0.1 wt%. In this embodiment, the initiator and inhibitor are part of the inactive state, with the inhibitor preventing spontaneous polymerization and allowing the initiator to thermally initiate polymerization of the electrolyte to form the active state. This exemplary composition may be particularly useful in flexible battery embodiments, but may generally be used in any battery embodiment.

[0057] In a second exemplary lithium battery embodiment, the composition can include a tough polymer component including a covalent crosslinker, the polymer component including polyacrylamide present in the range of 10-50 wt%, polyethylene glycol dimethacrylate (PEGDMA) present in the range of 5-20 wt%, and isobornyl acrylate (IBOA) present in the range of 5-20 wt%, a crosslinker N,N'-methylenebisacrylamide present in the range of 1-10 wt%, a salt component including LiTFSI present in the range of 1-20 wt%, LiPOF present in the range of 0.1-3 wt%, and LiBOB present in the range of 0.1-5 wt%, an additive component including TMP present in the range of 0.1-15 wt%, FEC present in the range of 0.1-10 wt%, VC present in the range of 0.1-10 wt%, and a plasticizer including DMC present in the range of 10-40 wt% and EC present in the range of 10-40 wt%. In one embodiment of this exemplary composition, the composition can further include an initiator, benzoyl peroxide, present in the range of 0.1-5 wt %, and an inhibitor, MEHQ, present in the range of 0.005-0.1 wt %. In this embodiment, the initiator and inhibitor are part of an inactive state, with the inhibitor preventing spontaneous polymerization and allowing the initiator to thermally initiate polymerization of the electrolyte to form an active state. This exemplary composition can be particularly useful in low-temperature polymer battery embodiments, but can generally be used in any battery embodiment.

[0058] In a third exemplary lithium battery embodiment, the composition can include a tough polymer component comprising dynamic and covalent crosslinks, the polymer component comprising a multifunctional polyetherurethane methacrylate present in the range of 2-40 wt % and butyl acrylate present in the range of 2-20 wt %, a crosslinker pentaerythritol tetraacrylate (PETA) present in the range of 1-10 wt %, a salt component comprising LiPF6 present in the range of 3-10 wt %, LiTFSI present in the range of 3-10 wt %, and LiFSI present in the range of 3-10 wt %, an additive component comprising ethoxy(pentafluoro)cyclotriphosphazene (PFPN) present in the range of 0.1-15 wt %, FEC present in the range of 0.1-10 wt %, VC present in the range of 0.1-10 wt %, and a plasticizer component comprising EMC present in the range of 10-40 wt %. In one embodiment of this exemplary electrolyte composition, the composition can further include an initiator, azobisisobutyronitrile (AIBN), present in the range of 0.1 to 5 wt %, and an inhibitor, MEHQ, present in the range of 0.005 to 0.1 wt %. In this embodiment, the initiator and inhibitor are part of an inactive state, with the inhibitor preventing spontaneous polymerization and allowing the initiator to thermally initiate polymerization of the electrolyte to form an active state. This exemplary composition can be particularly useful in high energy density battery embodiments, but can generally be used in any battery embodiment. This exemplary composition can also be particularly useful when combined with a silicon anode.

[0059] In a fourth exemplary lithium battery embodiment, the composition can include the same composition as the third example and is injected into a cell containing a high volume change anode containing 1-99% Si. Similarly, as part of an inactive state embodiment, this example can further include an initiator, azobisisobutyronitrile (AIBN), present in the range of 0.1-5 wt %, and an inhibitor, MEHQ, present in the range of 0.005-0.1 wt %. This electrolyte composition can be injected into the cell in the inactive state. Once the cell components are sufficiently "permeated," the initiator is thermally decomposed to initiate polymerization of the components, converting the electrolyte composition to the active state.

[0060] 4. Battery System In some embodiments, the polymer electrolyte composition may be a component in a battery embodiment. However, polymer electrolytes can additionally or alternatively be used in supercapacitors, capacitors, fuel cells, and / or other energy storage applications or systems. For example, as shown in FIG. 1 , a polymer electrolyte battery includes a case 110 (e.g., a housing for the battery components), a set of electrodes 120 (e.g., a cathode and an anode spaced apart within the case), a separator 130 (e.g., located between the cathode and anode), and an electrolyte 140 dispersed throughout the case, the electrolyte comprising a polymer electrolyte composition including a polymer component, which may include a crosslinker, a salt component, an additive component, a plasticizer component, and / or one or more other suitable components. The battery system can function as a "battery," and the polymer electrolyte composition provides enhanced embodiments of certain properties (e.g., battery stability, high energy density, improved ionic conductivity, reduced flammability, battery flexibility, mechanical properties, etc.).

[0061] The battery system can include a wide variety of battery embodiments having a variety of shapes, including rolled pouch cells, stacked pouch cells, Z-folded pouch cells, cylindrical cells, prismatic cells, or special form factor cells.

[0062] In one example, the battery system can include a case 110, a pair of electrodes 120 (cathode and anode), a separator 130, and an electrolyte composition. Depending on the embodiment, the cathode can include a cathode active material (e.g., lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), lithium nickel manganese oxide (LNMO), lithium iron phosphate (LFP), lithium manganese oxide (LMO), lithium nickel cobalt aluminum oxide (NCA), such as NCM811, NCM333, NCM523, NCM622, NCM111, etc.), a conductive additive (e.g., carbon black such as C45, C65, carbon super P, acetylene black, mesocarbon microbeads (MCMB), carbon nanotubes (CNTs) such as graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, semiconducting carbon nanotubes, metallic carbon nanotubes, reduced graphene oxide, electrochemical graphene oxide, graphite, fullerenes, conductive polymers, and combinations thereof). etc.), binders (e.g., carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR), poly(acrylic acid) (PAA), sodium alginate (SA), polyvinylidene fluoride (PVDF), polyaniline (PANI), poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoic ester) (PFM), polytetrafluoroethylene (PTFE), poly(ethylene oxide) (PEO), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), sodium carboxymethyl chitosan (CCTS), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), 3,4-propylenedioxythiophene (ProDOT), dopamine hydrochloride, polyrotaxane, polythiophene, combinations thereof, etc.), and / or other suitable materials.Depending on the embodiment, the anode may comprise an anode active material (e.g., carbon-based materials such as graphite, graphitic carbon, carbon fiber, carbon nanotubes, carbon spheres, carbon nanorods, etc.; alloy materials such as aluminum, tin, magnesium, silver, antimony, and alloys thereof; conversion-type materials (CTAMs) such as transition metal sulfides, oxides, hydroxides, phosphides, nitrides, carbides, fluorides, selenides, chalcogenides, oxalates, and niobates; silicon materials; combinations thereof, such as mixtures of graphite and silicon containing 1-99% silicon and the remainder graphite; lithium metal; and the like), one or more conductive additives (e.g., carbon black, carbon nanotubes, graphite, graphene, fullerenes, carbon fiber (VGCF), super P Li, Super C65, Super C45, SO, KS-6, KS-15, SFG-6, SFG-15, 350G, acetylene black, Kejin black, etc.), one or more binders (e.g., polyvinylidene fluoride (PVDF), styrene butadiene copolymer (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), poly(vinyl alcohol) (PVA), humin, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS), chitosan, alginate, etc.), and / or other suitable materials. Depending on the implementation, separator 130 can include (e.g., consist of) a polymer (e.g., a polyolefin such as polyethylene, polypropylene, polybutene, polymethylpentene, poly(tetrafluoroethylene), poly(vinyl chloride), etc.), a nonwoven fiber (e.g., cotton, nylon, glass, polyester, etc.), a natural substance (e.g., wood, rubber, asbestos, etc.), and / or any suitable material. In some embodiments, the separator can be ceramic coated. Electrolyte composition 140 can include a polymer component (as described above), a salt component, an additive component, a plasticizer component, and / or one or more other suitable components.Depending on the embodiment, the polymer component may be a urethane methacrylate and / or a urethane acrylate (e.g., polyester urethane acrylate, polyester urethane methacrylate, polyether urethane acrylate, polycarbonate urethane acrylate, polycarbonate-polyether urethane acrylate, polycarbonate-polyester urethane acrylate, polyether-polyester urethane acrylate, polyimide urethane acrylate, polycarbonate urethane methacrylate, polycarbonate-polyether urethane methacrylate, polycarbonate-polyester urethane methacrylate, polyether-polyester urethane methacrylate). The electrolyte composition may include, for example, acrylate, polyimide urethane methacrylate, polybutadiene urethane acrylate, polybutadiene urethane methacrylate, bisphenol A epoxy diacrylate, silicone urethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyether urethane acrylate, difunctional aromatic urethane acrylate, or difunctional aliphatic hydrophobic urethane acrylate, aminated urethane acrylate, aminated urethane methacrylate, etc.), butyl acrylate (or its monomer and / or oligomer components), and / or IBOA (e.g., when the components are polymerized in the active state). In an exemplary battery system embodiment, the electrolyte composition may include the polymer component, salt component, and additive component as described above. In another embodiment, the polymer component may include polyacrylamide, IBOA, and PEGDMA.

[0063] 4. Method As shown in Figure 2, an in-situ polymer electrolyte formation method for batteries includes steps S110 of preparing an electrolyte precursor, S120 of distributing the electrolyte precursor throughout the battery, and S130 of activating the electrolyte precursor, thereby converting it to a polymer electrolyte. The method functions to generate and incorporate a polymer electrolyte into cavity spaces and porous materials, which provides a flexible, electrically conductive medium for ion exchange (e.g., ion exchange between battery electrodes). Thus, the method can provide a means for generating and distributing fully functional electrolyte polymers throughout batteries (and / or other charge storage devices) and throughout battery components (e.g., battery separators and electrodes) that can function as a medium for ion exchange (i.e., enable or improve battery function). While the method can be practiced using compositions such as those described above, it can generally be practiced with any applicable polymer composition. Figure 3 shows a schematic diagram of an exemplary method for a simple battery including an anode, cathode, and separator, and Figure 4 shows an image of a battery produced by the same method.

[0064] The present method provides a general procedure for the fabrication, incorporation, and activation of polymer electrolytes with a wide range of use cases. These use cases span a variety of battery functions (e.g., structural batteries, high-energy density cells, general-purpose applications, flexible batteries, etc.), battery types (e.g., lithium, lithium-ion, cadmium, sodium-ion, potassium-ion, etc.), battery shapes (e.g., pouch-type, cylindrical, prismatic, coin-type, etc.), operational needs, operating conditions (e.g., operating temperature, operating voltage, charge and / or discharge rates, etc.), and / or other battery or electrolyte characteristics. Thus, the present method can have several different steps depending on the desired implementation. For example, in many embodiments, the method can include cycling the battery. In some embodiments, the method can include degassing the cell. The present method can additionally or alternatively include any other steps, including variations on electrolyte incorporation and activation.

[0065] The present method provides various embodiments for preparing and incorporating a polymer electrolyte into a battery. A first exemplary method can include a step S110 of preparing an electrolyte precursor, a step S130 of activating the electrolyte precursor outside the battery, and then a step S120 of distributing the polymer electrolyte throughout the battery. In this embodiment, the electrolyte polymer is first prepared and then distributed throughout the battery. This embodiment can be used when the polymer electrolyte is flowable and can be sufficiently distributed throughout the battery with minimal processing.

[0066] A second example method may include steps S110 of fabricating an electrolyte precursor, S120 of dispensing the electrolyte precursor throughout a battery, and S130 of activating the electrolyte precursor within the battery. This example method may have the ability to generate a polymer electrolyte within the battery (e.g., in situ gel electrolyte formation). Furthermore, this method may leverage functional properties of the electrolyte precursor that are different from those of the activated polymer electrolyte (e.g., having lower viscosity and improved wettability for dispensing within the battery).

[0067] A third example method can include a step S110 of preparing an electrolyte precursor, followed by a step S130 of distributing the electrolyte precursor throughout the battery while simultaneously forming a polymer electrolyte from the electrolyte precursor. This method can be performed in a similar manner to the second example method. Furthermore, this example method can be particularly useful when the electrolyte precursor includes multiple solutions. In one aspect of this third example, a first electrolyte precursor can be first distributed throughout the battery (S120). Once this distribution is complete, a second electrolyte precursor containing a polymerization initiator can be distributed throughout the battery, thereby simultaneously distributing the electrolyte precursor throughout the battery as it is converted into a polymer electrolyte.

[0068] A fourth example method can include simultaneously fabricating an electrolyte precursor S110 and distributing the electrolyte precursor throughout a battery S120, and activating the electrolyte precursor S130 within the battery to form a polymer electrolyte. This example method can be practiced in embodiments where the electrolyte precursor needs to be distributed as individual components. This is the case when the (polymeric) monomer and / or oligomer subunits or other components have low diffusivity or wettability, and "layering" the components throughout the battery can result in better distribution of the components within the battery.

[0069] Thus, depending on the desired use case, the method allows for the distribution of electrolyte precursors and / or electrolytes throughout the battery (e.g., in an active or inactive state). Thus, depending on the desired implementation, the method allows for the production of electrolyte precursors with different properties than polymer electrolytes, which can be exploited to improve battery manufacturing and, therefore, battery performance.

[0070] Preparation of the electrolyte precursor, S110, functions to combine one or more components of the polymer precursor. S110 preferably results in the formation of an inactive polymer electrolyte. However, S110 can (e.g., in combination with S130) result in an active polymer electrolyte.

[0071] S110 preferably forms an electrolyte precursor solution, which may include one or more solvents (e.g., plasticizers), one or more additives, polymer precursors (e.g., monomers, oligomers, polymer components, etc.), one or more salts, one or more initiators, one or more inhibitors, and / or other suitable components.

[0072] In one embodiment, S110 can form two solutions, where the first solution can include one or more plasticizers (e.g., one or more solvents), one or more additives, one or more salts, one or more inhibitors, and / or one or more polymer precursors, and the second solution can include one or more solvents (typically, but not necessarily, the same solvents as the first solution) and one or more initiators. In another embodiment, S110 can form a single solution (e.g., including one or more solvents, one or more additives, one or more salts, one or more initiators, one or more polymer precursors, and one or more initiators). In another embodiment, S110 includes forming a mixture of a polymer precursor and, optionally, one or more inhibitors or one or more initiators; in this embodiment, a liquid electrolyte can be prepared and can be combined with the mixture or already included in the battery. However, S110 can form any suitable solution.

[0073] The exact composition of the electrolyte precursor will vary depending on the implementation, but generally involves combining (e.g., mixing, combining, etc.) together polymer components (e.g., monomers, dimers, trimers, oligomers, etc. for polymeric compounds, initiators, inhibitors, etc.), plasticizers, and other electrolyte components (e.g., salts and additives). In some aspects, the more viscous components of the electrolyte precursor solution can be mixed first, followed by the less viscous components (e.g., polymer initiators). In other aspects (e.g., in the case of liquid oligomers, monomers, resins, polymer precursors, etc.), the initiator can be added first and then homogenized with the other components. However, the components of the electrolyte precursor can be mixed in any order (e.g., sequentially, simultaneously, contemporaneously, staggered, alternating, etc.) until the target mixture is achieved.

[0074] In some embodiments, the electrolyte precursor can be prepared as multiple solutions. In these embodiments, the separate solutions can be mixed before and / or during injection / dispensing into the battery (Block S120) and / or during construction of the polymer electrolyte (Block S130). For example, in one embodiment, the electrolyte precursor can be separated into two solutions, with the first solution comprising (e.g., consisting of, consisting essentially of) the polymer components, salts, and additives, and the second solution comprising (e.g., comprising only, consisting of, consisting essentially of, consisting essentially of, consisting essentially of) the polymerization initiator and potentially other auxiliary additives.

[0075] The viscosity of the electrolyte precursor is preferably less than about 50 cP (e.g., 1 cP, 2 cP, 5 cP, 10 cP, 12 cP, 15 cP, 17 cP, 18 cP, 20 cP, 22 cP, 25 cP, 27 cP, 30 cP, 33 cP, 35 cP, 40 cP, 45 cP, 50.5 cP, 51 cP, values ​​or ranges therebetween, etc.) at the infiltration temperature (e.g., 0-100°C, e.g., 10°, 20°C, 25°C, 30°C, 40°C, 50°C, 75°C, or other temperatures or ranges therebetween), which may be beneficial for subsequent steps of the method (e.g., dispersing the electrolyte precursor in the battery in S120) and / or for obtaining a homogenous electrolyte precursor solution. However, the viscosity may be greater than about 50 cP (e.g., one solution may have a viscosity greater than 50 cP and the second solution may have a viscosity less than 50 cP such that when the solutions are mixed, the mixture of the solutions has a viscosity less than 50 cP).

[0076] The one or more electrolyte precursor solutions can include one or more plasticizers (e.g., one or more solvents as described above, one or more solvent mixtures, one or more salts such as salt compounds as described above, one or more additives as described above, etc., which may promote plasticity, flexibility, etc. in the cured polymer as formed in S130), polymer precursors (e.g., oligomers, monomers, etc. as described above), one or more inhibitors (as described above), initiators (as described above), and / or any other suitable components.

[0077] The oligomer preferably functions to form a polymer matrix that allows ion transport throughout the polymer. In some embodiments, the oligomer may be a difunctional oligomer (e.g., one featuring two polymerizable groups at two sites, such as two accessible vinyl groups, as shown in Figure 4), which can facilitate and / or enable the formation (upon polymerization) of a crosslinked polymer network. The oligomer is typically a cooligomer (e.g., made from two or more monomers), but may also be a homo-oligomer. The cooligomer can be an alternating cooligomer (e.g., ABABAB for monomers A and B), a random cooligomer, a block cooligomer (e.g., AAAABBBB for monomers A and B), a graft cooligomer, and / or have any suitable structure.

[0078] The oligomer preferably has a non-polar backbone (e.g., hydrocarbon such as methylene, ethylene, propylene, butylene, pentalene, hexylene, heptylene, octylene, nonylene, decylene, etc., aliphatic, aromatic, etc., where the aliphatic groups can be linear, branched, cyclic, bridged, spiro, etc.) linked by polar groups (e.g., carbonate, ester, ketone, carbamide, carbamate, thiocarbamate, thiocarbamide, thiocarbonate, dithiocarbonate, ether, thioether, imide, imine, epoxide, amide, acid anhydride, nitrile, amidine, cyanate, isocyanate, nitrosoxy, nitro, nitroso, oxime, sulfinyl, sulfonyl, sulfonate ester, sulfone, thiocyanate, isothiocyanate, thioester, dithiocarboxylic acid ester, etc.).

[0079] The oligomers are preferably terminated with acrylate and / or methacrylate groups (to facilitate polymer formation). However, the oligomers can additionally or alternatively be terminated with any suitable end group (e.g., epoxy, thiol, imide, cyanoacrylate, etc.). In preferred embodiments, the oligomers can include urethane (e.g., carbamate functional groups), urea (e.g., ureido functional groups), and / or amide (e.g., carboxamide functional groups) between the acrylate and the remainder of the oligomer. In other embodiments, the functional groups can form pendant groups (e.g., in addition to or instead of functional groups within the backbone of the cured polymer and / or oligomer formed by polymerizing the oligomer and / or monomer). However, the oligomers can include any suitable structure.For example, urethane acrylates and / or urethane methacrylates (e.g., monofunctional aliphatic hydrophobic urethane acrylates, difunctional aliphatic hydrophobic urethane acrylates, aromatic hydrophobic urethane acrylates, monofunctional aliphatic hydrophobic urethane methacrylates, difunctional aliphatic hydrophobic urethane methacrylates, aromatic hydrophobic urethane methacrylates, polyester urethane acrylates, polyester urethane methacrylates, polyether urethane acrylates, polycarbonate urethane acrylates, polycarbonate-polyether urethane acrylates, polycarbonate-polyester urethane acrylates, polyether-polyester urethane acrylates, polyimide urethane acrylates) , polycarbonate urethane methacrylate, polycarbonate-polyether urethane methacrylate, polycarbonate-polyester urethane methacrylate, polyether-polyester urethane methacrylate, polyimide urethane methacrylate, polybutadiene urethane acrylate, polybutadiene urethane methacrylate, bisphenol A epoxy diacrylate, silicone urethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyether urethane acrylate, difunctional aromatic urethane acrylate, or difunctional aliphatic hydrophobic urethane acrylate, oligomers such as those mentioned above, can be used as the oligomer.

[0080] The monomer preferably functions to modify (e.g., decrease) the viscosity of the precursor solution. However, the monomer can additionally or alternatively modify the properties of the polymer (e.g., crosslink density, toughness, flexibility, adhesion, etc., resulting properties of the cured polymer). Exemplary monomers include isobornyl acrylate (IBOA), trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), (hydroxyethyl) methacrylate (HEMA), and / or other suitable monomers. In some examples, the polymer precursor can include 10-90% (e.g., weight %, volume %, stoichiometric %, etc.) of oligomer, with the remainder of the polymer precursor being monomer. In other examples, the polymer precursor can include oligomer (e.g., consist of, consist of, consist essentially of, or consist essentially of oligomer). However, the polymer precursor can have any suitable composition.

[0081] The step S120 of dispensing the electrolyte precursor functions to introduce the electrolyte precursor into the battery and distribute it among the appropriate battery components (e.g., the battery separator and electrodes). The step S120 of dispensing the electrolyte precursor into the battery varies depending on the battery (e.g., type, size, shape, electrode type, separator type, electrode material, electrode active material porosity, separator porosity, separator material, etc.). The battery is preferably a dry battery stack (e.g., a battery excluding only the electrolyte; an anode, separator, and cathode in a housing or casing; a battery cell without an electrolyte, etc.). However, the battery may also be a liquid battery (e.g., a functional battery cell, a battery stack including a liquid electrolyte, etc.). Although the step S120 of dispensing the electrolyte “precursor” into the battery is referred to, the order of the method steps is not fixed; in some embodiments, S120 can include dispensing a polymer electrolyte (e.g., an active polymer electrolyte precursor, a polymeric electrolyte precursor, etc.) or dispensing an electrolyte precursor solution. In these embodiments, S120 functions to distribute the active functional electrolyte throughout the battery or distribute the electrolyte components throughout the battery.

[0082] The electrolyte is preferably distributed uniformly throughout the battery such that each component is substantially uniformly distributed (e.g., there are minimal concentration gradients or differences in the concentrations of the electrolyte components in various regions of the battery). However, the electrolyte may be distributed non-uniformly throughout the battery (e.g., a high concentration of polymer precursor in the electrodes, a low concentration of polymer precursor in the electrodes, a high concentration of polymer precursor in the separator, a low concentration of polymer precursor in the separator, etc.).

[0083] In many embodiments, step S120 of dispensing the electrolyte precursor into the battery can include injecting the electrolyte precursor into the battery. This can depend on the type and / or shape of the battery. For example, in a battery pouch embodiment, the electrolyte precursor can be injected directly into the battery pouch, onto the separator, and / or onto the electrodes in the battery. This technique can also be implemented for other battery shapes (e.g., cylindrical cells and prismatic cells). In the case of coin cells, a pipette can be used to inject the electrolyte solution directly onto the electrodes and separator. Injecting the electrolyte precursor can include multiple injections. However, the electrolyte precursor can additionally or alternatively be added dropwise using a syringe pump, by injection, and / or using any suitable process or processes.

[0084] In some embodiments, multiple injections of electrolyte precursor solution can be performed. In one such embodiment, a first injection is performed using a low-viscosity (e.g., viscosity less than about 30 cP) electrolyte precursor solution, followed by an injection using a high-viscosity (e.g., viscosity greater than about 30 cP, formed by a solution having the same components as the low-viscosity solution but with a higher concentration of polymer precursor). In this case, the low-viscosity solution can facilitate penetration of the battery components as well as the components of the high-viscosity solution into the battery.

[0085] The electrolyte precursor solution is preferably injected into the battery in a controlled environment (e.g., a glove box or similar environmental control, an inert atmosphere, a clean room, etc.) to minimize the introduction of undesirable substances into the battery (particularly, but not limited to, water). However, the electrolyte precursor solution can be injected into the battery in any suitable environment.

[0086] To improve electrolyte uptake, S120 can include allowing time for the electrolyte to "soak" (e.g., penetrate the battery components—also known as aging or wet aging, the term wet aging being used to distinguish it from battery aging at a potential) within the battery and battery components. In some embodiments, the battery can be soaked for a set period of time (e.g., 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 24 hours, 30 hours, 36 hours, 48 ​​hours, 72 hours, 96 hours, 120 hours, 144 hours, any value or range therebetween, etc.).

[0087] In some embodiments, pressure or negative pressure (e.g., vacuum) can be applied to assist in drawing and / or forcing the electrolyte into the battery components. In some embodiments, a small, directional charge (e.g., charging the battery, discharging the battery) can be applied to the battery to assist in dispersing the electrolyte (e.g., via electrowetting). Additional measures (e.g., massaging, stirring, applying alternating pressure, rolling, centrifugation, etc.) can be used to improve penetration of the battery components. During wet aging, the battery and electrolyte (e.g., the polymer electrolyte precursor solution) can be maintained at ambient temperature, controlled temperature (e.g., room temperature, 20-25°C), elevated temperature (25-100°C or a range thereof, e.g., 30°C, 40°C, 50°C, 60°C, etc., where the temperature preferably does not exceed the boiling point of the components of the polymer precursor solution under vacuum pressure), and / or reduced temperature (e.g., below about 20°C, where the temperature preferably does not fall below the freezing point of the components of the polymer precursor solution).

[0088] In some instances, pulsed vacuum (e.g., two vacuum cycles, three vacuum cycles, four vacuum cycles, five vacuum cycles, seven vacuum cycles, ten vacuum cycles, twenty vacuum cycles, fifty vacuum cycles, etc., applying negative pressure followed by periods of ambient or increasing pressure) can be used to induce or promote infiltration of the polymer precursor solution into the battery components. The pressure during the vacuum phase is preferably less than about 100 kPa (e.g., <1 bar, <0.95 bar, <0.92 bar, <0.9 bar, <0.8 bar, <0.75 bar, <0.5 bar, <0.1 bar, <0.05 bar, <0.01 bar, etc.). Typically, the same vacuum pressure is used in each phase. However, different vacuum pressures can be used for successive phases (e.g., a lower vacuum pressure, i.e., a stronger vacuum, can be used in a later phase, and a higher vacuum pressure, i.e., a weaker vacuum, can be used in a later phase). Each phase (e.g., vacuum and ambient pressure phases, each vacuum phase, each ambient pressure phase) can have the same duration or different durations (e.g., each vacuum phase is the same duration, each ambient pressure phase is the same duration, but the vacuum phase and ambient pressure phase have different durations). Phase durations can be from about 1 minute to 24 hours (e.g., 30 seconds, 45 seconds, 60 seconds, 90 seconds, 120 seconds, 3 minutes, 5 minutes, 7 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes, 60 minutes, 90 minutes, 120 minutes, 3 hours, 5 hours, 6 hours, 8 hours, 12 hours, 16 hours, 24 hours, or any value or range therebetween). Pulsed vacuum infiltration can be carried out at ambient temperature (e.g., room temperature, about 20-25°C), elevated temperature (e.g., a temperature between or within a range of 25-100°C, where the temperature preferably does not exceed the boiling point of the components of the polymer precursor solution at vacuum pressure), and / or reduced temperature (e.g., below about 20°C, where the temperature preferably does not fall below the freezing point of the components of the polymer precursor solution). In some embodiments, rather than at atmospheric pressure, vacuum pressure can be alternated with elevated pressure phases.In other embodiments, phases of atmospheric pressure can be alternated with periods of high pressure (e.g., >1.05 bar, >1.1 bar, >1.2 bar, >1.3 bar, >1.4 bar, >1.5 bar, >2 bar, >5 bar, >10 bar, etc.) phases. In other embodiments, multi-phase (e.g., including vacuum, mixed atmospheric and high pressure, different temperature phases, etc.) processes can be used to improve infiltration of battery components. However, infiltration can also be promoted in other ways.

[0089] In some embodiments, the battery cells can be sealed after injection (e.g., immediately after injection, simultaneously with injection, etc.). Sealing the battery can include welding, gluing, bonding, loose sealing, curing in place, forming in place, using gaskets, using tape (e.g., low surface energy tape, acrylic foam tape, etc.), and / or can be sealed in any manner. Alternatively, the battery cells can be left open (e.g., to the environment adjacent to the battery during infiltration and curing).

[0090] Depending on the implementation (e.g., for a battery including a copper current collector), step S120 of dispensing the electrode precursor into the battery can include applying a tap charge to the battery. The tap charge can be beneficial in preventing, reducing, or preventing copper dissolution and / or improving battery stability by increasing the cell potential. The tap charge is preferably between 1.5 V and 2.2 V. However, the tap charge may be less than 1.5 V or greater than 2.2 V. The tap charge can be applied before, during, and / or after aging (e.g., wet aging) the battery and polymer electrolyte precursor solution. Similarly, the tap charge can be applied before, during, and / or after applying a vacuum pulse.

[0091] The step of activating the electrolyte precursor S130 functions to convert the electrolyte precursor solution (e.g., its polymer precursor) into a functioning, ionically conductive medium (e.g., a polymer electrolyte, a gel electrolyte, a polymerized polymer precursor, etc.). Activating the electrolyte precursor solution may also be referred to as and / or include curing the polymer electrolyte precursor solution, solidifying the polymer electrolyte precursor solution, polymerizing the polymer electrolyte precursor solution (e.g., its polymer precursor), initiating polymerization of the polymer precursor, and / or other related processes. Depending on the implementation, S130 may require additional steps (e.g., applying an electrical charge to or heating the electrolyte precursor) to build / activate the polymer electrolyte precursor solution in addition to electrolyte polymerization. S130 is preferably performed inside the battery (e.g., after in situ polymerization, in situ activation, S120). However, S130 can be performed outside the battery (e.g., ex situ polymerization, ex situ activation, prior to S120) and / or while the polymer electrolyte precursor solution is in contact with the battery components (e.g., during S120).

[0092] As part of the step S130 of activating the electrolyte precursor, properties of the electrolyte composition are typically changed. In addition to improving ionic conductivity, the composition may change state (e.g., from a liquid state to a solid or gel state), reducing wettability, improving adhesion, improving toughness, and increasing battery flexibility. As noted above, depending on the implementation, the step S130 of activating the polymer electrolyte precursor solution may occur simultaneously with or separately from S110 and / or S120.

[0093] In many embodiments, step S130 of activating the electrolyte precursor includes a curing process. The curing process depends on the polymer precursor, the initiator, and / or other suitable aspects of the system. Examples of curing processes include mechanical curing (e.g., curing initiated by a threshold pressure or force), thermal curing (e.g., curing initiated by increasing the temperature of the polymer electrolyte precursor solution), electrochemical curing (e.g., curing initiated by an electrical potential applied to the polymer electrolyte precursor solution), electromagnetic curing (e.g., curing initiated by irradiating the polymer electrolyte precursor solution with electromagnetic radiation of sufficient wavelength, intensity, photon flux, etc.), combinations thereof, and / or other suitable curing mechanisms.

[0094] Curing the polymer electrolyte precursor solution preferably results in a crosslinked polymer electrolyte (e.g., as shown in Figure 16). In specific examples, the crosslinked polymer electrolyte can be in a gel-like state containing plasticizers, salts, and / or additives, and the crosslinked polymer electrolyte forms an interconnect structure through the battery electrodes and separator. In some embodiments, the crosslinked polymer electrolyte can form a ladder-like compound. In other specific examples, the polymer can include one or more hydrocarbon backbones (e.g., formed by polymerization of vinyl groups from acrylates, methacrylates, etc.) with oligomeric and / or monomeric moieties forming pendant or side groups (e.g., in the example shown in Figure 16, the oligomeric backbones shown in gray can be considered pendant or side groups of the polymer backbone shown in black, resulting from polymerization between the vinyl groups of the oligomers and / or monomers). The oligomers and / or monomers can be bonded to a single polymer backbone at a single position, at multiple positions, or at multiple polymer backbones (e.g., each end of the oligomer can be integrated into a different polymer backbone within the crosslinked network), and / or can be otherwise bonded to any suitable backbone region. The polymer may additionally or alternatively be linear, block, branched, and / or have any suitable architecture.

[0095] The crosslinked polymer (e.g., gel electrolyte, covalently bonded gel electrolyte network, etc.) preferably contains ion-conducting domains. The ion-conducting domains can be formed, for example, from polar functional groups within the oligomers that form the ion-transport network. This results in an ion-conducting polymer electrolyte (e.g., with an ionic conductivity of greater than 0.1 mS / cm at 25°C).

[0096] The operating parameters of the curing process, such as cure temperature, cure time, cure pressure, cure mechanism, and / or other operating parameters, can depend on the battery application, the target battery properties (e.g., toughness, flexibility, energy density, charge rate, etc.), the target electrolyte properties (e.g., ionic conductivity, crosslink density, state of matter, etc.), the solution components (e.g., initiator material, polymer precursor, etc.), and / or other factors. For example, a lower crosslink density (which correlates with the degree of completion of the polymerization process, the degree of full cure, etc., and can be measured using swelling tests according to ASTM standards D2765 or F2214, rheological measurements, dynamic mechanical analysis, etc.) can be achieved by conducting the curing process for a shorter period of time, conducting the curing process at a lower activation energy (e.g., lower temperature), increasing the inhibitor concentration in the precursor solution, and / or otherwise controlling the crosslink density.

[0097] Depending on the battery type, battery cell geometry, curing method, and electrolyte composition used, external pressure may or may not be applied to the battery and / or electrolyte (e.g., 5-1000 psi may be applied). This process is sometimes referred to as fixing the battery. External pressure is preferably applied uniformly throughout the battery, but may also be applied non-uniformly (e.g., more pressure along the edges of the battery, more pressure in the center of the battery, etc.).

[0098] Depending on the embodiment, curing of the electrolyte precursor solution can take from about 30 minutes to 1 week (e.g., 15 minutes, 30 minutes, 45 minutes, 60 minutes, 90 minutes, 120 minutes, 240 minutes, 6 hours, 8 hours, 12 hours, 15 hours, 18 hours, 24 hours, 36 hours, 48 ​​hours, 72 hours, 96 hours, 144 hours, values ​​or ranges therebetween, etc.). In some embodiments, curing can take even longer.

[0099] In embodiments using thermal curing, the electrolyte precursor solution can be cured at a temperature of about 60-80° C. However, lower temperatures can also be used.

[0100] In embodiments using electrochemical curing, the electrolyte precursor solution can be cured at a nominal potential of about 2.4 to 4.2 V. However, the electrolyte precursor can be cured at any suitable potential.

[0101] In one example of a coin cell, the coin cell can be cured for 2 hours on an 80°C hot plate or in an 80°C oven. In one example of a pouch cell, the pouch is clamped in place so that 5 psi of pressure is applied evenly to the cell and cured for 2 hours at 80°C. In one curing process, the temperature is increased directly to the desired cure temperature (e.g., 80°C). Another example of a curing process incorporates a temperature gradient, increasing the temperature stepwise to the desired cure temperature. In a second example of a pouch cell, the cell is cured for 7 hours without applying external pressure, gradually increasing the temperature in small increments (e.g., 5°C) up to 80°C, allowing the cell to fully equilibrate at one temperature before increasing the temperature to the next increment.

[0102] Alternatively, other methods of electrolyte polymerization / activation can be incorporated, or multiple activation methods can be used in combination. In another embodiment, step S120 of activating the electrolyte precursor can include initiating the polymerization process by applying an electrochemical technique. That is, an electrical charge can be passed through a battery or through the electrolyte solution alone, thereby solidifying the electrolyte through interaction with other electrolyte components (e.g., salts). In another embodiment, a time delay for the initiation of polymerization can be incorporated.

[0103] In some embodiments, when step S110 of preparing the electrolyte precursor includes creating multiple solutions, S130 can include mixing the multiple solutions. For example, S130 can include mixing a polymerization initiator solution and a polymer electrolyte precursor solution. This can be done as part of a curing process in which the compositions are heated simultaneously and / or as part of a separate activation / polymerization process (e.g., premixing the solutions before introducing them into the activation mechanism).

[0104] In some embodiments, the method can include a step S140 of cycling the battery. Cycling the battery can form a solid-electrode interface (SEI) between the electrode and the electrolyte, prelithiate the anode, store energy in the battery (or other energy storage device), and / or perform other functions. S140 (and S130) can be performed in a forming cabinet (e.g., a cabinet configured to maintain multiple batteries, each at a target temperature, pressure, potential, current, atmosphere, and / or other suitable conditions) and / or in any suitable system. S140 is typically performed after S130. However, S140 can also be performed before and / or simultaneously with S130. As a specific example, S140 can be performed before one or more polymer electrolyte precursor solutions are fully cured (e.g., before achieving a final crosslink density, a target ionic conductivity, a target toughness, a target adhesion, a target sufficient penetration, etc.). In this example, the applied polarization allows for additional or complete curing processes.

[0105] Immersion and in-situ incorporation of electrolyte can reduce the time required to form a battery compared to conventional batteries (e.g., electrochemical aging time can be reduced compared to embodiments that do not include wet aging). In some embodiments, initial cycling of the battery can include application of external pressure and cycling at elevated temperatures. Furthermore, as shown in Figures 5 and 6, in-situ incorporation of electrolyte can result in improved electrode / electrolyte adhesion and a unique combination of high conductivity and toughness. Furthermore, as shown in Figure 7, incorporation of an electrolyte polymer can enable the battery to withstand significant flex cycles without a decrease in cycling performance or loss of cell capacity. Similarly, the introduction of a polymer electrolyte can facilitate improved resistance to puncture in the battery (e.g., the battery can continue to function after puncture without significant thermal runaway).

[0106] In some battery cycling embodiments, the battery cell can be placed in a potentiostat or cycler through which a voltage hold is applied to the battery, a constant current (e.g., charging / discharging the cell) is applied to the battery for a specified time, an elevated temperature or temperature gradient is applied to the battery, and / or the battery is clamped at a target pressure.

[0107] In some embodiments, the method can further include degassing the cell. Degassing the cell serves to remove gas, and possibly liquid, that forms within the battery cell during the introduction and / or activation of the electrolyte (e.g., initiator decomposition, polymerization reaction, etc.) and / or the formation of the SEI layer. Degassing the cell can vary greatly depending on the type of battery. This can be done using a degassing method built into the battery. Alternatively, degassing the cell can include opening the cell (e.g., via piercing, unsealing, etc.), releasing gas (e.g., applying a vacuum, degassing, etc.), and sealing the cell after degassing is complete.

[0108] As used herein, terms such as first, second, third, etc. are used to characterize and distinguish various elements, components, regions, layers, and / or sections. These elements, components, regions, layers, and / or sections should not be limited by these terms. The use of numerical terms may be used to distinguish one element, component, region, layer, and / or section from another element, component, region, layer, and / or section. The use of such numerical terms does not imply a sequence or order unless clearly indicated by context. Such numerical references may be used interchangeably without departing from the teachings of the embodiments and aspects herein.

[0109] As used herein, "substantially" or other approximation terms (e.g., "about," "approximately," etc.) may be within a preset error threshold or tolerance of a measurement standard, component, or other standard (e.g., within 0.001%, 0.01%, 0.1%, 1%, 5%, 10%, 20%, 30% of the standard) or may be otherwise interpreted.

[0110] Those skilled in the art will recognize from the above detailed description, and from the drawings and claims that modifications and variations can be made to the embodiments of the invention without departing from the scope of the invention as defined in the following claims.

[0111] Specific examples In a first specific example, the electrolytic polymer composition comprises a polymer component at a concentration of 8% to 80% by weight of the electrolyte composition, which provides dynamic and covalent crosslinks in an activated state; a salt component at a concentration of 8% to 40% by weight of the electrolyte composition, which comprises at least one salt compound; and a plasticizer component at a concentration of 1% to 80% by weight of the electrolyte composition, which comprises at least one plasticizer compound. In a variation of the first specific example, the electrolytic polymer composition has two states: a pre-activated state in which the electrolytic polymer composition comprises a solution; and an activated state in which the electrolytic polymer composition comprises a free-standing form comprising a gel state or a solid state. In a variation of the first specific example, the polymer component comprises an oligomer comprising at least one polar functional group and at least one polymerizable functional group. In a variation of the first embodiment or variations thereof, the at least one polar functional group is selected from the list consisting of carbamide, carbamate, imine, boronate ester, and ionic chelating domain; the at least one polymerizable functional group is selected from the list consisting of acrylate, methacrylate, cyanoacrylate, epoxy, imide, and thiol; and the plasticizer is selected from the list consisting of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (ETC), or methyl methyl carbonate (MMCO). The alkyl group is selected from the list consisting of ethylene glycol methyl ether (EMC), propylene carbonate (PC), vinylene carbonate (VC), dimethoxyethane (DME), diethyl ether, tetrahydrofuran (THF), methyl formate (MF), ethyl formate (EF), methyl propionate (MP), methyl butanoate, ethyl formate (EF), ethyl acetate (EA), ethyl propionate (EP), propyl formate, propyl acetate (PA), propyl propionate (PP), glyme, diglyme, triglyme, tetraglyme, and combinations thereof.In a variation of the first embodiment, the electrolyte formulation further comprises an additive (e.g., 1-10 wt %), the additive being selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide (DTD), vinyl acetate (VA), 2-vinylpyridine (VP), fluoroethylene carbonate (FEC), trivinylcyclotriboroxane (tVCBO), VC, LiDFOB, LiBOB, sulfone, ethyl methyl sulfone, tetramethyl sulfone (TMS), prop-1-ene-1,3-sulfone (PES), 1,3-propane sultone (PS), cyclic sulfate, dioxolone, 5-methyl-4-((trifluoromethoxy)methyl)-1,3-dioxol-2-one, phenylboronic acid glycol ester (PBE), 5-methyl-4-((trimethylsilyloxy)methyl)-1,3-dioxol-2-one, trimethyl phosphate (TMP), triethyl phosphate (TE), and the like. P), tributyl phosphate (TBP), triphenyl phosphate (TPP), tris(2,2,2-trifluoroethyl)phosphate (TFP), methyl P,P-bis(2,2,2-trifluoroethyl)phosphate (BMP), trimethyl phosphite (TMPi), tris(2,2,2-trifluoroethyl)phosphite (TTFPi), dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate (DEEP), bis(2,2,2-trifluoroethyl)methyl phosphate (TFMP), bis(2,2,2-trifluoroethyl)ethyl phosphate (TFEP), hexa(methoxy)cyclotriphosphazene (HMOCPN), (ethoxy)pentafluorocyclotriphosphazene (PFPN), (phenoxy)pentafluorocyclotriphosphazene (FPPN), and combinations thereof.In a variation of the first embodiment or variations thereof, the electrolyte formulation includes an initiator (e.g., 1-10 wt. % based on the polymer precursor, oligomer, monomer, etc.), and the initiator is selected from the group consisting of 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobisisobutyronitrile (AIBN), 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2'-azobis[2-(2 -imidazolin-2-yl)-propane] dihydrochloride, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peracetate, tert-butyl hydroperoxide (TBH) HP), cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN or ACHN), ammonium persulfate, potassium persulfate (or other persulfates), lauroyl peroxide, tert-butyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide (BPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), 2,2-dimethoxy-2-phenylacetophenone (DMPA), and combinations thereof.In a variation of the first embodiment or variations thereof, the electrolyte formulation further comprises an inhibitor (e.g., 500 ppm to 1% by weight of the polymer precursor, oligomer, or monomer), wherein the inhibitor is selected from the list consisting of phenothiazine (PTZ), butylated hydroxytoluene (BHT), hydroquinone (HQ), 4-methoxyphenol (MEHQ), monobenzone, hydroquinone, guaiacol, 2-hydroxy-5-methoxybenzaldehyde, 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, chloranil, quinone methides, p-phenylenediamine, diethylhydroxylamine, hydroxylhydroxylamine, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), 4-hydroxy-TEMPO (TEMPOL), and combinations thereof. In a variation of the first embodiment or variations thereof, the oligomer is at least one of a urethane acrylate or a urethane methacrylate (e.g., polyester urethane acrylate, polyester urethane methacrylate, polyether urethane acrylate, polycarbonate urethane acrylate, polycarbonate-polyether urethane acrylate, polycarbonate-polyester urethane acrylate, polyether-polyester urethane acrylate, polyimide urethane acrylate, polycarbonate urethane methacrylate, polycarbonate-polyether urethane methacrylate). urethane acrylate, polycarbonate-polyester urethane methacrylate, polyether-polyester urethane methacrylate, polyimide urethane methacrylate, polybutadiene urethane acrylate, polybutadiene urethane methacrylate, bisphenol A epoxy diacrylate, silicone urethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyether urethane acrylate, difunctional aromatic urethane acrylate, difunctional aliphatic hydrophobic urethane acrylate, aminated urethane acrylate, aminated urethane methacrylate).In another variation or variations of the first embodiment, the oligomer comprises at least one of a urethane epoxy or a urea epoxy, and optionally a crosslinked epoxy (e.g., a multifunctional epoxy having two or more epoxy head groups available for covalent crosslinking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof). In another variation or variations of the first embodiment, the oligomer comprises at least one of a urethane imide or a urea imide, and optionally a crosslinked imide (e.g., a multifunctional imide having two or more imide head groups available for covalent crosslinking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof). In another variation or variations of the first embodiment, the oligomer comprises at least one of a urethane thiol or a urea thiol, and optionally a crosslinked thiol (e.g., a multifunctional thiol having two or more thiol head groups available for covalent crosslinking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof).In a variation of the first embodiment or variations thereof, the salt compound is selected from the group consisting of lithium hexafluorophosphate (LiPF), lithium hexafluoroarsenate (LiAsF), lithium tetrafluoroborate (LiBF), lithium perchlorate (LiClO), lithium tetracyanoborate (LiB(CN)), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluorosulfonyl)imide (LiTFSI), lithium tris(trifluoromethanesulfonyl)methide (LiTFSM), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium fluoroalkylphosphates (e.g., lithium tris(pentafluoroethyl)trifluorophosphate), and the like. FAP), lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide (LiDMSI), lithium-cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide (LiHPSI), lithium-cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide (LiBETI), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(monofluoromalonato)borate (LiBFMB), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), lithium 4,5-dicyano-2-(pentafluorylethyl)imidazole (LiPDI), and combinations thereof. In a variation of the first embodiment or variations thereof, the composition has two states: a liquid state before curing having a viscosity of less than 40 cP at 25° C., and a free-standing state. In a variation of the first embodiment or a variation thereof, the polymer component in a liquid state before curing comprises subunits of a polymeric compound. In a variation of the first embodiment or a variation thereof, the active state of the composition comprises a composition having a modulus of at least 0.1 MPa at 25° C. In a variation of the first embodiment or a variation thereof, the active state of the composition has a lithium cation conductivity of at least 0.1 mS / cm.

[0112] In an exemplary embodiment of the battery system, the battery system includes a casing, a set of electrodes including an anode and a cathode, a separator positioned between the cathode and the anode, and an electrolyte distributed throughout the casing, the electrolyte including a polymer electrolyte including a polymer component, a salt component, and an additive component. In a variation of the second embodiment or variations thereof, the cathode includes a cathode active material selected from the list consisting of lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), lithium nickel manganese oxide (LNMO), lithium iron phosphate (LFP), lithium manganese oxide (LMO), and lithium nickel cobalt aluminum oxide (NCA), and a cathode active material selected from the list consisting of carbon black, carbon nanotubes, graphite, graphene, fullerenes, carbon fiber (VGCF), super P an anode comprising a conductive material selected from the list consisting of Li, Super C65, Super C45, SO, KS-6, KS-15, SFG-6, SFG-15, 350G, acetylene black, and Kejin black, and a binder selected from the list consisting of polyvinylidene fluoride (PVDF), styrene butadiene copolymer (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyvinyl alcohol (PVA), humin, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS), chitosan, and alginic acid; an anode active material selected from the list consisting of graphite, graphitic carbon, carbon fiber, carbon nanotubes, carbon spheres, carbon nanorods, alloy materials including aluminum, tin, magnesium, silver, antimony or alloys thereof, transition metal sulfides, transition metal oxides, transition metal hydroxides, transition metal phosphides, transition metal nitrides, transition metal carbides, transition metal fluorides, transition metal selenides, transition metal oxalates, transition metal niobates, and silicon; and anode active materials selected from the list consisting of carbon black, carbon nanotubes, graphite, graphene, fullerene, carbon fiber (VGCF), Super P Li, Super C65, Super C45, SO, KS-6, KS-15, SFG-6, SFG-15, 350G, acetylene black,and Kejin black; and a binder selected from the list consisting of polyvinylidene fluoride (PVDF), styrene butadiene copolymer (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), poly(vinyl alcohol) (PVA), humic acid, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), chitosan, and alginic acid, wherein the polymer component of the electrolyte is polyester urethane acrylate, polyester Urethane methacrylate, polyether urethane acrylate, polycarbonate urethane acrylate, polycarbonate-polyether urethane acrylate, polycarbonate-polyester urethane acrylate, polyether-polyester urethane acrylate, polyimide urethane acrylate, polyester acrylate, epoxy acrylate, polycarbonate acrylate, polyester-polycarbonate acrylate, polyether acrylate, polyether-polyester acrylate, polyether-polycarbonate acrylate acrylates, polyether-polyester-polycarbonate (or other sequences such as polyether-polycarbonate-polyester, polyester-polyether-polycarbonate, etc.) acrylates, aminated urethane acrylates, polycarbonate urethane methacrylates, polycarbonate-polyether urethane methacrylates, polycarbonate-polyester urethane methacrylates, polycarbonate-polyester urethane methacrylates, polyether-polyester urethane methacrylates, polyimide urethane methacrylates, polyester methacrylates, epoxy methacrylates, polycarbonate methacrylates, polyester-polycarbonate methacrylates, polyether methacrylates, polyether-polyester methacrylates, polyether-polycarbonate methacrylates, polyether-polyester-polycarbonate (or other sequences such as polyether-polycarbonate-polyester, polyester-polyether-polycarbonate, etc.) methacrylates, aminated urethane acrylates, aminated urethane methacrylates, aminated urethane methacrylates, polybutadiene urethane acrylates,and at least one of polybutadiene urethane methacrylate, bisphenol A epoxy diacrylate, silicone urethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyether urethane acrylate, difunctional aromatic urethane acrylate, or difunctional aliphatic hydrophobic urethane acrylate (in some variations of this embodiment, a subset of the list of materials may be selected, e.g., as a result of toughening properties arising from the urethane domains, viscosity of the oligomer, etc.). Various urethane-containing oligomers can be selected), and the salt component of the electrolyte is lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium tetracyanoborate (LiB(CN)4), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluorosulfonyl)imide (LiTFSI), lithium tris(trifluoromethanesulfonyl)methide (LiTFSM), lithium bis(oxalate) ) borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium fluoroalkyl phosphates (LFAPs such as lithium tris(pentafluoroethyl)trifluorophosphate), lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide (LiDMSI), lithium-cyclohexafluoropropane-1,1-bis(sulfonyl)imide (LiHPSI), lithium-cyclohexafluoropropane-1,1-bis(sulfonyl)imide (LiBETI), lithium difluoro(oxalato) ) borate (LiDFOB), lithium bis(monofluoromalonato)borate (LiBFMB), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), and lithium 4,5-dicyano-2-(pentafluorylethyl)imidazole (LiPDI), and the additive component of the electrolyte is ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC),The solvent may include at least one of propylene carbonate (PC), vinylene carbonate (VC), dimethoxyethane (DME), diethyl ether, tetrahydrofuran (THF), methyl formate (MF), ethyl formate (EF), methyl propionate (MP), methyl butanoate, ethyl formate (EF), ethyl acetate (EA), ethyl propionate (EP), propyl formate, propyl acetate (PA), propyl propionate (PP), glyme, diglyme, triglyme, or tetraglyme. In a variation of the second embodiment or variations thereof, the additive component is selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide (DTD), vinyl acetate (VA), 2-vinylpyridine (VP), fluoroethylene carbonate (FEC), trivinylcyclotriboroxane (tVCBO), VC, LiDFOB, LiBOB, sulfone, ethyl methyl sulfone, tetramethyl sulfone (TMS), prop-1-ene-1,3-sulfone (PES), 1,3-propane sultone (PS), cyclic sulfate, dioxolone, 5-methyl-4-((trifluoromethoxy)methyl)-1,3-dioxol-2-one, phenylboronic acid glycol ester (PBE), 5-methyl-4-((trimethylsilyloxy)methyl)-1,3-dioxol-2-one, trimethylphosphine phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), triphenyl phosphate (TPP), tris(2,2,2-trifluoroethyl)phosphate (TFP), methyl P,P-bis(2,2,2-trifluoroethyl)phosphate (BMP), trimethyl phosphite (TMPi), tris(2,2,2-trifluoroethyl)phosphite (TTFPi), dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate (DEEP), bis(2,2,2-trifluoroethyl)methyl phosphate (TFMP), bis(2,2,2-trifluoroethyl)ethyl phosphate (TFEP), hexa(methoxy)cyclotriphosphazene (HMOCPN), (ethoxy)pentafluorocyclotriphosphazene (PFPN),or (phenoxy)pentafluorocyclotriphosphazene (FPPN). In a variation of the second embodiment or a variation thereof, the electrolyte has an ionic conductivity of at least 0.1 mS / cm at 25° C. In a variation of the second embodiment or a variation thereof, the electrolyte has an elastic modulus of at least 0.1 MPa at 25° C.

[0113] In a first method embodiment (e.g., as shown in FIG. 15 ), an in-situ polymer electrolyte formation method for a battery includes preparing an electrolyte precursor, the electrolyte precursor including monomeric and oligomeric subunits of at least one polymer compound, at least one salt compound, and at least one additive compound; dispensing the electrolyte precursor into the battery, thereby allowing sufficient penetration into the battery electrode and separator components; and activating the electrolyte precursor, thereby converting the electrolyte precursor into a polymer electrolyte. In a variation of the first method embodiment or variation thereof, the step of activating the electrolyte precursor includes polymerizing at least one tough polymer in the electrolyte. In a variation of the first method embodiment or variation thereof, the step of activating the electrolyte precursor includes curing the electrolyte precursor. In a variation of the first method embodiment or variation thereof, the step of curing the electrolyte precursor includes curing the electrolyte precursor in the presence of a thermal initiator. In a variation of the first method embodiment or variation thereof, the activating the electrolyte precursor occurs within the battery.

[0114] In a second method embodiment (e.g., for in situ polymer electrolyte formation), a method for forming a gel electrolyte battery includes receiving a first gel precursor solution including a plasticizer and a polymer precursor; receiving a second gel precursor solution including a solvent and a polymerization initiator; mixing the first and second gel precursor solutions to form a gel electrolyte precursor having a viscosity of 10 to 50 centipoise; adding the gel electrolyte precursor to a battery immediately after mixing (e.g., within 30 minutes); and forming a cathode, anode, and cathode of the battery by pulsed vacuum infiltration. The method includes the steps of thoroughly permeating the electrolyte precursor through the cathode, anode, and separator, wherein the vacuum pressure during each vacuum pulse is up to 0.95 bar; and curing the gel electrolyte precursor by clamping the battery with a force of 5 to 1000 psi for at least 6 hours after permeating the cathode, anode, and separator of the battery and heating the gel electrolyte precursor to a temperature of 60 to 80°C for 30 minutes to 24 hours, whereupon the gel electrolyte precursor forms a gel electrolyte throughout the cathode, anode, and separator. A variation of the first method embodiment or variation thereof includes tap charging the battery to 1.5 to 2.2 V before permeating the cathode, anode, and separator. A variation of the second method embodiment or variation thereof includes cycling the battery to form a solid electrolyte interface (SEI) layer before curing the gel electrolyte. In a variation of the second embodiment or variations thereof, the polymer precursor is at least one of a urethane acrylate or a urethane methacrylate (e.g., polyesterurethane acrylate, polyesterurethane methacrylate, polyetherurethane acrylate, polycarbonateurethane acrylate, polycarbonate-polyetherurethane acrylate, polycarbonate-polyesterurethane acrylate, polyether-polyesterurethane acrylate, polyimideurethane acrylate, polycarbonateurethane methacrylate, polycarbonate-polyetherurethane methacrylate, polycarbonate-polyesterurethane methacrylate, polyether-polyesterurethane methacrylate,The polymer precursor may comprise one or more of polyimide urethane methacrylate, polybutadiene urethane acrylate, polybutadiene urethane methacrylate, bisphenol A epoxy diacrylate, silicone urethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyether urethane acrylate, difunctional aromatic urethane acrylate, difunctional aliphatic hydrophobic urethane acrylate, aminated urethane acrylate, aminated urethane methacrylate. In another variation of the second specific example or variations thereof, the polymer precursor comprises at least one of a urethane epoxy or a urea epoxy, and optionally a crosslinked epoxy (e.g., a multifunctional epoxy having two or more epoxy head groups available for covalent crosslinking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof). In another variation of the second specific example or variations thereof, the polymer precursor comprises at least one of a urethane imide or a urea imide, and optionally a crosslinked imide (e.g., a multifunctional imide having two or more imide head groups available for covalent crosslinking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof). In another variation of the second embodiment or variations thereof, the polymer precursor comprises at least one of a urethane thiol or a urea thiol, and optionally a crosslinking thiol (e.g., a multifunctional thiol having two or more thiol head groups available for covalent crosslinking, such as a polyether, a polycarbonate, a polyester, a polyurethane, or combinations thereof). In another variation of the second method embodiment or variations thereof, the plasticizer comprises a polar aprotic solvent, the polar aprotic solvent being selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, vinylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, trifluoropropylene carbonate, methyleneethylene carbonate, dioxazolone, hexahydroxybenzene triscarbonate, ethylene tetracarboxylic dianhydride, lactic acid O-carboxyanhydride, tetrahydroxy-1,4-benzoquinone biscarbonate,the salt comprises at least one of di-tert-butyl carbonate, di-tert-butyl decarbonate, diethyl carbonate, diethyl pyrocarbonate, dimethyl carbonate, ethyl methyl carbonate, diallyl carbonate, diphenyl carbonate, methyl (2,2,2-trifluoroethyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethoxyethane, diethyl ether, tetrahydrofuran (oxolane), tetraethoxymethane, tetramethoxymethane, triethyl orthoacetate, triethyl orthoformate, trimethyl orthoformate, 2,2-diethoxytetrahydrofuran, methyl formate, ethyl formate, methyl propionate, methyl butanoate, ethyl formate, ethyl acetate, ethyl propionate, propyl formate, propyl acetate, or propyl propionate; The compound may comprise at least one of lithium tetrafluoroborate, lithium chlorate, lithium 2,3,7,8-tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4.4]nonane-5-wid, lithium difluorophosphate, lithium difluorooxalatoborate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium fluoromalonato(difluoro)borate, lithium trifluoromethanesulfonate, lithium tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4,4]nonane-5-wid, lithium trifluoro[(trifluoromethanesulfonylazanidyl)sulfonyl]methane, lithium nitrate, or lithium 2,2-difluoro-4,5-dioxo-1,3,2-dioxaborolane-2-wid. In this variation of the second method embodiment or variations thereof, the solvent is a polar aprotic solvent.

[0115] A third method embodiment includes receiving a gel electrolyte precursor solution, the gel electrolyte precursor solution including an oligomer containing functional groups capable of dynamic bonding (e.g., hydrogen bonding, ion pair bonding, metal chelates, dynamic covalent bonding, etc.) and / or toughening domains (typically toughening domains, toughening functional groups, etc., enabled by functional groups capable of dynamic bonding), an initiator, and a plasticizer; adding the gel electrolyte precursor solution to a battery stack including a cathode, an anode, and a separator; allowing the gel electrolyte precursor solution to fully penetrate the battery stack; and curing the gel electrolyte precursor solution to form a covalently bonded gel electrolyte network interspersed throughout the cathode, anode, and separator. In a variation of the third method embodiment or variations thereof, the viscosity of the gel electrolyte precursor is at most 50 cP at 25° C. In a variation of the third method embodiment or variations thereof, the covalently bonded gel electrolyte network includes ion-conducting domains. In this variation of the third method embodiment or variations thereof, the plasticizer comprises a polar aprotic solvent, and the polar aprotic solvent is selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, vinylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, trifluoropropylene carbonate, methyleneethylene carbonate, dioxazolone, hexahydroxybenzene triscarbonate, ethylene tetracarboxylic dianhydride, lactic acid O-carboxyanhydride, tetrahydroxy-1,4-benzoquinone biscarbonate, , di-tert-butyl carbonate, di-tert-butyl decarbonate, diethyl carbonate, diethyl pyrocarbonate, dimethyl carbonate, ethyl methyl carbonate, diallyl carbonate, diphenyl carbonate, methyl (2,2,2-trifluoroethyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethoxyethane, diethyl ether, tetrahydrofuran (oxolane), tetraethoxymethane, tetramethoxymethane, triethyl orthoacetate, triethyl orthoformate, trimethyl orthoformate, 2,2-diethoxytetrahydrofuran, methyl formate,and a salt comprising at least one of ethyl formate, methyl propionate, methyl butanoate, ethyl formate, ethyl acetate, ethyl propionate, propyl formate, propyl acetate, or propyl propionate, and the salt is selected from the group consisting of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chlorate, lithium 2,3,7,8-tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4.4]nonane-5-ide, lithium difluorophosphate, lithium difluorooxalatoborate, lithium bis(fluorosulfonyl)imide, and lithium bis(fluorosulfonyl)imide. (trifluoromethanesulfonyl)imide, lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide, lithium fluoromalonato(difluoro)borate, lithium trifluoromethanesulfonate, lithium tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4,4]nonane-5-wid, lithium trifluoro[(trifluoromethanesulfonylazanidyl)sulfonyl]methane, lithium nitrate, or lithium 2,2-difluoro-4,5-dioxo-1,3,2-dioxaborolane-2-wid. In a variation of the third method embodiment or variations thereof, the plasticizer further comprises an additive, the additive being selected from the group consisting of fluoroethylene carbonate, vinylene carbonate, methylene ethylene carbonate, 3-fluoro-1,3-propane sultone, prop-1-ene-1,3-sultone, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, bis(2,2,2-trifluoroethyl)methyl phosphate phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, tris(2,2,2-trifluoroethyl)phosphite, dimethyl methyl phosphonate, diethyl ethyl phosphonate, bis(2,2,2-trifluoroethyl)methyl phosphonate, bis(2,2,2-trifluoroethyl)ethyl phosphonate, hexamethoxycyclotriphosphazene, N-methyl-2-pyrrolidone, ethoxy(pentafluoro)cyclotriphosphazene, pentafluoro(phenoxy)cyclotriphosphazene,The gel electrolyte precursor solution may include at least one of tris(trimethylsilyl) phosphite, tris(trimethylsilyl) phosphite, or diethylphenylphosphonite. In a variation of the third method embodiment or its variation, the step of receiving the gel electrolyte precursor includes mixing a first solution including a plasticizer and an oligomer with a third solution including an initiator and a solvent. In a variation of the third method embodiment or its variation, the first solution and the second solution are mixed immediately before (e.g., within no more than one hour) adding the gel electrolyte precursor solution to the battery stack. In a variation of the third method embodiment or its variation, the plasticizer includes a solvent. In a variation of the third method embodiment or its variation, the step of curing the gel electrolyte precursor includes thermally curing the gel electrolyte precursor by maintaining the temperature of the gel electrolyte precursor and the battery stack at 60 to 80°C for 0.5 to 24 hours. In a variation of the third method embodiment or a variation thereof, the step of curing the gel electrolyte precursor includes mechanically clamping the gel electrolyte precursor and the battery stack at a pressure of 5 psi to 1000 psi. In a variation of the third method embodiment or a variation thereof, the oligomer includes at least one of a urethane epoxy or a urea epoxy, and optionally a crosslinked epoxy (e.g., a multifunctional epoxy having two or more epoxy head groups available for covalent crosslinking, such as a polyether, a polycarbonate, a polyester, a polyurethane, or a combination thereof). In another variation of the third embodiment or variations thereof, the oligomer is at least one of a urethane acrylate or a urethane methacrylate (e.g., polyester urethane acrylate, polyester urethane methacrylate, polyether urethane acrylate, polycarbonate urethane acrylate, polycarbonate-polyether urethane acrylate, polycarbonate-polyester urethane acrylate, polyether-polyester urethane acrylate, polyimide urethane acrylate, polycarbonate urethane methacrylate, polycarbonate-polyether urethane methacrylate, polycarbonate-polyester urethane methacrylate,The oligomer may comprise at least one of: polyether-polyesterurethane methacrylate, polyimideurethane methacrylate, polybutadieneurethane acrylate, polybutadieneurethane methacrylate, bisphenol A epoxy diacrylate, siliconeurethane acrylate, thioether dendritic acrylate, thioether dendritic methacrylate, functional aliphatic polyetherurethane acrylate, difunctional aromatic urethane acrylate, difunctional aliphatic hydrophobic urethane acrylate, aminated urethane acrylate, aminated urethane methacrylate. In another variation of the third specific example or variations thereof, the oligomer comprises at least one of a urethane imide or a urea imide, and optionally a crosslinked imide (e.g., a multifunctional imide having two or more imide head groups available for covalent crosslinking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof). In another variation of the third embodiment or variations thereof, the oligomer comprises at least one of a urethane thiol or a urea thiol, and optionally a cross-linking thiol (e.g., a multifunctional thiol having two or more thiol head groups available for covalent cross-linking, such as a polyether, polycarbonate, polyester, polyurethane, or combinations thereof). In another variation of the third method embodiment or variations thereof, the covalently linked gel electrolyte network comprises at least one functional group that forms an ion transport network. In a variation of the third method embodiment or variations thereof, the oligomer and / or polymer formed by activation (e.g., curing, polymerizing, etc., of the oligomer and / or monomer) contains at least one functional group within the backbone of the oligomer selected from carbonate, ester, ketone, carbamide, carbamate, thiocarbamate, thiocarbamide, thiocarbonate, dithiocarbonate, ether, thioether, imide, imine, epoxide, amide, acid anhydride, nitrile, amidine, cyanate, isocyanate, nitrosoxy, nitro, nitroso, oxime, sulfinyl, sulfonyl, sulfonate ester, sulfone, thiocyanate, isothiocyanate, thioester, or dithiocarboxylic acid ester (e.g.,The gel electrolyte precursor further comprises a repeating monomer, a pendant group, etc., containing the functional group. In a variation of the third method embodiment or a variation thereof, the gel electrolyte precursor further comprises tap charging the battery stack to a voltage of 1.5 to 2.2 V before infiltrating the battery stack. In a variation of the third method embodiment or a variation thereof, the infiltrating the battery stack comprises applying a plurality of vacuum pulses (e.g., 2, 3, 4, 5, 7, 10, 20, 50 pulses, values ​​or ranges therebetween, etc.) to the battery stack, each vacuum pulse of the plurality of vacuum pulses comprising a pressure of up to about 0.95 bar. In other embodiments, a single vacuum pulse can be used. In a variation of the third method embodiment or a variation thereof, the infiltrating the battery stack further comprises aging the battery stack for up to 48 hours before curing the gel electrolyte precursor.

Claims

1. receiving a gel electrolyte precursor solution, the gel electrolyte precursor solution comprising: an acrylate or methacrylate oligomer comprising a toughening domain; an initiator; a plasticizer; adding the gel electrolyte precursor solution to a battery stack including a cathode, an anode, and a separator; - infiltrating the battery stack with the gel electrolyte precursor solution; and curing the gel electrolyte precursor solution to form a covalently bonded gel electrolyte network interspersed throughout the cathode, the anode, and the separator.

2. 10. The method of claim 1, 2. The method of claim 1, wherein the viscosity of the gel electrolyte precursor is at most 50 cP at 25°C.

3. 10. The method of claim 1, The method of claim 1, wherein the covalently bonded gel electrolyte network has an ionic conductivity of at least 0.1 mS / cm at 25°C.

4. 10. The method of claim 1, the plasticizer comprises a polar aprotic solvent and a salt; The polar aprotic solvent is selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, vinylene carbonate, trimethylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, trifluoropropylene carbonate, methyleneethylene carbonate, dioxazolone, hexahydroxybenzene triscarbonate, ethylene tetracarboxylic dianhydride, lactic acid O-carboxyanhydride, tetrahydroxy-1,4-benzoquinone biscarbonate, di-tert-butyl carbonate, di-tert-butyl decarbonate, diethyl carbonate, diethylpyrocarbonate, dimethyl carbonate, at least one of methyl carbonate, ethyl methyl carbonate, diallyl carbonate, diphenyl carbonate, methyl (2,2,2-trifluoroethyl) carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethoxyethane, diethyl ether, tetrahydrofuran (oxolane), tetraethoxymethane, tetramethoxymethane, triethyl orthoacetate, triethyl orthoformate, trimethyl orthoformate, 2,2-diethoxytetrahydrofuran, methyl formate, ethyl formate, methyl propionate, methyl butanoate, ethyl formate, ethyl acetate, ethyl propionate, propyl formate, propyl acetate, or propyl propionate; The salt is selected from the group consisting of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium chlorate, lithium 2,3,7,8-tetraoxo-1,4,6,9-tetraoxa-5-boraspiro[4.4]nonane-5-ide, lithium difluorophosphate, lithium difluorooxalatoborate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide, fluorinated alkyl acrylate, lithium ...

5. 5. The method of claim 4, The plasticizer further comprises an additive, and the additive is selected from the group consisting of fluoroethylene carbonate, vinylene carbonate, methylene ethylene carbonate, 3-fluoro-1,3-propane sultone, prop-1-ene-1,3-sultone, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, bis(2,2,2-trifluoroethyl)methyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, tris ...ethyl phosphite, triethyl phosphite, tris(2,2,2-trifluoroethyl)methyl phosphate, trimethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phosphite, triethyl phos bis(2,2,2-trifluoroethyl)methyl phosphate, bis(2,2,2-trifluoroethyl)ethyl phosphate, hexamethoxycyclotriphosphazene, N-methyl-2-pyrrolidone, ethoxy(pentafluoro)cyclotriphosphazene, pentafluoro(phenoxy)cyclotriphosphazene, tris(trimethylsilyl)phosphite, tris(trimethylsilyl)phosphite, or diethylphenylphosphonite.

6. 10. The method of claim 1, 1. The method, wherein the step of receiving a gel electrolyte precursor comprises mixing a first solution comprising a plasticizer and an acrylate or methacrylate oligomer with a second solution comprising an initiator and a solvent.

7. 7. The method of claim 6, mixing the first solution and the second solution immediately before adding the gel electrolyte precursor solution to the battery stack.

8. 7. The method of claim 6, The method of claim 1, wherein the plasticizer comprises a solvent.

9. 10. The method of claim 1, the step of curing the gel electrolyte precursor comprises thermally curing the gel electrolyte precursor by maintaining a temperature of the gel electrolyte precursor and the battery stack at 60 to 80°C for 0.5 to 24 hours.

10. 10. The method of claim 9, 10. The method of claim 9, wherein the step of curing the gel electrolyte precursor comprises mechanically clamping the gel electrolyte precursor and the battery stack at a pressure of 5 psi to 1000 psi.

11. 10. The method of claim 1, The method, wherein the toughening region comprises functional groups capable of dynamic binding via hydrogen bonding or ion pair interactions.

12. 10. The method of claim 1, The method, wherein the covalent gel electrolyte network further comprises at least one functional group that forms an ion transport network.

13. 13. The method of claim 12, The method, characterized in that the at least one functional group comprises, within the backbone of an acrylate oligomer or a methacrylate oligomer, at least one functional group selected from carbonate, ester, ketone, carbamide, carbamate, thiocarbamate, thiocarbamide, thiocarbonate, dithiocarbonate, ether, thioether, imide, imine, epoxide, amide, acid anhydride, nitrile, amidine, cyanate, isocyanate, nitrosoxy, nitro, nitroso, oxime, sulfinyl, sulfonyl, sulfonic acid ester, sulfone, thiocyanate, isothiocyanate, thioester, and dithiocarboxylic acid ester.

14. 10. The method of claim 1, 10. The method of claim 9, further comprising tap charging the battery stack to a voltage of 1.5 to 2.2 V prior to infiltrating the battery stack.

15. 10. The method of claim 1, 10. The method of claim 9, wherein the infiltrating the cell stack step comprises applying a plurality of vacuum pulses to the cell stack, each vacuum pulse in the plurality of vacuum pulses comprising a pressure of up to about 0.95 bar.

16. 10. The method of claim 1, 10. The method of claim 9, wherein the step of infiltrating the battery stack further comprises aging the battery stack for up to 48 hours before curing the gel electrolyte precursor.

17. 1. An electrolytic polymer composition for a battery, comprising: a polymer component comprising a concentration of 8% to 80% by weight of the electrolyte composition, the polymer component providing dynamic and covalent crosslinks in an active state; a salt component comprising at least one salt compound, the salt component comprising a concentration of 8% to 40% by weight of the electrolyte composition; an electrolytic polymer composition comprising a plasticizer component comprising at least one plasticizer compound at a concentration of 1% to 80% by weight of the electrolyte composition;

18. 18. The composition of claim 17, The electrolytic polymer composition is in two states: a pre-activation state in which the electrolytic polymer composition comprises a solution; A composition characterized in that the electrolytic polymer composition has an active state, including a self-supporting form consisting of a gel state or a solid state.

19. 19. The composition of claim 18, The polymer component comprises an oligomer, the oligomer comprising: at least one polar functional group; and at least one polymerizable functional group.

20. 20. The composition of claim 19, the at least one polar functional group is selected from the list consisting of carbamide, carbamate, imine, boronate ester, and ionic chelating domain; the at least one polymerizable functional group is selected from the list consisting of acrylate, methacrylate, cyanoacrylate, epoxy, imide, and thiol; the plasticizer is selected from the list consisting of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), propylene carbonate (PC), vinylene carbonate (VC), dimethoxyethane (DME), diethyl ether, tetrahydrofuran (THF), methyl formate (MF), ethyl formate (EF), methyl propionate (MP), methyl butyrate, ethyl formate (EF), ethyl acetate (EA), ethyl propionate (EP), propyl formate, propyl acetate (PA), propyl propionate (PP), glyme, diglyme, triglyme, tetraglyme, and combinations thereof; The composition further comprises an additive, and the additive is selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide (DTD), vinyl acetate (VA), 2-vinylpyridine (VP), fluoroethylene carbonate (FEC), trivinylcyclotriboroxane (tVCBO), VC, LiDFOB, LiBOB, sulfone, ethyl methyl sulfone, tetramethyl sulfone (TMS), prop-1-ene-1,3-sulfone (PES), 1,3-propane sultone (PS), cyclic sulfate, dioxolone, 5-methyl-4-((trifluoromethoxy)methyl)-1,3-dioxol-2-one, phenylboronic acid glycol ester (PBE), 5-methyl-4-((trimethylsilyloxy)methyl)-1,3-dioxol-2-one, trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TB P), triphenyl phosphate (TPP), tris(2,2,2-trifluoroethyl)phosphate (TFP), methyl P,P-bis(2,2,2-trifluoroethyl)phosphate (BMP), trimethyl phosphite (TMPi), tris(2,2,2-trifluoroethyl)phosphite (TTFPi), dimethyl methyl phosphate (DMMP), diethyl ethyl phosphate (DEEP), bis(2,2,2-trifluoroethyl)methyl phosphate (TFMP), bis(2,2,2-trifluoroethyl)ethyl phosphate (TFEP), hexa(methoxy)cyclotriphosphazene (HMOCPN), (ethoxy)pentafluorocyclotriphosphazene (PFPN), (phenoxy)pentafluorocyclotriphosphazene (FPPN), and combinations thereof; the oligomer comprises at least one of a urethane acrylate or a urethane methacrylate; The salt compound is lithium hexafluorophosphate (LiPF ６ ), lithium hexafluoroarsenate (LiAsF ６ ), lithium tetrafluoroborate (LiBF ４ ), lithium perchlorate (LiClO ４ ), lithium tetracyanoborate (LiB(CN) ４ ), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluorosulfonyl)imide (LiTFSI), lithium tris(trifluoromethanesulfonyl)methide (LiTFSM), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium fluoroalkylphosphates (LFAPs such as lithium tris(pentafluoroethyl)trifluorophosphate), lithium-cyclo-difluoromethane-1,1-bis(sulfonyl)imide (LiDMSI), lithium-cyclo-hexafluoropropane-1,1-bis 1. A composition comprising a compound selected from the list consisting of lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI), lithium 4,5-dicyano-2-(pentafluorylethyl)imidazole (LiPDI), lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiPDI), lithium 4,5-dicyano-2-(pentafluorylethyl)imidazole (LiPDI), and combinations thereof.

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