Methods of preparing electrodes and electrochemical devices containing the electrode

Abstract

Provided herein are methods of preparing electrodes. The method comprises: combining an electron conductive material, a polymer as binder, an electrolyte, and an active material to form an active mixture; and shaping the active mixture to form an electrode. In some embodiments, the electrolyte comprises a salt and a solvent of the salt. In some embodiments, the solvent of the salt does not dissolve the polymer binder. In some embodiments, the method does not include a drying step to remove the solvent and the solvent remains in the active mixture and the electrode. In some embodiments, the electrode as prepared has an areal capacity of at least 2 mAh / cm2 and a thickness of at least 30 µm.

Description

METHODS OF PREPARING ELECTRODES AND ELECTROCHEMICAL DEVICES CONTAINING THE ELECTRODECROSS-REFERENCE

[0001] The present application claims priority of US Serial No. 63 / 511,266, filed June 30, 2023, the entire content of which is incorporated herein by reference into this application.TECHNICAL FIELD

[0002] This disclosure relates to methods of preparing electrodes and electrochemical devices such as batteries, capacitors, sensors, condensers, electrochromic elements, and photoelectric conversion elements containing the electrodes.BACKGROUND

[0003] Electrodes can be prepared by a slurry method which usually involves a certain amount of solvent, or a dry film making method (solvent-free method) in which electroactive materials, electric conductive material, and a polymer binder are mixed. Typically, organic solvents such as N-methyl-2-pyrrolidone (NMP) with a weight percentage of around 30% are used in a slurry method to provide certain flowability. Due to the existence of a large amount of solvent, other components such as electrolyte salts and surface modifiers can be feasibly added into the slurry. However, such solvent must be removed by a dry step after the slurry is applied to a substrate and does not eventually form a part of the final electrode. Furthermore, the slurry method is usually less capable of forming a thick electrode.

[0004] On the other hand, a dry film making method usually includes powder compression, vapor deposition, powder spray, binder fibrillation, and melt stretching. As no solvent is used, dry film making methods are usually more cost-effective, more environmentally friendly and more capable of forming an electrode with a high thickness and uniform distribution. However, the exclusion of liquid component in dry film making methods has some disadvantages. For example, the electrodes prepared by a dry film making method may exhibit a less desirable wettability and electrolytes may require a longer soaking time so that the pores of the electrode are pre-filled or filled with electrolytes. To modify the surface wettability in an efficient and homogeneous way, a modifying agent in a liquid form is usually needed. Since a dry film making method is typically solvent free, it is challenging to modify the surface by incorporating a solid surface modifier into a mixture of solid components. Thus, there remains a need for a new method of preparing electrodes in addressing all the challenges above.SUMMARY

[0005] The present disclosure generally relates to various methods of preparing an electrode and electrochemical devices thereof. The subject matter of the present disclosure involves, in some cases, interrelated products, alternative solutions to a particular problem, and / or a plurality of different uses of one or more systems and / or articles.

[0006] Provided herein are methods of preparing an electrode comprising: combining an electron conductive material, a polymer, an electrolyte, and an active material to form an active mixture; and shaping the active mixture to form an electrode.

[0007] Also provided herein are electrochemical devices comprising the electrodes as prepared by the methods disclosed herein.

[0008] Preparing electrodes as described herein can reduce the time required for soaking electrodes with electrolyte (e.g., reduce the time needed for infiltration of electrode by electrolyte) because the electrolyte added to the active mixture is combined with the other parts of the electrode when forming the active mixture. Preparing electrodes can reduce the environmental impact and / or improve the safety of the electrode by reducing the amount of or being substantially free of hazardous solvents (e.g., N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), and dimethylsulfoxide (DMSO)). Since the electrolyte is combined with the other materials of the electrode when forming the active mixture rather than allowing it to soak into pores of an already formed electrode, a solvent for dissolving a polymer binder is not necessary, thereby reducing the environmental impact and / or improving the safety of the electrode.

[0009] The details of one or more embodiments of the subject matter of this disclosure are set forth in the accompanying drawings and the description. Other features, aspects, and advantages of the subject matter will become apparent from the description, the drawings, and the claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Non-limiting embodiments of the present disclosure will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the disclosure shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure. FIG. l is a graph of voltage versus specific capacity of various batteries as described herein with differing electrode thicknesses.

[0011] FIG. 2 is a graph of specific capacity versus C-rate of various batteries as described herein with differing electrode thicknesses.

[0012] FIG. 3 is a graph of voltage versus specific capacity of a battery described herein.

[0013] FIG. 4 is a graph of voltage versus specific capacity of a battery with an electrode formed according to the disclosure and a battery with a comparative electrode.DETAILED DESCRIPTION

[0014] The present disclosure generally relates to methods of preparing an electrode suitable for various electrochemical devices. In some embodiments, the method of preparing an electrode comprises combining an electron conductive material, a polymer, an electrolyte (e.g., as an additive), and an active material to form an active mixture, and shaping the active mixture to form an electrode.

[0015] The term “% by weight” or “wt%” refers to the components represented with the percent calculated as percent by weight of all components, unless otherwise noted.

[0016] As used herein, “about” means ± 20% of the stated value, and includes more specifically values of ± 10%, ± 5%, ± 2% and ± 1% of the stated value.

[0017] As used herein, the term “substantially free of’ an ingredient(s) is intended to mean that the mixture or material(s) contain less than about 0.1 wt% (percent by weight of the total weight of the mixture or material(s)), or insignificant or negligible amounts of said ingredient(s) unless specifically indicated otherwise.

[0018] Preparing the electrodes can include combining an electron conductive material, a polymer, an electrolyte, and an active material to form an active mixture. Combining the electron conductive material, the polymer, the electrolyte, and the active material to form an active mixture be achieved by blending. The blending can occur for a length of time of about 10 seconds to about 10 hours (e.g., about 10 seconds to about 1 hour, or about 10 seconds to about 30 minutes, about 10 seconds to about 10 minutes, or about 10 seconds to about 1 minute). The blending can occur for a length of time, stopped, and can be repeated at least once. In some embodiments, the blending is repeated at least twice. In some embodiments, the blending step is repeated at least 3 times.

[0019] Combining the electron conductive material, the polymer, the electrolyte, and the active material to form an active mixture can include blending the electron conductive material, the polymer, and the active material to form an intermediate mixture. The intermediate mixture is blended with the electrolyte to form the active mixture. Blending the electron conductive material, the polymer, and the active material can be repeated at least once. In some embodiments, blending the intermediate mixture and the electrolyte is repeated at least once. In some embodiments, blending occurs for a length of time of about 10 seconds to about 10 hours (e.g., about 10 seconds to about 1 hour, or about 10 seconds to about 30 minutes, about 10 seconds to about 10 minutes, or about 10 seconds to about 1 minute).

[0020] In some embodiments, the electron conductive material, the polymer, the electrolyte, and the active material are combined into the active mixture by blending and / or mixing via a one-stepprocedure. In some embodiments, the electron conductive material, the polymer, the electrolyte, and the active material are combined into the active mixture by two steps, i.e., a first step which simply blends them into a first mixture and a second step which further mix them typically with a shear force to achieve a uniform distribution. In some embodiments, the first step is conducted at room temperature. In some embodiments, the second step is performed at an elevated temperature. In some embodiments, the shear force in the second step is generated by grinding the first mixture in a heated container such as mortar, rolling on a set of heated rollers, or both. In some embodiments, the second step is part of the shaping step, which is usually conducted on rollers. In some embodiments, the elevated temperature is sufficiently high to soften the polymer binder and lower than the melting point of the polymer binder. In some embodiments, the elevated temperature is lower than the boiling point of the electrolyte solvent. In some embodiments, the elevated temperature is in a range from 30 °C to 150 °C.

[0021] Combining the electron conductive material, the polymer, the electrolyte, and the active material can occur in the presence of an electrolyte solvent that dissolves salt in the electrolyte. In some embodiments, the electrolyte solvent that dissolves that salt in the electrolyte is the only solvent in the combining or blending the conductive material, the polymer, and the active material. In some embodiments, the electrolyte solvent dissolves the salt in the electrolyte but does not dissolve the polymer which is a binder. In some embodiments, combining the conductive material, the polymer, the electrolyte, and the active material occurs in the absence of polymer binder solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), and dimethylsulfoxide (DMSO). In some embodiments, preparing the electrode occurs without the addition of NMP, DMF, DMAc, and DMSO. In some embodiments, the electrode as prepared according to the disclosure is substantially free of NMP, DMF, DMAc, and DMSO.

[0022] Preparing the electrodes can include heating the active mixture prior to and / or during the shaping of the active mixture to form an electrode. In some embodiments, heating the active mixture occurs during the shaping of the active mixture. In some embodiments, heating the active mixture occurs prior to the shaping of the active mixture. In some embodiments, heating the active mixture comprises grinding the active mixture. In some embodiments, grinding occurs via a grinder, a mortar and pestle, or the like

[0023] Preparing the electrodes can include shaping the active mixture to form an electrode. Shaping the active mixture to form an electrode can include flattening the active mixture into an electrode in the shape of a film. In some embodiments, shaping can include calendaring the active mixture. In some embodiments, shaping can include extruding the active mixture. Shaping the active mixture can be repeated at least once, twice, or 3 times.

[0024] Heating the active mixture can occur at a temperature in a range of about 30°C to about 150°C. For example, heating the active mixture occurs at a temperature in a range of about 30°C to about 100°C, or about 40°C to about 90°C, or about 50°C to about 100°C, or about 60°C to about 85°C, or about 70°C to about 90°C. In some embodiments, heating the active mixture occurs at a temperature in a range of about 70°C to about 95°C. In some embodiments, the active mixture as formed is in a dough-like form. In some embodiments, the active mixture is ready for a subsequent shaping step. In some embodiments, the shaping step includes rolling or compressing.

[0025] Preparing the electrodes can further include laminating the electrode onto a current collector. In some embodiments, laminating the electrode further includes shaping the electrode with heated rollers. The heated rollers can be at a temperature in a range of about 50°C to about 100°C.

[0026] The electron conductive material can include conductive carbon. In some embodiments, the electron conductive material is electron conductive carbon. The electron conductive carbon can include one or more selected from the group consisting of carbon black, carbon nanotubes, graphite, artificial graphite, graphene, and carbon fiber. In some embodiments, the electron conductive carbon includes one or more selected from the group consisting of carbon black, carbon nanotubes, graphene, and carbon fiber. In some embodiments, the electron conductive carbon includes carbon black. In some embodiments, the electron conductive carbon is carbon black. In some embodiments, the electron conductive carbon includes graphene. In some embodiments, the electron conductive carbon is graphene. In some embodiments, the electron conductive carbon includes carbon nanotubes. In some embodiments, the electron conductive carbon is carbon nanotubes. In some embodiments, the electron conductive carbon includes carbon fiber. In some embodiments, the electron conductive carbon is carbon fiber. In some embodiments, the carbon fiber is a vapor grown carbon fiber.

[0027] The electron conductive material can be present in an amount of about 0.1 wt% to about 10 wt%, based on the total weight of the electrode (e.g., about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 3.5 wt%, or about 1.5 wt% to about 3.5 wt%, based on the total weight of the electrode). In some embodiments, the electron conductive material is present in an amount of about 0.5 wt% to about 2.5 wt%, based on the total weight of the electrode.

[0028] The polymer can be a polymer binder. In some embodiments, the polymer binder is a fibrillizable binder. The fibrillizable binder can be fibrillized during process to provide fibrils, thus providing mechanical support to components within the electrode film. In some embodiments, the fibrillizable binder includes, without limitation, polytetrafluoroethylene (PTFE), ultra-high molecular weight polyethylene (UHMWPE), and a combination thereof. In some embodiments, a dry fibrillizable binder is combined with the electron conductive material, the electrolyte, and theactive material to form the active mixture. In some embodiments, the polymer includes a noncrosslinked polymer. In some embodiments, the polymer includes a non-crosslinked polymer and a crosslinked polymer.

[0029] The polymer can include a fluorinated polymer. In some embodiments, the non-crosslinked polymer includes a fluorinated polymer. In some embodiments, the fluorinated polymer includes one or more of polytetrafluoroethylene (PTFE), poly vinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyvinylfluoride (PVF), perfluoroalkoxy polyme (PF A), fluorinated ethylene-propylene (FEP), and perfluoropolyene (PFPE). In some embodiments, the polymer includes polytetrafluoroethylene (PTFE). In some embodiments, the polymer includes polyvinylidene fluoride (PVDF).

[0030] The crosslinked polymer can have a heterogeneous polymer network obtained from a crosslinking reaction of a composition that includes one or more crosslinkers. In some embodiments, the polymer is synthesized from one or more crosslinkers, wherein at least one of the crosslinkers has three or more polymerizable or crosslinkable terminals. In some embodiments, at least one of the one or more crosslinkers has three or more polymerizable or crosslinkable terminals.

[0031] A crosslinker with three or more polymerizable or crosslinkable terminals can be represented as follows:where X is C, Si, N, P, B, or a cyclic ring,Rl, R2, and R3 are polymerizable or crosslinkable terminals covalently connected to X directly or through spacer chain or group. Rl, R2, R3 and their spacer chains or groups may be same or different from each other.

[0032] In certain embodiments, the three or more polymerizable or crosslinkable terminals (Rl, R2, R3 and R4) are independently selected from C2-20 alkenyl, C2-20 alkynyl, epoxy, amino, hydroxyl, carboxylic acid, or any substituted form thereof.

[0033] In certain embodiments, the crosslinker with three or more polymerizable or crosslinkable terminals is a tri-acrylate, tetra-acrylate, modified tri-acrylate, modified tetra-acrylate, silane, siloxane or triazinane-trione (triazine-trione).

[0034] In certain embodiments, the crosslinker with three or more terminals has a structural formula selected from:where R4 and Rs are independently selected from:where Ri, R2, R3, Re are each independently selected from hydrogen, methyl, ethyl, phenyl, methyl phenyl, benzyl, acryl, epoxy ethyl, isocyanate, cyclic carbonate, lactone, lactam, and vinyl; n is an integer between 0 and 50,000 and * indicates a point of attachment.

[0035] In certain embodiments, the crosslinker is a structural formula selected from:

[0036] In certain embodiments, tri-acrylates and tetra-acrylates are modified tri-acrylates and tetra-acrylates. In some embodiments, the modified tri-acrylates and tetra-acrylates include substituents such as -CN, -SO2H, -CO2H, -CO2-, F, Cl, Br, or I.

[0037] In certain embodiments, the crosslinker with three or more terminals is a silane or siloxane.

[0038] In some embodiments, one or more of the crosslinkers or the spacer chains or groups contain a structure including, but not limited to, -O-, -NRC-, -S-, -C(=O)-, -C(=O)O-, -C(=O)NRC-, -C(=O)S-, -OC(=O)O-, -NRCC(=O)O-, -NRCC(=O)NRC-, -S(=O)-, -S(=O)2-, -OS(=O)2-, - OS(=O)2O-, -NRCS(=O)2-, -NRCS(=O)2NRC-, -OS(=O)2NRC-, C 1-6 alkylenyl, C2-6 alkenylenyl, C2- 6 alkynylenyl, Ce-14 arylenyl, 5- to 14-membered heteroaryl enyl, C3-10 carbocyclenyl, or 3- to 10- membered heterocyclenyl, wherein the alkylenyl, alkenylenyl, alkynylenyl, arylenyl, heteroaryl enyl, carbocyclenyl, or heterocyclenyl is optionally substituted with halogen, -CN, -NO2, C1-6 alkyl, Ci-e haloalkyl, Ci-e hydroxyalkyl, C1-6 aminoalkyl, C2-6 alkenyl, C2-e alkynyl, Ce-uaryl, 5- to 14-membered heteroaryl, C3-10 carbocyclyl, 3- to 10-membered heterocyclyl, -SRb, -S(=O)Ra, -S(=O)2Ra, -S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRcS(=O)2Ra, -NRcS(=O)2Ra, -NRcS(=O)2ORb, -NRcS(=O)2NRcRd, -NRbC(=O)NRcRd, -NRbC(=O)Ra, -NRbC(=O)ORb, -ORb, -OS(=O)2Ra, - OS(=O)2ORb, -OS(=O)2NRcRd, -OC(=O)Ra, -OC(=O)ORb, -OC(=O)NRcRd, -C(=O)Ra, - C(=O)ORb, or -C(=O)NRcRd; wherein Ra, Rb, Rc, and Rdare independently C1-6 alkyl, C1-6 haloalkyl, C1-6 hydroxyalkyl, C1-6 aminoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-10 carbocyclyl, 3- to 10-membered heterocyclyl, Ce-14 aryl, or 5- to 14-membered heteroaryl, wherein the alkyl, haloalkyl, hydroxyalkyl, aminoalkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is optionally substituted with one or more oxo, halogen, -CN, -OH, -OMe, -NH2, - C(=O)Me, -C(=O)OH, -C(=O)OMe, C1-6 alkyl, or C1-6 haloalkyl.

[0039] In some embodiments, Rcand Rd, together with the heteroatom (such as N, O, S, P), form a 3- to 10-membered heterocyclyl, where the heterocyclyl is optionally substituted with one or more oxo, halogen, -CN, -OH, -OMe, -NH2, -C(=O)Me, -C(=O)OH, -C(=O)OMe, C1-6 alkyl, or C1-6 haloalkyl.

[0040] In certain embodiments, one of the crosslinkers or the spacer chains or groups include a structure of -XC(=O)CR3=C(R4)2, where X is independently O or NRe, where Reis independently H or C1-6 alkyl, and each R3and R4is independently H or C1-6 alkyl.

[0041] In certain embodiments, one of the crosslinkers is selected from:

[0042] In some embodiments, the crosslinker includes one or more functional groups selected

[0043] In some embodiments, the crosslinker is a monomer for ring opening polymerization. In some embodiments, the crosslinker is a monomer for ring opening polymerization and can be represented as follows:and any substituted form thereof, where x is an integer ranging from 1 to 1000.

[0044] In some embodiments, the monomer for ring opening polymerization includes:

[0045] In some embodiments, the monomer for ring opening polymerization comprises an unsubstituted or substituted oxirane ring, oxetane ring, furan ring, aziridine ring, and azetidine ring.

[0046] As described herein, some compositions can be used with polymer solid electrolytes, batteries, or other electrochemical devices including same, and methods for producing same. In some cases, the incorporation of vinyl and / or allyl functional groups with UV crosslinking or thermal crosslinking can be used to improve various electrochemical performance, especially when the crosslinker has polymerizable or crosslinkable terminals, such as vinyl and allyl, in at least three directions of the chemical structure of the crosslinker (i.e., the crosslinker has three crosslinkable terminals), the electrochemical performance can be improved more obviously.

[0047] In one aspect, the present disclosure is generally directed to an electrochemical cell, such as a battery, including an electrode as disclosed herein. In certain embodiments, the battery is an LIB, such as a lithium-ion solid-state battery. The electrochemical cell may include an anode, a cathode, and / or a separator. Many of these are available commercially. In some embodiments, the electrode may be used as the electrolyte of the electrochemical cell, alone or in combination with other electrolyte materials.

[0048] Polymerizable and crosslinkable terminals (alternatively groups) can include without limitation C2-20 alkenyl, C2-20 alkynyl, epoxy, amino, hydroxyl, carboxylic acid, or any substituted form thereof. In certain embodiment, they are vinyl and / or allyl.

[0049] In some embodiments, the terminals or groups, such as vinyl and / or allyl, can be crosslinked together. For example, such functional groups can be crosslinked using UV light, at an elevated temperature (e.g., between 20 °C and 100 °C), in the presence of an initiator, or other methods including those described herein. In some cases, the incorporation of three crosslinkable terminals leads to a disorganized or disordered network, resulting in improved electrochemical performances, or the like, such as relatively high ionic conductivities, decomposition voltages.

[0050] The polymer can be present in an amount of about 0.1 wt% to about 10 wt%, based on the total weight of the electrode (e.g., about 0.1 wt% to about 3 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 2.5 wt%, based on the total weight of the electrode). In some embodiments, the polymer is present in an amount of about 1.5 wt% to about 3.5 wt%, based on the total weight of the electrode.

[0051] The electrolyte can include a salt (e.g., a lithium salt). The electrolyte can include, for example, a lithium salt, or other salts such as sodium, potassium, magnesium, calcium salts, and the like.

[0052] In some embodiments, the electrolyte includes a lithium salt. In some embodiments, the electrolyte includes one or more of lithium perchlorate (LiCICh), lithium hexafluorophosphate (LiPFe), lithiumborofluoride (LiBF4), lithium hexafluoroarsenide (LiAsFe), lithium trifluorometasulfonate (LiCFsSCh), bis-trifluorom-ethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate(LiNO3), Li-fluoroalkyl-phosphates (LiPF3(CF2CF3)3), lithium bisperfluoro-ethysulfo-nylimide (LiBETI), lithium bis(trifluoromethanesulphonyl) imide, lithium bis(fuorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium difluoro(oxalato)borate (LiDFOB), lithium perchlorate (LiCICh), LiC(CF3SO2)3, LiF, LiCl, LiBr, Lil, Li2SO4, LiNCh, LisPCh, Li2CO3, LiOH, lithium acetate, lithium trifluoromethyl acetate, and lithium oxalate. For example, the electrolyte includes one or more of LiFSI and LiTFSI. In some embodiments the electrolyte comprises LiFSI.

[0053] The electrolyte can include an electrolyte solvent and an electrolyte salt such as lithium salt. In some embodiments, the electrolyte includes a lithium salt and a solvent of the lithium salt. In some embodiments, the solvent (e.g., the electrolyte solvent) includes one or more of 1,2- di ethoxy ethane, 1,1 -di ethoxy ethane, 1,1 -dipropoxy-ethane, 1,2-dipropoxy-ethane, di ethylene glycol, 2-(2-ethoxyethoxy)ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, tri(ethylene glycol) monomethyl ether,tri(ethylene glycol) monoethyl ether, tri(ethylene glycol) monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol, tetra(ethylene glycol) monomethyl ether, tetra(ethylene glycol) monoethyl ether, tetra(ethylene glycol) monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, ethylene carbonate, diethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, fluoroethylene carbonate, vinylene carbonate, succinonitrile, succinonitrile, glutaronitrile, hexonitrile, malononitrile, dimethyl sulfoxide, prop-l-ene-l,3-sultone, sulfolane, ethyl vinyl sulfone, tetramethylene sulfone, vinyl sulfone, methyl vinyl sulfone, phenyl vinyl sulfone, Af-propyl-A-methyl pyrrol i di nium bis(fluorosulfonyl)imide, l-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethyl phosphate, triethyl phosphate, and poly(ethylene oxide). In some embodiments, the electrolyte solvent dissolves the electrolyte salt (e.g., the lithium salt). In some embodiments, the electrolyte solvent dissolves the electrolyte salt (e.g., the lithium salt) but does not dissolve the polymer (e.g., the polymer binder). In some embodiments, the electrolyte solvent does not dissolve the fibrillizable polymer binder. The electrolyte solvent can be used to dissolve or otherwise facilitate the mixing or distribution of the electrolyte salts in the active mixture. The amount of the electrolyte solvent used can depend on multiple factors, such as its interaction with other components. The specific amount of an electrolyte solvent may vary from case to case. In general, the minimum amount of an electrolyte solvent would allow the electrolyte salts uniformly distributed within the active mixture and enable the final electrode exhibiting a desired wettability. A maximum amount of an electrolyte solvent would keep the active mixture as a dough rather than a slurry so that it can be subsequently proceeded by calendaring. In some cases, because the electrolyte solvent is not removed from the active mixture, the maximum amount of the electrolyte solvent should not be higher than a threshold value that deteriorates the overall electrochemical performance of the battery. In some embodiments, the electrolyte solvent is present in an amount in a range from 0.5wt% to 5wt%, from 0.5wt% to 7.5wt%, from 0.5wt% to 10wt%, from 0.5wt% to 12.5wt%, from 0.5wt% to 15wt%, from 0.5wt% to 17.5wt%, from 0.5wt% to 20wt%, from 0.5wt% to 22.5wt%, from 0.5wt% to 25wt%, from 0.5wt% to 27.5wt%, from 0.5wt% to 30wt%, lwt% to 5wt%, from lwt% to 7.5wt%, from lwt% to 10wt%, from lwt% to 12.5wt%, from lwt% to 15wt%, from lwt% to 17.5wt%, from lwt% to 20wt%, from lwt% to 22.5wt%, from lwt% to 25wt%, from lwt% to 27.5wt%, from lwt% to 30wt%, from 2wt% to 5wt%, from 2wt% to 7.5wt%, from 2wt% to 10wt%, from 2wt% to 12.5wt%, from 2wt% to 15wt%, from 2wt% to 17.5wt%, from 2wt% to 20wt%, from 2wt% to 22.5wt%, from 2wt% to 25wt%, from 2wt% to 27.5wt%, from 2wt% to 30wt%, from 3wt% to 5wt%, from 3wt% to 7.5wt%, from 3wt% to 10wt%, from 3wt% to 12.5wt%, from 3wt% to 15wt%, from 3wt% to 17.5wt%, from 3wt% to 20wt%, from3wt% to 22.5wt%, from 3wt% to 25wt%, from 3wt% to 27.5wt%, from 3wt% to 30wt%, or any and all ranges and subranges therebetween.

[0054] The lithium salt can be present in the solvent in an amount of about 5 wt% to about 75 wt% (e.g., about 15 wt% to about 75 wt%, or about 25 wt% to about 75 wt%, or about 30 wt% to about 70 wt%, or about 40 wt% to about 60 wt%, or about 15 wt% to about 50 wt%, based on the total weight of the solvent).

[0055] The electrolyte can be present in an amount of about 1 wt% to about 30 wt%, based on the total weight of the electrode (e.g., about 5 wt% to about 25 wt%, or about 10 wt% to about 30 wt%, about 10 wt% to about 20 wt%, or about 1 wt% to about 10 wt%). In some embodiments, the electrolyte is present in an amount of about 5 wt% to about 15 wt%, based on the total weight of the electrode.

[0056] In some embodiments, the solvent for the electrolyte may be an ionic liquid. In some embodiments, the cations of the ionic liquid may be, for example, organic nitrogen cation. Nonlimiting examples of suitable cations of the ionic liquid include l-ethyl-3-methylimidazolium (Iml2+), (N,N-diethyl-N-methyl-N(2methyoxyethyl)ammonium, 1,3-dimethylimidazolium, l-(4- sulfobutyl)-3-methylimidazolium, 1 -butyl- 1-methylpyrrolidinium, l-butyl-3-methylimidazolium, 1 -hexyl-3 -methylimidazolium, 1 -methyl- 1 -(2 -m ethoxy ethyl)pyrrolidinium, 1 -methyl- 1 - octylpyrrolidinium, 3 -methyl- 1-propylimidazolium, N,N-diethyl-N-methyl-N-propylammonium, N-butyl-N-methylpiperidinium, N-propyl-N-methylpiperidinium, 1 -ethyl -3 -methylimidazolium (EMI), l-Butyl-3 -methylimidazolium (BMI), l-Octyl-3 -methylimidazolium (C8MI), 1 -decyl-3 - methylimidazolium (C10MI), l-methyl-3-[2,6-(S)-dimethylocten-2-yl]imidazolium (MDI), 1,2- dimethyl-3-ethylimidazolium (M1,2E3I), l,2-dimethyl-3-propylimidazolium (DMPI), N-methyl- N-propyl-pyrrolidinium (P13), N-methyl-N-butyl-pyrrolidinium (P14), imidazolium, pyrrolidinium, quaternary ammonium, alicyclic cation, pyrrolidine cation, iminazole cation, ethylmethylimidazolium cation, and quaternary ammonium cation.

[0057] Anions of ionic liquidss can be important in lithium battery applications. Non-limiting examples of suitable anions of the ionic liquid include Cl", bis(fluorosulfonyl)imide (FSE), BFE, difluoro(oxalato)borate (DFOB ), N, N-bis(trifluoromethane)sulphonamide (TFSE), Bi sperfluoroethyl sulfonyl imide (BETI), bis(methanesulfonyl)imide (MSI), trifluoromethanesulfonate (OTf), Trifluoroacetate (TA), Hexafluorophosphate ((PFe )s), CF3SO3 , [(CF3SO2)2N] , [(FSO2)2N] , [(CF3SO2)2N] , bis(trifluoromethanesulfonyl)imide (TFSF), iodide, methyl-phosphate, trifluoromethanesulfonate, bis(oxalate)borate (BOB ), acetate, dicyanamide, diethyl phosphate, and hexafluorophosphate. In some cases, the anion includes organic anions. In some cases, the anion includes a ‘plasticizing anion’ which is an anion having a delocalized charge and multiple conformations differing only marginally in energy.

[0058] Various kinds of ionic liquids can be used as the solvent for the electrolyte salt in the active mixture. The ionic liquid has a melting point of, for example, less than 100 °C. Non-limiting examples of suitable ionic liquid include N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ionic liquid, N-alkyl-N-methylpyrrolidinium, perfluorosulfonylimide (PFSI), N-alkyl-N-methylpyrrolidinium (PYR1A) perfluorosulfonylimide (PFSI), l-ethyl-3- methylimidazolium bis(fluorosulfonyl)imide (IM12FSI), l-Propyl-3-methylimidazolium Bis(fluorosulfonyl)imide (IM13FSI), N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyl4TFSI), N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide (Pyl3FSI), and N-Butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (Pyl4FSI).

[0059] In some embodiments, when an ionic liquid is used as the electrolyte solvent in the active mixture, the electrolyte salt such as lithium salt may be needed with a relatively smaller amount as the ionic liquid itself is an electrolyte salt and plays a similar rule like lithium salt, for example, in ion conduction.

[0060] In some embodiments, the electrolyte solvent remains in the active mixture and the final electrode. In some embodiments, preparing the electrode do not include a drying, which is typically required for a traditional slurry method.

[0061] The active material can include an oxide salt (e.g., lithium oxide salts). In some embodiments, the active material includes one or more of lithium nickel manganese cobalt oxide (NMC), LiCoCh, lithium manganese oxide (LMO), lithium iron phosphate (LFP), LiMnPCh, LiCoPCh, lithium nickel cobalt aluminum oxide, or lithium titanate, and Li2MMnsO8, wherein M is selected from Fe or Co.

[0062] The active material can include one or more selected from the group consisting of LiFePCh, LixMCh, LixNii-y-zCoyMlzCh and LixNii-y-zMnyM2zO2, wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, wherein Ml is one or more selected from the group consisting of Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, wherein M2 is one or more selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and wherein 0.95 < x < 1.1, l-y-z>0, 0< y < 0.5, 0 < z < 0.5.

[0063] The active material can be present in an amount of about 50 wt% to about 98.8 wt%, based on the total weight of the electrode (e.g., about 60 wt% to about 97 wt%, or about 75 wt% to about 95 wt%, or about 85 wt% to about 98 wt%, or about 50 wt% to about 75 wt%, based on the total weight of the electrode). In some embodiments, the active material is present in an amount of about 85 wt% to about 95 wt%, based on the total weight of the electrode.

[0064] Advantageously, the electrode prepared according to the disclosure can have a thickness of about 30 pm to about 200 pm, about 50 pm to about 170 pm, or about 60 pm to about 160 pm, and an areal capacity of about 2 mAh / cm2to about 15 mAh / cm2, about 3.5 mAh / cm2to about 15 mAh / cm2, about 4 mAh / cm2to about 10 mAh / cm2, or about 5.5 mAh / cm2to about 10 mAh / cm2. For example, the electrode prepared according to the disclosure has an areal capacity of at least 2 mAh / cm2when the electrode has a thickness of at least 30 pm. For example, the electrode prepared according to the disclosure has an areal capacity of at least 5 mAh / cm2when the electrode has a thickness of at least 80 pm.

[0065] Provided herein is an electrochemical device comprising the electrode as prepared by the methods described herein.

[0066] The electrochemical device described herein can be anode-free or can include an anode. In some embodiments, the electrochemical device includes an anode.

[0067] The anode can be a carbon anode, Li anode, Si anode, Alloy anode, LiMisOn, or made from conversion anode materials. In some embodiments, the carbon anode includes graphite, soft carbon, hard carbon, or combinations of thereof. In some embodiments, the Li anode includes Li metal foil, Li metal on Cu, Ni, or stainless steel. In some embodiments, the Si anode includes Si, Si / Carbon composite, SiOx (0<x<2), SiOx (0<x<2) / carbon composite or a combination thereof. In some embodiments, the alloy anode includes Sn, SnCh, Sb, Al, Mg, Bi, In, As, Zn, Ga, B, or a combination thereof. In some embodiments, the conversion anode materials include MaXb, M is Mn, Fe, Co, Ni, or Cu, X is O, S, Se, F, N, or P, a and b are respectively 1 to 4. In some embodiments, the anode is Li metal foil or Li metal on Cu, Ni, or stainless steel.

[0068] As used herein, the term “Coulombic efficiency” refers to the result of discharge capacity divided by the charge capacity in the same charge and discharge cycle.

[0069] In some embodiments, the electrochemical device includes the electrode as prepared according to the disclosure having a thickness of at least 30 pm and has an areal capacity of at least 2 mAh / cm2.

[0070] In some embodiments, the electrochemical device comprises the electrode as prepared according to the disclosure having a thickness of at least 80 pm and has an areal capacity of at least 5 mAh / cm2.

[0071] The present disclosure generally relates to a device with the electrodes disclosed herein. The device may be a battery, an LIB or a lithium-ion solid-state battery. The battery may be configured for applications such as, portable applications, transportation applications, stationary energy storage applications, and the like. Non-limiting examples of the ion-conducing batteries include lithium-ion conducting batteries, and the like. The device may also be a battery comprising one or more lithium ions electrochemical cells.

[0072] In various examples, a battery includes an electrode as prepared according to the disclosure and an anode.

[0073] Some crosslinkers, electrolyte salts, additives and other materials as described in US application publication Nos. 20200144665 Al and 20200144667 Al which are incorporated herein by reference in their entirety.

[0074] The following examples are intended to illustrate certain embodiments of the present disclosure, but do not exemplify the full scope of the disclosure.

[0075] The foregoing description and following examples detail certain specific embodiments as described herein and describe the best mode that the inventors contemplated. It will be appreciated, however, that no matter how detailed the foregoing may appear in text, the disclosure may be practiced in many ways, and the disclosure should be construed in accordance with the appended claims and equivalents thereof.

[0076] Although the disclosed teachings have been described with reference to various applications, methods, compounds, compositions, and materials, it will be appreciated that various changes and modifications to them may be made without departing from the teachings herein. The following examples are provided to better illustrate the disclosed teachings and are not intended to limit the scope of the teachings presented herein. While the present teachings have been described in terms of these exemplary embodiments, the skilled artisan will readily understand that numerous variations and modifications of these exemplary embodiments are possible without undue experimentation. All such variations and modifications are within the scope of the teachings of this disclosure.EXAMPLESExample 1A - Preparation of Electrochemical DevicesPreparation of an Electrode as described herein (cathode A1-A6)

[0077] To a blender 47 g of NMC811 and 1.5 g of vapor grown carbon fiber (VGCF) were added and then blended in three intervals of 30 seconds. To the same blender, 1.5 g of PTFE was added and then blended for 30 seconds. To the same blender, 5 g of 2.5M LiFSI in an electrolyte solvent was added and blended for 30 seconds to form the active mixture. 5 g of the active mixture was added to a mortar at 80 °C and the active mixture was ground using a pestle for 10 minutes. The active mixture was then calendared multiple times to reach the target thickness to form the cathode film. The cathode film was laid on a carbon coated aluminum foil and fed through with rollers heated to 90°C to laminate the film, complete the fabrication and obtain the cathode. Each cathode includes the following formulation: 91 wt% of NMC811, VGCF, and PTFE (94 wt% NMC811 + 3 wt% VGCF + 3 wt% PTFE), and 9 wt% 2.5M LiFSI in an electrolyte solvent. The various cathode thicknesses are shown below in Table 1.Table 1Preparation of Coin Cells (Coin Cells 1-6)Table 2

[0078] Each cathode A1-A6, independently, was assembled in a different 2032-coin cell with Li metal as the anode. The cycling test was performed with a Neware cycling tester. All the batteries were tested using the same charging and discharging rate. The charge / discharge voltage window was from 2.8 V to 4.3 V. The battery was charged and discharged at a current rate of 0.1C at room temperature as formation and areal capacity is calculated based on the total capacity divided by the active area. The coin cells functioned at all thicknesses tested (Table 2 and FIG. 1). In the cycling step, the battery was charged at C / 3 and discharged at various C-rates up to 1C at room temperature. FIG. 2 shows the results of the battery testing and that samples A4 through A6 had suitable discharge capability.Example IB - Preparation of Electrochemical DevicesPreparation of an Electrode (cathode A7-A8)

[0079] To a blender 47 g of NMC811 and 1.5 g of carbon black (LITX®HP) were added and then blended in three intervals of 30 seconds. To the same blender, 1.5 g of PTFE was added and then blended for 30 seconds. To the same blender, 5 g of 2.5M LiFSI in an electrolyte solvent was added and blended for 30 seconds to form the active mixture. 5 g of the active mixture was added to a mortar at 80 °C and the active mixture was ground using a pestle for 10 minutes. The active mixture was then calendared multiple times to reach the target thickness (e.g., 140 pm for cathode A7 and 66 pm for cathode A8) to form the cathode film. The cathode film was laid on a carbon coated aluminum foil and fed through with rollers heated to 90°C to laminate the film, completethe fabrication and obtain the cathode. Each cathode includes the following formulation: 85.6wt% NMC81 1, 2.7wt%VGCF, 2.7wt%LITX-HP, and 9wt% 2.5M LiFSI in an electrolyte solvent.Preparation of Coin Cells (Coin Cells 7-8)[00801 Each cathode A7 and A8, independently, was assembled in a different 2032-coin cell with Li metal as the anode. The cycling test was performed with a Neware cycling tester. All the batteries were tested using the same charging and discharging rate. The charge / discharge voltage window was from 2.8 V to 4.3 V. The battery was charged and discharged at a current rate of 0.1C as formation and areal capacity is calculated based on the total capacity divided by the active area. In the cycling step, the battery was charged at C / 3 and discharged at various C-rates up to 1C. The reference electrode was prepared by mixing a NMC811 cathode, LITX-HP, and PVDF in a NMP solution. The mixture was then cast on the current collector. The coated film was then dried to remove the NMP and calendared. The final cathode formulation is 94% NMC811, 3% LITX-HP, and 3% PVDF with the loading of 3.0 mAh / cm2. Table 3 shows the results of the battery testing. FIG. 3 shows the testing results of the battery with the A7 electrode and FIG. 4 shows the testing results of the battery with the A8 electrode. All electrodes including the reference electrode were tested under the same condition including the same soaking time. Compared to the preparation and performance of the reference electrode, the methods disclosed herein, e.g., methods of preparing electrodes A7 and A8, can improve the battery formation and result in a higher 1stcycle Coulombic efficiency. As used herein, the term “Coulombic efficiency” refers to the result of discharge capacity divided by the charge capacity in the same charge and discharge cycle. In comparison with the cell with the reference electrode, the 1stcycle Coulombic efficiency of the cell with A7 and A8 was increased by 3.13% and 5.88%, respectively, which was unexpected.Table 3Aspects

[0081] In a first aspect of the present disclosure, a method of preparing an electrode comprises: combining an electron conductive material, a polymer, an electrolyte, and an active material to form an active mixture; and shaping the active mixture to form an electrode. In some embodiments, the electrode can be cathode or anode.

[0082] In a second aspect according to the first aspect, the method further comprises heating the active mixture prior to the shaping, during the shaping, or both.

[0083] In a third aspect according to the first or second aspect, the electron conductive material, the polymer, and the active material are first combined into an intermediate mixture.

[0084] In a fourth aspect according to the third aspect, intermediate mixture is subsequently combined with the electrolyte to form the active mixture.

[0085] In a fifth aspect according to any preceding aspect, the electron conductive material, the polymer, the electrolyte, and the active material are combined in the presence of a solvent that dissolves salts in the electrolyte.

[0086] In a sixth aspect according to the fifth aspect, the solvent that dissolves salts in the electrolyte is the only solvent present in the combining step.

[0087] In a seventh aspect according to any preceding aspect, the electron conductive material, the polymer, the electrolyte, and the active material are combined in the absence of N-methyl-2- pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), and dimethylsulfoxide (DMSO).

[0088] In an eighth aspect according to any preceding aspect, the active mixture is shaped by calendaring to form the electrode.

[0089] In a nineth aspect according to any preceding aspect, the electrode has a thickness of about 30 pm to about 200 pm, about 50 pm to about 170 pm, or about 60 pm to about 160 pm, and an areal capacity of about 2 mAh / cm2to about 15 mAh / cm2, about 3.5 mAh / cm2to about 15 mAh / cm2, about 4 mAh / cm2to about 10 mAh / cm2, or about 5.5 mAh / cm2to about 10 mAh / cm2.

[0090] In a tenth aspect according to any preceding aspect, wherein the electrode has an areal capacity of at least 2 mAh / cm2and a thickness of at least 30 pm.

[0091] In an eleventh aspect according to any preceding aspect, the polymer comprises a fluorinated polymer.

[0092] In a twelfth aspect according to any preceding aspect, the fluorinated polymer comprises one or more selected from the group consisting of polytetrafluoroethylene (PTFE), poly vinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyvinylfluoride (PVF), perfluoroalkoxy polyme (PF A), and fluorinated ethyl ene-propylene (FEP).

[0093] In a thirteenth aspect according to any preceding aspect, the polymer is present in an amount of about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about 0.5 wt% to about 2.5 wt%, based on the total weight of the electrode.

[0094] In a fourteenth aspect according to any preceding aspect, the electron conductive material is a conductive carbon.

[0095] In a fifteenth aspect according to any preceding aspect, the electron conductive material is present in an amount of about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, or about0.5 wt% to about 3.5 wt%, or about 1.5 wt% to about 3.5 wt%, based on the total weight of the electrode.

[0096] In a sixteenth aspect according to any preceding aspect, the active material comprises one or more of Li F ePO4, LixMCh, LixNii-y-zCoyMLCh and LixNii-y-zMnyM2zO2, wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, wherein Ml is one or more selected from the group consisting of Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, wherein M2 is one or more selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and wherein 0.95 < x < 1.1, l-y-z>0, 0< y < 0.5, 0 < z < 0.5.

[0097] In a seventeenth aspect according to any preceding aspect, the active material is present in an amount of about 50 wt% to about 98.8 wt%, or about 60 wt% to about 97 wt%, or about 75 wt% to about 95 wt%, or about 85 wt% to about 98 wt%, based on the total weight of the electrode.

[0098] In an eighteenth aspect according to any preceding aspect, the electrolyte comprises one or more selected from the group consisting of lithium perchlorate (LiCICh), lithium hexafluorophosphate (LiPFe), lithiumborofluoride (LiBF4), lithium hexafluoroarsenide (LiAsFe), lithium trifluoro-metasulfonate (LiCFsSCh), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2, LiTFSI), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitratefLiNCh), lithium fluoroalkylphosphates (Li[PFx(CyF2y+i-zHz)6-x]) (l<x<5, l<y<8, and 0<z<2y-l)„ lithium bisperfluoroethysulfonylimide (LiBETI), lithium bis(fluorosulphonyl)imide, lithium difluoro(oxalato)borate (LiDFOB), lithium fluorophosphate (IXPChF), lithium difluoro(bisoxalato)phosphate (LiC4PO8F2), lithium tetrafluoro oxalato phosphate (LiC2PO4F4), lithium difluorophosphate (LiDFP), LiC(CF3SCh)3, LiF, LiCl, LiBr, Lil, Li2SO4, LisPCh, Li2CO3, LiOH, lithium acetate, lithium trifluoromethyl acetate, and lithium oxalate.

[0099] In a nineteenth aspect according to any preceding aspect, the electrolyte further comprises a salt in a solvent.

[0100] In a twentieth aspect according to the nineteenth aspect, the salt is present in the solvent in an amount of about 5 wt% to about 75 wt%, or about 15 wt% to about 75 wt%, or about 25 wt% to about 75 wt%, or about 30 wt% to about 70 wt%, or about 40 wt% to about 60 wt%, or about 15 wt% to about 50 wt%, based on the total weight of the solvent.

[0101] In a twenty-first aspect according to any preceding aspect, wherein the electrolyte is present in an amount of about 1 wt% to about 30 wt%, or about 5 wt% to about 25 wt%, or about10 wt% to about 30 wt%, or about 1 wt% to about 10 wt%, based on the total weight of the electrode.

[0102] In a twenty-second aspect according to the nineteenth aspect, the solvent comprises one or more selected from the group consisting of 1,2-di ethoxy ethane, 1,1 -di ethoxy ethane, 1,1- dipropoxy-ethane, 1,2-dipropoxy-ethane, di ethylene glycol, 2-(2-ethoxyethoxy)ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, tri(ethylene glycol) monomethyl ether, tri(ethylene glycol) monoethyl ether, tri(ethylene glycol) monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol, tetra(ethylene glycol) monomethyl ether, tetra(ethylene glycol) monoethyl ether, tetra(ethylene glycol) monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, ethylene carbonate, diethyle carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, fluoroethylene carbonate, vinylene carbonate, succinonitrile, succinonitrile, glutaronitrile, hexonitrile, malononitrile, dimethyl sulfoxide, prop-l-ene-l,3-sultone, sulfolane, ethyl vinyl sulfone, tetramethylene sulfone, vinyl sulfone, methyl vinyl sulfone, phenyl vinyl sulfone, 7V-propyl-7V-methylpyrrolidinium bis(fluorosulfonyl)imide, l-ethyl-3- methylimidazolium bis(fluorosulfonyl)imide, trimethyl phosphate, triethyl phosphate, and poly(ethylene oxide).

[0103] In a twenty-third aspect, the present disclosure provides an electrochemical device comprising the electrode as prepared by the methods according to any preceding aspect.

[0104] In a twenty -fourth aspect according to the twenty -third aspect, the electrochemical device further comprises an anode, wherein the anode is a carbon anode, Li anode, Si anode, alloy anode, Li4TisOi2, or made from conversion anode materials.

[0105] In a twenty -fifth aspect according to the twenty -third or twenty-fourth aspect, the electrode of the electrochemical device has a thickness of at least 30 pm, at least 50 pm, at least 100 pm, or about 50 pm to about 200 pm, or about 120 pm to about 170 pm.

[0106] In a twenty-sixth aspect according to any of the twenty -third through twenty-fifth aspects, the electrode of the electrochemical device has a thickness of at least 80 pm and has an areal capacity of at least 5 mAh / cm2.

[0107] Various embodiments of the features of this disclosure are described herein. However, it should be understood that such embodiments are provided merely by way of example, and numerous variations, changes, and substitutions can occur to those skilled in the art without departing from the scope of this disclosure. It should also be understood that various alternatives to the specific embodiments described herein are also within the scope of this disclosure.

Claims

We claim;1. A method of preparing an electrode, the method comprising: combining an electron conductive material, a polymer as a binder, an electrolyte, and an active material to form an active mixture; and shaping the active mixture to form an electrode, wherein the electron conductive material, the polymer, the electrolyte and the active material are present in an amount in a range from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 10 wt%, from about 1 wt% to about 30 wt%, and from about 50 wt% to about 98.8 wt% based on the total weight of the electrode, respectively.

2. The method of claim 1, further comprising heating the active mixture prior to the shaping, during the shaping, or both.

3. The method of claim 1, wherein the electron conductive material, the polymer, the electrolyte, and the active material are first combined into an intermediate mixture followed by combining with the electrolyte to form the active mixture.

4. The method of claim 1, wherein the electrolyte comprises a salt and a solvent of the salt.

5. The method of claim 4, wherein the salt is present in the solvent in an amount of about 5 wt% to about 75 wt% based on the total weight of the solvent.

6. The method of claim 4, wherein the solvent of the salt does not dissolve the polymer.

7. The method of claim 4, wherein the method does not include a drying step and the solvent remains in the active mixture and the electrode.

8. The method of claim 6, wherein the solvent is substantially free of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), and dimethylsulfoxide (DMSO).

9. The method of claim 1 wherein the active mixture is shaped by calendaring to form the electrode.

10. The method of claim 1 or 4, wherein the electrode has an areal capacity of at least 2 mAh / cm2and a thickness of at least 30 pm.

11. The method of claim 10, wherein the electrode has a thickness in a range from about 50 pm to about 170 pm, and an areal capacity in a range from about 2 mAh / cm2to about 15 mAh / cm2.

12. The method of claim 1 or 3, wherein the polymer comprises a fluorinated polymer.

13. The method of claim 12, wherein the fluorinated polymer comprises one or more of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyfvinylidene fluoride-co- hexafluoropropylene) (PVDF-HFP), polyvinylfluoride (PVF), perfluoroalkoxy polyme (PF A), and fluorinated ethylene-propylene (FEP).

14. The method of claim 1, wherein the electron conductive material is a conductive carbon.

15. The method of claim 1, wherein the active material comprises one or more selected from the group consisting of LiFePO4, LixMCh, LixNii-y-zCoyMlzCh and LixNii-y-zMnyM2zO2, wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, wherein Ml is one or more selected from the group consisting of Mn, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, wherein M2 is one or more selected from the group consisting of Co, Al, B, Fe, Mg, Ca, Sr, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Rh, Pd, Cu, Zn, Cd, Ga, In, Sn, and rare earth elements, and wherein 0.95 < x < 1.1, l-y-z>0, 0< y < 0.5, 0 < z < 0.5.

16. The method of claim 4, wherein the salt comprises at least one selected from the group consisting of lithium perchlorate (LiCICh), lithium hexafluorophosphate (LiPFe), lithiumborofluoride (LiBF4), lithium hexafluoroarsenide (LiAsFe), lithium trifluoro-metasulfonate (LiCFsSCh), lithium bis(trifluoromethanesulfonyl)imide (LiN(CFsSO2)2, LiTFSI), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate(LiNO3), lithium fluoroalkylphosphates (Li[PFx(CyF2y+i-zHz)6-x]) (l<x<5, l<y<8, and 0<z<2y-l)„ lithium bisperfluoroethysulfonylimide (LiBETI), lithium bis(fluorosulphonyl)imide, lithium difluoro(oxalato)borate (LiDFOB), lithiumfluorophosphate (I 2PO3F), lithium difluoro(bisoxalato)phosphate (LiC4POsF2), lithium tetrafluoro oxalato phosphate (I C2PO4F4), lithium difluorophosphate (LiDFP), LiC(CF3SO2)3, LiF, LiCl, LiBr, Lil, Li2SO4, LL3PO4, Li2CC>3, LiOH, lithium acetate, lithium trifluoromethyl acetate, and lithium oxalate.

17. The method of claim 4, wherein the solvent comprises one or more selected from the group consisting of 1,2-di ethoxy ethane, 1,1 -di ethoxy ethane, 1,1 -dipropoxy-ethane, 1,2-dipropoxy- ethane, diethylene glycol, 2-(2-ethoxyethoxy)ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, tri(ethylene glycol) monomethyl ether, tri(ethylene glycol) monoethyl ether, tri(ethylene glycol) monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol, tetra(ethylene glycol) monomethyl ether, tetra(ethylene glycol) monoethyl ether, tetra(ethylene glycol) monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, ethylene carbonate, diethyle carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, fluoroethylene carbonate, vinylene carbonate, succinonitrile, succinonitrile, glutaronitrile, hexonitrile, malononitrile, dimethyl sulfoxide, prop-l-ene-l,3-sultone, sulfolane, ethyl vinyl sulfone, tetramethylene sulfone, vinyl sulfone, methyl vinyl sulfone, phenyl vinyl sulfone, A-propyl- -methylpyrrolidinium bis(fluorosulfonyl)imide, l-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, trimethyl phosphate, triethyl phosphate, and poly(ethylene oxide).

18. An electrochemical device comprising the electrode as prepared by the methods of any one of claims 1-17.

19. The electrochemical device of claim 18, wherein the electrode has a thickness of in a range from about 50 pm to about 200 pm.

20. The electrochemical device of claim 18, wherein the electrode has a thickness of at least 80 pm and has an areal capacity of at least 5 mAh / cm2.