High energy cathode and method for manufacturing the same

Abstract

To allow cathodes to be economically incorporated into batteries that can provide high energy density.SOLUTION: A cathode active material includes a metal compound having the formula MaRb, where M is a metal and each R is independently selected such that MaRb is an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers, and a metal oxide having the formula MxOy, where M is the same metal in the metal compound, and x and y are independently non-zero positive real numbers, provided that the metal compound and the metal oxide are in contact.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] Technical Field The present disclosure relates to cathode active materials, to cathodes including the cathode active materials, and to methods of manufacturing batteries incorporating such cathodes.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part under 35 U.S.C. § 120 of U.S. patent application Ser. No. 17 / 175,267, filed February 12, 2021, and a continuation-in-part under 35 U.S.C. § 120 of U.S. patent application Ser. No. 17 / 220,823, filed April 1, 2021, the contents of each of which are incorporated herein by reference for all purposes. [Background technology]

[0003] background Batteries are ubiquitous in modern technology and are used in a wide range of applications, from small batteries for industrial and medical devices to larger batteries for electric vehicles and grid energy storage systems. Perhaps the most well-known and widely used battery technology currently is the lithium-ion battery, which uses an intercalated lithium compound as one electrode material and shuttles lithium ions between a cathode and an anode within a reservoir of electrolyte. Although lithium-ion batteries have many advantages, they offer relatively low energy density and can require expensive materials for manufacture.

[0004] Lithium-air or lithium-oxygen batteries are considered to be the "next generation" lithium-ion battery technology and are known to outperform today's lithium-ion batteries in many respects, such as energy density and material cost. These batteries consume oxygen and generate active oxygen species that function as cathode active materials. However, such batteries are prone to oxygen desorption at relatively low temperatures during operation, resulting in electrochemically irreversible by-products that severely impede the rechargeability of the battery. Such oxygen desorption or active oxygen species dissociation can also cause thermal runaway reactions in the battery.

[0005] What is needed is an improved cathode that incorporates improved cathode active materials and can provide greater energy density, more economical manufacturing costs, and lower material costs while simultaneously exhibiting greater electrochemical reversibility and resistance to oxygen evolution during use. Summary of the Invention [Problem to be solved by the invention]

[0006] overview The present disclosure is directed to cathode active materials and methods for their manufacture, as well as cathodes incorporating the cathode active materials, and batteries incorporating such cathodes.

[0007] In one embodiment, the present disclosure provides a R b wherein M is a metal and each R is independently M a R b is selected to be an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers; x O y wherein M is the same metal in the metal compound, and x and y are independently positive real numbers other than zero, and a metal oxide having an empirical formula of:

[0008] In another embodiment, the present disclosure provides a method for producing a R b wherein M is a metal and each R is independently M a R b is selected to be an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers; x O y wherein M is the same metal in the metal compound, and x and y are independently non-zero positive real numbers, wherein the metal compound and the metal oxide are in contact, and an electrically conductive material, wherein one or both of the metal compound and the metal oxide are in contact with the electrically conductive material.

[0009] In another embodiment, the present disclosure is directed to a battery having a cathode and an electrolyte, the cathode being selected from the group consisting of M a R b wherein M is a metal and each R is independently M a R b is selected to be an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers; x O y where M is the same metal in the metal compound, and x and y are independently positive real numbers other than zero, and a metal oxide having an empirical formula of: [Means for solving the problem]

[0010] The disclosed features, functions, and advantages of the disclosed cathode active materials, cathodes, and batteries can be achieved independently in various embodiments of the present disclosure or can be combined in yet other embodiments, further details of which can be found in reference to the following description and drawings. [Brief description of the drawings]

[0011] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] 1 is a flow chart of an exemplary method of making a cathode active material according to the present disclosure. [Diagram 2] 1 is a flow chart of an exemplary method for manufacturing a cathode according to the present disclosure. [Diagram 3] 1 is a semi-schematic diagram of an exemplary battery including a cathode made in accordance with the present disclosure. [Figure 4] 1 is a plot illustrating the high specific capacity and high voltage performance of an exemplary battery incorporating a cathode active material according to the present disclosure, as described in Example 2. [Diagram 5] 1 is a plot illustrating the advantageously high rechargeability of an exemplary battery incorporating a cathode active material according to the present disclosure, as described in Example 3. [Figure 6] 1 is a bar graph comparing the specific capacity of selected battery cathode materials compared to cathodes made in accordance with the present disclosure, as described in Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Detailed Description The present disclosure provides high energy density cathode active materials that can be inexpensively manufactured and used to make cathodes for use in batteries. Selected cathodes made according to the present disclosure do not generate substantially gaseous oxygen during the operation of a battery that includes the cathode. In some embodiments, cathodes made according to the present disclosure generate gaseous oxygen at a rate of less than about 1 mg / 1 mAh during the full life of a battery that includes the cathode. As used herein, the term "full life of a battery" is intended to mean that the life of a battery is considered to be beyond its normal useful life, which is considered here to be the point at which the battery first exhibits 80% of its original capacity.

[0013] The cathode active material determines the difference in composition when making the positive electrode of the battery cell, and therefore it is the cathode active material that determines the type of the battery. For example, the LFP battery (deevs.com / news / 563506 / tesla-transition-ess-lfp-batteries) is a battery that contains LFP (LiFePO4) as its cathode active material. The cathode active material is responsible for supplying ions through the electrolyte and supplying electrons through the external circuit while the battery is charging, and is responsible for receiving ions through the electrolyte and receiving electrons through the external circuit while the battery is discharging. On the other hand, the anode active material is responsible for supplying ions through the electrolyte and supplying electrons through the external circuit while the battery is discharging, and is responsible for receiving ions through the electrolyte and receiving electrons through the external circuit while the battery is charging. Both the cathode active material and the anode active material participate in electrochemical redox reactions by transporting ions through the electrolyte and / or electrons through the external circuit.

[0014] Any coatings, natural or artificial layers, protective layers of any kind on the surface of the cathode or anode active materials that do not participate in the electrochemical redox reactions during charging and discharging of the battery are not considered to be part of the respective active materials.

[0015] "Redox reaction" means a type of chemical reaction in which the oxidation number of the participating atoms, molecules, radicals, or ions changes by gaining or losing electrons. Redox reactions are characterized by the actual or formal transfer of electrons between chemical species, most often one species undergoes oxidation while another species undergoes reduction.

[0016] "Current collector" means a component adjacent to an electrode configured to carry electrical current from a fixed portion to a moving portion of a circuit in an electrochemical cell, or vice versa. A current collector is a bridging component that collects electrical current generated at an electrode and provides a connection to an external circuit. A current collector is typically adjacent to a cathode or anode. In some embodiments, the current collector comprises an electrically conductive material that is a porous carbon material that may be selected from carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, reduced graphene oxide, and graphene nanoribbons.

[0017] "Electrolyte" or "electrolyte solution" means a material that provides for ion transport in an electrochemical cell. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes. In particular, the electrolyte can facilitate the movement of ions from the cathode to the anode during charging of the electrochemical cell, and can facilitate the movement of ions from the anode to the cathode during discharge.

[0018] As used herein, "room temperature" refers to any temperature within the range of temperatures that most people prefer for their indoor environment, that is, a temperature that feels comfortable when wearing typical indoor clothing. More specifically, room temperature includes temperatures between 15 and 30° C. (or 59 and 86° F.).

[0019] "Substantially" means more or less conforming to a particular size, area, shape, concept, or other aspect that is modified by the term, and does not require an exact conformance of features or components. For example, a "substantially cylindrical" object means that the object resembles a cylinder, but may have one or more deviations from a true cylinder.

[0020] "Comprising," "including," and "having" (and combinations thereof) are open-ended terms that are used interchangeably to mean the inclusion, but not necessarily limitation, of additional, unrecited elements or method steps and are not intended to be exclusive.

[0021] Terms such as "first," "second," and "third" may be used to distinguish or identify various elements of a group or the like and are not intended to denote sequential or quantitative limitations.

[0022] Unless relating to specific examples, all recitations of amounts and parts, particularly those intended to define the scope of the invention, indicate a tolerance of ±10%, for example: 11% means 9.9% to 12.1%. With respect to terms such as "a solvent," the word "a" should not be regarded as a numerical term, but rather as an indefinite article or pronoun, unless the context dictates otherwise.

[0023] The term "combination" or "combinations" means, unless otherwise specified, all types of combinations starting from two of the elements in question to a plurality or all of such elements.

[0024] Preparation of cathode active material An exemplary method for making a high energy cathode active material according to the present disclosure is illustrated in Flowchart 10 of Figure 1. The method includes preparing a solution of a hygroscopic species and an active oxygen species in step 12 of Flowchart 10, heating the solution at a temperature below about 400°C for a sufficient time to form a precipitate of cathode active material in step 14 of Flowchart 10, collecting the precipitated cathode active material in step 16 of Flowchart 10, and drying the collected cathode active material at a temperature below about 400°C in step 18 of Flowchart 10. The precipitate can be an active oxygen species derivative, an active oxygen species derivative combined with a hygroscopic species, or an active oxygen species combined with a hygroscopic species.

[0025] The hygroscopic species used to prepare the cathode active material can be any hygroscopic species that forms a precipitate when heated as a solution with an appropriate active oxygen species. Typically, the hygroscopic species is a compound or substance that draws water from its environment, either by chemical reaction, by mixing water of hydration, or by physical adsorption. In particular, the hygroscopic species can be substantially free of transition metals. Particularly useful hygroscopic materials can include one or more ionic materials and / or one or more organic materials.

[0026] When the hygroscopic species includes one or more ionic materials, the ionic materials can include one or more ionic compounds, where the ionic compounds are typically salts, more typically chloride, bromide, pentoxide, sulfide, and / or sulfate salts, and the ionic materials can be acids capable of donating a proton.

[0027] When the hygroscopic species includes one or more organic materials, the organic materials can be selected from any suitable organic compound or fragment of an organic compound that incorporates one or more nitrogen or oxygen atoms. For example, the one or more organic materials can be selected from among truxenone, truxenone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives, quinone, quinone derivatives, diamine derivatives, phenazine, phenazine derivatives, quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, triazine, triazine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropenium derivatives, and amide derivatives.

[0028] Selected examples of hygroscopic species for the present disclosure include, among others, CH 14 Cl4N4 (benzenetetramine tetrahydrochloride), C6H 16 O 14 (Hexaketocyclohexane octahydrate), C8H6O4 (Terephthalic acid), LiOH (Lithium hydroxide), NaOH (Sodium hydroxide), C 13 H 22NO3 (Tetramethylpiperidin-1-oxyl-4-yl methacrylate), LiCl (Lithium chloride), NaCl (Sodium chloride), HCl (Hydrogen chloride), HBr (Hydrogen bromide), LiBr (Lithium bromide), NaClO3 (Sodium chlorate), P2O5 (Phosphorus pentoxide), H2S (Hydrogen sulfide), H2SO4 (Hydrogen sulfide), HClO3 (Chloric acid), C7H6O2 (Benzoic acid), C2HF3O2 (Trifluoroacetic acid), HBO (Metaboric acid), C7H6O3 (Salicylic acid), C2H4O2 (Acetic acid), C 16 H 32 O2 (palmitic acid), HSCN (thiocyanic acid), C3H6O3 (lactic acid), H3PO4 (phosphoric acid), CH2O2 (formic acid), C 12 H 23 N (dicyclohexylamine), C2H6N (dimethylamine), C6H5SH (thiophenol), C6H2O6 (rhodizonic acid), C 16 H8O6 (anthraquinone-2,3-dicarboxylic acid), C6H2Cl2O4 (chloranilic acid), and C 22 H 24 N4O4 (naphthalene diimide) may be included.

[0029] The reactive oxygen species can be any species that includes one or more reactive oxygen moieties. For example, the reactive oxygen species can include one or more reactive oxygen moieties, such as peroxide, superoxide, superoxide radical, hydroxyl radical, peroxyl radical, perhydroxyl radical, hydroperoxyl radical, alkoxyl radical, singlet oxygen, hypochlorous acid, and alpha oxygen. In one embodiment of the present disclosure, the reactive oxygen species includes at least one peroxide moiety. The reactive oxygen species can include, among others, Li2O2 (lithium peroxide), H2O2 (hydrogen peroxide), HOCl (hypochlorous acid), O2 *- (superoxide radical), NaO2 (sodium superoxide), NO * (Nitroxyl radical), C6H5O * (phenoxyl radical), and 1 O2 (singlet oxygen).

[0030] During the reaction, the reactive oxygen species is typically converted to a reactive oxygen species derivative. The reactive oxygen species derivative can be any species derived from the reactive oxygen species, and can be distinguished from the reactive oxygen species in that it no longer contains a reactive oxygen moiety such as a peroxide, a superoxide, a superoxide radical, a hydroxyl radical, a peroxyl radical, a perhydroxyl radical, a hydroperoxyl radical, an alkoxyl radical, singlet oxygen, hypochlorous acid, and alpha oxygen.

[0031] Any method of preparing a solution of hygroscopic species and active oxygen species is a suitable method for the method of Flowchart 10. For example, preparing a solution of one or more hygroscopic species and one or more active oxygen species can include adding each of the desired hygroscopic species and active oxygen species to a single solution to form the desired combined solution. Alternatively, one or both of the hygroscopic species and active oxygen species can be initially dissolved in a solvent, and then the hygroscopic species solution and the active oxygen species solution can be combined to form the combined solution, or both can be added to an existing solution to form the combined solution.

[0032] The resulting solution is then heated to a temperature less than about 400° C. but high enough to result in the formation of a precipitate of the desired cathode active material. The heating temperature is preferably less than about 300° C., more preferably less than about 200° C. It should be understood that it is not usually possible to heat a solution to a temperature above the boiling point of the solution under standard conditions, so the combined solution may be transferred to a sealed container or autoclave for heating under high pressure. During heat treatment, the atmosphere of the sealed container or autoclave may be replaced with high purity oxygen gas.

[0033] When the combined solution has been heated for a sufficient time to form a precipitate of the cathode active material, the cathode active material can be collected. Any suitable separation method can be used to collect the cathode active material precipitate, but typically the precipitate mixture is filtered and washed. The filtered and washed cathode active material included in the step of collecting the cathode active material can be dried under vacuum or in an inert gas atmosphere at a temperature of less than about 400°C. The drying temperature is preferably less than about 300°C, more preferably less than about 200°C.

[0034] Testing or further handling of the collected and dried cathode active material may be performed under dry conditions, e.g., at a relative humidity of less than about 25%. Preferably, such handling is performed in a dry room.

[0035] Cathode Active Material During the preparation of the cathode active material, the hygroscopic species and the active oxygen species typically undergo a reaction to produce a cathode active material that includes one or more new materials. In one aspect of the present disclosure, the combination of the hygroscopic species and the active oxygen species produces a cathode active material that includes a metal compound and a metal oxide. The metal compound and the metal oxide can be separate components of the cathode active material, such as when the cathode active material includes a homogeneous mixture. Alternatively, or in addition, the metal compound and the metal oxide can be bound to each other in a complex, in a cluster, or in a crystalline, pseudocrystalline, or amorphous matrix. In one embodiment, one or more of the hygroscopic species is a metal compound. Typically, the cathode active material includes a metal compound and a metal oxide such that the metal compound and the metal oxide are in contact with each other.

[0036] The metal compound of the cathode active material has the empirical formula M a R b where M is a metal, and each R moiety is independently selected from any suitable atom, molecule, or radical, and M a R bis an inorganic or organometallic compound or complex. Each R moiety can independently have a formal oxidation number of -1, -2, or -3. Typically, each R moiety has a formal oxidation number of -1. The values ​​of a and b are independently positive real numbers that are not zero. Each R can be a fragment or a substituent of a larger compound.

[0037] In one embodiment, one or more R moieties can independently be or include one or more of hydrogen, nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron. Alternatively, or in addition, each R can independently be an inorganic moiety, or an organic moiety.

[0038] Each R moiety that is an inorganic moiety may be selected from hydrides, halides, oxides, hydroxides, chlorates, sulfides, sulfates, metaborate, thiocyanates, amides, nitrides, and azides, among others.

[0039] Each R moiety that is an organic moiety optionally further comprises one or more heteroatoms independently selected from nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron. In some embodiments, each R moiety that is an organic moiety excludes an alkali metal, an alkaline earth metal, or a transition metal. In some embodiments, the R moiety can include carbon, hydrogen, or oxygen. In some embodiments, the R moiety is an organic moiety having 1 to 6 carbons.

[0040] Non-limiting examples of suitable R moieties for the present disclosure can include, among others, -H (hydride), -OH (hydroxyl), -COOH (carboxyl), -CH (alkyne), -CH2 (alkene), -CHO (aldehyde), -CO- (carbonyl), -COO- (ester), -O- (ether), -NH2 (amine), -CN (nitrile), alkyl halide, oxyhalide, alkane, alkene, alkyne, arene, phenyl, thiol, thial, sulfide, sulfoxide, sulfone, ketone, amide, haloalkane, methoxide, ethoxide, epoxide, phenoxide, nitride, nitrate, nitroso, quinone, imine, imide, azide, lactate, phosphate, formate, and cyanate.

[0041] Selected examples of metal compounds of the cathode active material include, among others, LiOH (lithium hydroxide), LiCl (lithium chloride), NaCl (sodium chloride), LiBr (lithium bromide), NaClO3 (sodium chlorate), Li2S (lithium sulfide), Li2SO4 (lithium sulfate), LiC7H5O (lithium benzoate), LiC2F3O2 (lithium trifluoroacetate), LiCH3O (lithium methoxide), LiBO2 (lithium metaborate), LiC7H5O3 (lithium salicylate), LiC2H3O2 (lithium acetate), LiC 16 H 31 O2 (lithium palmitate), LiSCN (lithium thiocyanate), LiC9H 18 N (lithium 2,2,6,6-tetramethylpiperidide), LiC3H5O (lithium lactate), Li3PO4 (lithium phosphate), LiCHO2 (lithium formate), LiBH4 (lithium borohydride), LiC 12 H 22N (lithium dicyclohexylamide), LiNH2 (lithium amide), LiH (lithium hydride), LiC2H5S (lithium thioethoxide), LiCH3O (lithium ethoxide), LiC2H6N (lithium dimethylamide), LiC6H5O (lithium phenoxide), LiC6H5S (lithium thiophenolate), Li3N (lithium nitride), LiN3 (lithium azide), LiC3H7O (lithium isopropoxide), Li2C8H4O4 (lithium terephthalate), Li2C6O6 (lithium rhodizonate), LiC 16 H8O6 (lithium dicarboxylate anthraquinone), Li2C6H4O4 (dilithium dihydroxybenzoquinone), and LiC 22 H 24 N4O4 (lithium naphthalene diimide) may be included.

[0042] The metal oxide of the cathode active material has the empirical formula M' x O y where M' is a metal which may be the same or different from M of the metal compound, and x and y are each a non-zero positive real number which may be the same or different. The metal oxide may be or include a metal superoxide, a metal superoxide radical, and / or a metal peroxide.

[0043] M and M' may be the same or different and may be selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum.

[0044] The resulting cathode active material can include at least a portion of the metal compound and at least a portion of the metal oxide that, when taken in combination, form a cluster. In one embodiment of the present disclosure, the resulting cluster has the empirical formula M a M' b R c O d where a, b, c, and d are each a non-zero positive real number and may be the same or different.

[0045] The resulting cathode active material composition can have a weight ratio of metal compound:metal oxide that can vary from 5:95 to 75:25. a R b The composition ratio of :M'xOy can be about 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, or 75:25. Typically, the cathode active material is at least 25% by weight metal oxide. Preferably, the cathode active material is at least about 50% by weight metal oxide. More preferably, the cathode active material is at least about 75% by weight metal oxide.

[0046] The average particle size of the cathode active material can vary from about 5 nm to about 50 μm, and exhibits an average pore size of about 0.1 nm to about 1 μm. Typically, the average particle size of the cathode active material is less than about 50 μm. Preferably, the average particle size of the cathode active material is greater than about 500 nm and less than about 50 μm. More preferably, the average particle size of the cathode active material is greater than about 5 μm and less than about 50 μm. Typically, the average pore size of the cathode active material is less than about 1 μm. Preferably, the average particle size of the cathode active material is greater than about 1 nm and less than about 500 nm. More preferably, the average particle size of the cathode active material is greater than about 5 nm and less than about 200 nm.

[0047] In some embodiments, the cathode active material is at least partially encapsulated at its exterior surface by a coating layer. The coating layer can vary in thickness from about 1 nm to about 1 μm. Preferably, the coating layer has a thickness of from about 2 nm to about 500 nm. More preferably, the coating layer has a thickness of from about 5 nm to about 200 nm. When present, the coating layer can include carbon and oxygen.

[0048] High Energy Cathode High energy cathodes can be made using the cathode active materials disclosed herein, as illustrated in Flowchart 20 of Figure 2. As shown, a method of manufacturing a cathode for use in a battery includes preparing a solution of a hygroscopic species and an active oxygen species in step 21 of Flowchart 20, heating the solution at a temperature below about 400°C for a sufficient time to form a precipitate of the cathode active material in step 22 of Flowchart 20, collecting the cathode active material in step 24 of Flowchart 20, drying the collected cathode active material at a temperature below about 400°C in step 26 of Flowchart 20, combining the collected cathode active material with one or more of an electrically conductive material, a polymeric binder, a plasticizer, and a carboxylic acid in step 28 of Flowchart 20, and depositing the combined cathode material onto a current collector to form a cathode in step 30 of Flowchart 20.

[0049] As noted above, steps 21, 22, 24, and 26 of flowchart 20 are entirely analogous to corresponding steps 12, 14, 16, and 18 of flowchart 10.

[0050] As illustrated in step 28 of Flowchart 20, the cathode active material can be combined with one or more of an electrically conductive material, a polymeric binder, a plasticizer, and a carboxylic acid. Typically, the cathode active material is combined with an electrically conductive material. Additionally, the cathode active material can be further combined with one or more of a polymeric binder, a plasticizer, and a carboxylic acid.

[0051] If the cathode includes an electrically conductive material, it can be added to one of the hygroscopic species or active oxygen species prior to preparation of the cathode active material, or the cathode active material can be combined with the electrically conductive material after it is formed. Typically, the cathode active material is in contact with the electrically conductive material.

[0052] When the cathode active material includes a metal compound and a metal oxide, each of the metal compound and the metal oxide is in contact with the other, and one or both of the metal compound and the metal oxide is in contact with an electrically conductive material.

[0053] When the cathode comprises a cathode active material and an electrically conductive material, the cathode composition can have a weight ratio of cathode active material:electrically conductive material that can vary from 20:80 to 99:1. The composition ratio of cathode active material:electrically conductive material can be about 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 96:4, 97:3, 98:2, 99:1. Typically, the cathode composition is at least 20% by weight of cathode active material. Preferably, the cathode composition is at least 40% by weight of cathode active material. More preferably, the cathode composition is at least 60% by weight of cathode active material.

[0054] Any electrically conductive material that promotes the performance of the resulting cathode is a suitable electrically conductive material for the purposes of this disclosure. In some embodiments, the electrically conductive material comprises a porous carbon material that is or includes one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, microporous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, reduced graphene oxide, graphene nanoribbons, nitrogen-doped carbon, nitrogen-doped graphene, and nitrogen-doped graphene oxide. The electrically conductive material can have any suitable and compatible physical form, such as particles, powders, paper, foams, fibers, sheets, disks, rods, foils, or any combination thereof. When the cathode comprises a porous carbon material, carbon nanotubes and / or carbon nanofibers, and carbon nanotubes are particularly preferred due to their high aspect ratio and durability.

[0055] In one embodiment, the electrically conductive material comprises a porous carbon material having particles with an average particle size or diameter of about 5 nm to about 50 μm and exhibiting an average pore size of about 0.1 nm to about 1 μm. Typically, the average particle size or diameter of the electrically conductive material is less than about 50 μm. Preferably, the average particle size of the electrically conductive material is greater than about 50 nm and less than about 50 μm. More preferably, the average particle size of the electrically conductive material is greater than about 500 nm and less than about 50 μm. Typically, the average pore size of the electrically conductive material is less than about 1 μm. Preferably, the average particle size of the electrically conductive material is greater than about 1 nm and less than about 500 nm. More preferably, the average particle size of the electrically conductive material is greater than about 5 nm and less than about 200 nm.

[0056] In some embodiments, the average particle size or diameter of the cathode active material and the electrically conductive material are inversely proportional. In such embodiments, when the average particle size of the cathode active material is in the range of about 10 μm to about 50 μm, the average particle size of the electrically conductive material can be about 10 nm to about 50 nm, and vice versa. Typically, one or more of the cathode active material and the electrically conductive material comprises particles having an average particle size or diameter greater than about 50 nm and less than about 50 μm, preferably greater than about 500 nm and less than about 50 μm, and more preferably greater than about 1 μm and less than about 30 μm.

[0057] In one embodiment, the step of combining the cathode active material with the electrically conductive material comprises combining the cathode active material with a porous carbon material. The porous carbon material is optionally doped with one or more heteroatoms selected from boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine, and bromine. A cathode comprising a porous carbon material doped with nitrogen and / or fluorine is preferred as it allows for lower charge transfer resistance, with nitrogen being particularly preferred. When present, the porous carbon material can comprise one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

[0058] Any suitable electrically conductive material can be used for the cathodes disclosed herein, which may have the same or different formulations. The cathode active material and / or the electrically conductive material can be shaped into a planar surface and / or can be a granular solid. When the cathode active material, the electrically conductive material, and / or the electrolyte are granular, the particles can have any suitable shape, such as spheres, cubes, rectangular prisms, cones, pyramids, cylinders, rectangular prisms, hexagonal prisms, hemispheres, triangular prisms, pentagonal prisms, octagonal prisms, rings, octahedrons, and dodecahedrons, among others.

[0059] If the cathode includes a polymeric binder, the hygroscopic species or one of the active oxygen species can be added prior to preparation of the cathode active material, or the cathode active material can be combined with the polymeric binder after it is formed.

[0060] A polymer binder can be added to aid in forming a solid cathode from the cathode active material. Suitable polymer binders for the purposes of the present disclosure can include one or more of the following, among others: polycaprolactone, poly(acrylic acid), poly(methyl methacrylate), polytetrafluoroethylene, poly(vinylidene fluoride), polyacrylonitrile, poly(ethylene terephthalate), polyvinylpyrrolidone, poly(4-vinylpyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate. In certain embodiments, the polymer binder includes one or more of poly(ethylene oxide) or poly(vinylidene fluoride).

[0061] Alternatively, or in addition, the cathode can incorporate a plasticizer, which can be used to make the resulting cathode softer and more flexible. The plasticizer can include one or more of succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, sulfolane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitates, adipates, sebacates, and maleates, among others. In certain embodiments, the plasticizer can include succinonitrile.

[0062] Alternatively, or in addition, the cathode may incorporate one or more carboxylic acids. When present, the carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid. When the carboxylic acid is a polycarboxylic acid, it is optionally oxalic acid.

[0063] As illustrated in step 30 of Flowchart 20, the combined cathode materials, including the cathode active material and optionally including one or more of a conductive material, a polymeric binder, a plasticizer, and a carboxylic acid, are deposited onto a current collector to form the desired cathode.

[0064] The current collector may comprise any suitable and compatible conductive material. In some embodiments, the cathode current collector comprises one or more metals, such as alkaline earth metals, transition metals, rare earth metals, post-transition metals, and alkali metals. In some embodiments, the cathode current collector comprises at least one of aluminum, aluminum alloys, nickel, nickel alloys, duplex steels, and stainless steels. In one embodiment, the cathode current collector is a metal current collector comprising a metal or metal alloy further comprising one or more of molybdenum, titanium, and zirconium. In an alternative embodiment, the cathode current collector is an electrically conductive material comprising porous carbon in electrical contact with the cathode active material.

[0065] The cathode current collector can be solid or porous. When porous, the pore size of the cathode current collector can vary from about 500 nm to about 1 mm, with the separation distance between the pores being from about 10 μm to about 100 mm.

[0066] The cathode material, along with any additional conductive material, polymeric binder, and plasticizer, if present, can be applied to the current collector using any suitable application technique, for example, the combined cathode material can be cast into a film and deposited onto the desired current collector.

[0067] The resulting cathode can be incorporated into a battery 32, as shown in FIG. 3. The battery 32 typically comprises a cathode 34 according to the present disclosure. The cathode 34 can include the combined cathode materials 36 described above, such as the cathode active material applied to a cathode current collector 38. The anode 40 of the battery 32 includes an anode material 42 applied to an anode current collector 44. The cathode 34 and the anode 40 are typically separated by an electrolytic separator 46. The battery components are typically held within a battery case 48, which can enclose the battery components and keep them under a desired gas composition or atmosphere 50. Regardless of how the battery 32 is illustrated herein, it should be understood that the batteries of the present disclosure can take any conventional or suitable battery configuration, for example, by being formed as alternating plate or jelly roll, button cells, pouch cells, prismatic cells, cylindrical cells, flow cells, among others.

[0068] The anode 40 can include an active anode material. In some embodiments, the anode includes one or more of lithium, sodium, potassium, magnesium, calcium, vanadium, aluminum, zinc, silicon, graphite, graphene, porous carbon, activated carbon, silicon compounds, metal oxides, and combinations thereof. The active anode material can be present as a coating, foil, mesh or screen, or other interspersed anode component. Alternatively, or in addition, the active anode material can be introduced into the anode as a component or constituent compound. In some embodiments, the anode 40 can include a non-metal oxide as the active anode material. In some embodiments, the anode can include graphite. In some embodiments, the anode can include silicon, graphite, graphene, activated carbon, or a metal, or combinations thereof. When the anode includes a metal, the metal can be an alkali metal or an alkaline earth metal. In some embodiments, the anode includes a metal oxide. In some embodiments, the anode includes Li4Ti5O 12 , TiO2, TiNb2O7, Nb2O5, Li3VO4, H2Ti6O 13 , LiMnBO3, LiV 0.5 Ti 0.5 S2, Li3V2O5, Li 3+ x Metal oxides such as V2O5, Li3MoO4, Li5W2O7, or any combination thereof.

[0069] The anode active material 20 can be generated in situ by careful selection of the components of the electrochemical cell 10, such as the electrolyte 30 and / or further components thereof, and optionally by applying an anode current collector 26 to the electrochemical cell 10. The selection of the anode active material 20 is not particularly limited, provided that the material selected is capable of storing and releasing ions. For example, the anode active material 20 can be selected from a variety of metals, including alkali metals (such as lithium, sodium, and / or potassium), alkaline earth metals (such as magnesium and / or calcium), amphoteric metals (such as aluminum and / or zinc), metalloids (such as boron, germanium, arsenic, antimony, tin, tellurium, polonium, and / or silicon), metal complexes, inorganic carbon (such as graphite, graphene, graphene oxide, reduced graphene oxide, activated carbon, carbon nanotubes, and / or carbon dots), sulfur, sulfides (metal titanium disulfide MV 0.5 Ti 0.5 S2 (wherein M is a metal), metal sulfides (M2S), metal polysulfides (e.g., M2S2, M2S4, M2S6, M2S8), etc.), sulfur-containing compounds or materials (sulfates or organosulfur compounds (e.g., poly(sulfur-random-(1,3-diisopropenylbenzene)), sulfurized polyacrylonitrile), etc.), oxides (e.g., M x Ti5O 12 , TiO2, TiNb2O7, Nb2O5, M x VO4, H2Ti6O 13 , M x MnBO3, M x V2O5, M x MoO4, M x W2O7, M' 1-x M”O2, M' 1-w (M” x M'” y)O2 form of materials, and / or metal titanates), organic materials or compounds (e.g., truxenone, truxenone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives (e.g., 10-acetylphenothiazine, 10-[2-(2-methoxyethoxy)ethyl]-10H-phenothiazine), quinone, quinone derivatives (e.g., 2,2'-(2-vinylanthracene-9,10-diylidene) dimalononitrile, 2-vinylanthraquinone, anthraquinone-2,6-disulfonate, anthraquinone-1,8-di Sulfonates, anthraquinone-1-sulfonate, anthraquinone-1,5-disulfonic acid, 2,2'-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol)), diamine derivatives, phenazine, phenazine derivatives, quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, cyclohexane, cyclohexane derivatives, triazine, triazine derivatives, melamine, melamine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropenium derivatives, amide derivatives, amino acids, amino acid derivatives, violoncello viologen derivatives (e.g., ethyl viologen), nitroxide derivatives), organic groups (e.g., piperidine derivatives (e.g., 4-isothiocyanato-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-(2-iodoacetamido)-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6, 6-Tetramethylpiperidine 1-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-(2-chloroacetamido)-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6,6-tetramethyl-4-(2-propynyloxy)piperidine 1-oxyl, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-glycidyloxy-2,2,6,6-Tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl), pyrrolidine derivatives (e.g., 3-carboxy-2,2,5,5-tetramethylpiperidine 1-oxyl), methylpyrrolidine 1-oxyl, 16-DOXYL-stearic acid), imidazoline derivatives (e.g., 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl, 2-(4-nitrobiphenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl), 1,1-diphenyl-2-picrylhydrazyl, galvinoxyl), or any combination thereof.

[0070] In some embodiments, the anode active material can include one or more organic materials, as described above. When the anode active material includes an organic material, the organic material can be selected from any suitable organic compound or fragment of an organic compound, as described above. In one aspect, the anode active material includes an organic compound that includes heteroatoms such as boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine, and bromine, among others. Alternatively, or in addition, the anode active material can include an organic material that includes one or more aromatic groups.

[0071] Materials used as part of the cathode, except for the cathode active material, such as the electrically conductive material, polymer binder, plasticizer, carboxylic acid, etc., may also be part of the anode. When the anode includes an electrically conductive material along with one or more additional materials, polymer binders, and plasticizers, the electrically conductive material can be applied to the current collector using any suitable application technique. For example, the electrically conductive material can be cast into a film and then deposited on the desired current collector.

[0072] The anode 40 can include an anode material 42 that is an anode active material, where the anode active material is at least partially encapsulated at an exterior surface by a coating layer. The coating layer can vary in thickness from about 1 nm to about 1 μm. Preferably, the coating layer has a thickness of about 2 nm to about 500 nm. More preferably, the coating layer has a thickness of about 5 nm to about 200 nm. When present, the surface coating is optionally electrically insulating. By "electrically insulating" it is meant that the anode surface coating exhibits an electrical conductivity of 10-3 S / cm or less. Preferably, the anode surface coating exhibits an electrical conductivity of 10-5 S / cm or less. More preferably, the anode surface coating has an electrical conductivity of 10-7 S / cm or less. In one embodiment, the anode surface coating includes one or more of carbon, oxygen, nitrogen, boron, sulfur, silicon, tin, and selenium, where each element may be present as a compound or complex.

[0073] The anode current collector 44 can include a metal or metal alloy, such as copper, copper alloy, nickel, nickel alloy, duplex steel, stainless steel, silver, silver alloy, or any combination thereof. In some embodiments, the anode current collector 44 can be in contact with (e.g., coated with) an electrically conductive material, such as a porous carbon material that is or includes carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, microporous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, graphene nanoribbons, nitrogen-doped carbon, nitrogen-doped graphene, nitrogen-doped graphene oxide, and combinations thereof. In some embodiments, the electrically conductive material is in the form of particles, powder, paper, foam, fiber, sheet, disk, rod, foil, or any combination thereof.

[0074] In some embodiments, battery 32 may be a so-called "anode-less" battery, in which anode 40 includes anode current collector 44 but no anode material 42. In such embodiments, anode current collector 44 may be disposed on or in an electrolyte and / or separator, such that the electrolyte and / or separator are between cathode 34 and anode current collector 44. Alternatively, or in addition, anode current collector 44 may be or include the battery's outer housing (i.e., battery case 48).

[0075] The electrolytic separator 46 can be in contact with the cathode 34, or the separator 46 can be in contact with the electrolyte. If the electrochemical cell includes an anode, the separator 46 can be disposed between the cathode 34 and the anode 40. To avoid contact between the cathode 34 and the anode 40, between the cathode 34 and the anode current collector, between the cathode current collector and the anode 40, or between the cathode current collector and the anode current collector, the separator 46 can be longer in either or both of its width and length than either or both of the cathode and anode current collectors.

[0076] The electrolytic separator 46 may be disposed between the cathode 34 and the anode 40 and typically includes an electrolyte that provides ion transport within the battery 32 and acts as a conduit for ion transport through its interaction with the anode material 42 and the cathode material 36. The electrolytic separator 46 may be in contact with the electrolyte and may include a polymeric material such as a polymeric film such as polyethylene, polypropylene, poly(tetrafluoroethylene), or poly(vinyl chloride), among others. Typically, the polymeric film, when present, includes polypropylene and / or polyethylene. Alternatively, or in addition, the electrolytic separator 46 may include non-woven fibers (such as nylon, polyester, and glass, among others), glass, ceramic, or any combination thereof. In some embodiments, the separator includes glass fibers. In some embodiments, the separator includes a surfactant coating or treatment that enhances wettability of the liquid-based electrolyte.

[0077] The electrolyte 32 is a material that can act as a conduit for ion transport within the electrochemical cell of the battery by its interaction with the electrodes of the cell. The electrolyte 32 can be a liquid, solid, gel, or liquefied gas that includes an electrolyte material that is ionically conductive. The electrolyte can include an electrolyte solvent. The electrolyte can include water as the electrolyte solvent. The electrolyte material can be any of the following: -10 Ionic conductivity of 10 S / cm or more -1 The electrolyte material may be selected to have an electrical conductivity of 10 S / cm or less. -8 Ionic conductivity of 10 S / cm or more -3 More preferably, the electrolyte material has an electrical conductivity of 10 -6 Ionic conductivity of 10 S / cm or more -5 It has an electrical conductivity of less than S / cm.

[0078] When electrolyte 32 is present in the electrochemical cell as a solid, electrolyte 32 is optionally present in the form of a film, foil, tape, paper, sheet, layer, etc. Solid electrolyte materials include one or more of polymers, glasses, phosphates, fluorophosphates, carbonates, amines, borates, fluoroborates, halides, halates, oxohalides, oxides (e.g., MO2, MO3, MO2B2O5, MO, MOH, MO2, M2CO3, PO5, MPO4, M2M'3O7, where M is a metal or metalloid), perovskites, antiperovskites (e.g., MOBr, MOCl, MOHC1, MOHCl, where M is a metal or metalloid), LISICON type electrolytes (e.g., M 1+x M' x M” 2-x (PO4)3, M 2+2x M' 1-x M”O4, M (3+x) M' x V (1-x) O4, M (4-x) M' (1-x) P x O4, M 1+x+y M' x M” 2-x S y P 3-y O 12 , M 1+x M' x M” y Ti 2-x-y P3O 12 , M 1+x+3y M' x M” 2-x (Si y PO4)3, M 14 M'M"4O 16 , M 4-x M' x V x O4, where M is a metal or metalloid), garnets (e.g., M7M'3M"2O 12 , M 7-x M'3M” 2-x Nb x O 12 , M7M' 3-x M” x Zr 2-x Nb x O 12, M 6+x M'3M” 1+x Ta 1-x O 12 , where M is a metal or metalloid), sulfides (e.g., MPS5Cl, M 9.54 M' 1.74 P 1.44 S 11.7 Cl 0.3 , M 10 M'P2S 12 , M7PS6, M7P3S 11 , M 3.25 P 0.95 S4, M 3+x M' x P 1-x S4, where M is a metal or metalloid), thio-LISICON type electrolytes (e.g., M (4-x) M' (1-x) P x S4, where M is a metal or metalloid), oxynitrides, nitrides, etc. (LISICON is an acronym for lithium superionic conductor).

[0079] When the electrolyte 32 is present in the electrochemical cell as a solid, the electrolyte 32 is optionally present as a composition of solid particles. Suitable electrolyte materials can vary in average particle size from about 5 nm to about 30 μm and can exhibit an average pore size of about 0.1 nm to about 500 nm. Typically, suitable electrolyte materials have an average particle size or diameter less than about 30 μm. Preferably, the electrolyte material has an average particle size greater than about 10 nm and less than about 20 μm. More preferably, the electrolyte material has an average particle size greater than about 20 nm and less than about 10 μm. When the electrolyte 30 is present as a composition of solid particles, the electrolyte material can have an average pore size less than about 500 nm. Preferably, the electrolyte material has an average pore size greater than about 0.5 nm and less than about 200 nm. More preferably, the electrolyte material has an average pore size greater than about 1 nm and less than about 100 nm.

[0080] When the electrolyte 32 includes a liquefied gas, the liquefied gas can include one or more of methane (e.g., methane, fluoromethane, difluoromethane), ethane (e.g., ethane, fluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane), propane (e.g., propane, 2-fluoropropane), butane (e.g., butane, fluorobutane), ethylene, acetylene, propylene, carbon monoxide, and carbon dioxide. The liquefied gas can be produced from a gas below the condensation temperature of the gas at its critical pressure or above the vapor pressure of the gas at its critical temperature.

[0081] When the electrolyte 32 includes an organic liquid, the organic liquid may include one or more organic carbonates, ethers, esters, amides, halogenated liquids, nitriles, or ionic liquids.

[0082] When electrolyte 32 includes an organic carbonate, the organic carbonate can be, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, dipropyl carbonate, 4-vinyl-1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, diethyl 2,5-dioxahexanedioate, bis(2,2,2-trifluoroethyl)carbonate, 4-fluoro-1,3-dioxolan-2-one, dimethyl 2,5-dioxahexanedioate, or dibutyl carbonate, among others.

[0083] When electrolyte 32 includes an ether, the ether can be, for example, dimethoxyethane, dimethoxymethane, dimethyl ether, diethyl ether, ethylene glycol, ethylene glycol derivatives (diglyme, triglyme, tetraglyme), tetrahydrofuran, dioxolane, or dioxane, among others.

[0084] When electrolyte 32 includes an ester, the ester can be, for example, triethylborate, trimethylborate, tris(2,2,2-trifluoroethyl)borate, 2,4,6-trimethoxyboroxine, tributylborate, trihexylborate, or tripropylborate, among others.

[0085] When electrolyte 32 includes an amide, the amide can be, for example, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylpropionamide, diethylpropionamide, 2,2,2-trifluorodimethylacetamide, or dipropylacetamide, among others.

[0086] When the electrolyte 32 includes a halogenated liquid, the halogenated liquid can include, for example, a chlorinated liquid (such as dichloromethane) or a fluorinated liquid (such as, for example, fluoroethylene carbonate, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, difluoromethyl 2,2,3,3-tetrafluoropropyl ether, methyl 2,2,3,3,3-pentafluoropropyl ether, methyl 1,1,2,2-tetrafluoroethyl ether, bis(2,2,2-trifluoroethyl)ether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, or ethyl 1,1,2,2-tetrafluoroethyl ether, etc.).

[0087] When electrolyte 32 includes a solvent that is a nitrile, the nitrile can include, for example, acetonitrile, propionitrile, methoxyacetonitrile, 3-methoxypropionitrile, succinonitrile, glutaronitrile, adiponitrile, tetracyanoethylene, 3,3'-oxydipropionitrile, 3-ethoxypropionitrile, 1,3,6-hexanetricarbonitrile, 1,2,2,3-propanetetracarbonitrile, malononitrile, fumaronitrile, valeronitrile, acrylonitrile, tolunitrile, methoxybenzonitrile, or 3-butoxypropionitrile, among others.

[0088] When the electrolyte 32 includes an ionic liquid, the ionic liquid may be, for example, an imidazolium derivative (e.g., 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium bis(trifluoro-methanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoro-methanesulfonyl)imide, 2,3-dimethyl-1-propylimidazolium bis(trifluoro-methanesulfonyl), ... 1-Decyl-3-methyl-imidazolium tetrafluoroborate, 1-Decyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide, 1,3-Dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-Dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-Ethyl-3-methyl-imidazolium nitrate, 1-Ethyl-3-methyl-imidazolium trifluoromethanesulfonate, 1-Vinylimidazole bis(trifluoro -methanesulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazolium trifluoro-methanesulfonate, 3-ethyl-1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoro-borate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methyl-imidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium trifluoro-methanesulfonate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-(4-sulfobutyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1-methylimidazole bis(trifluoromethanesulfonyl)imide, 1-methyl-1H-imidazol-3-ium hexafluorophosphate, or 3,3'-(butane-1,4-diyl)bis(1-vinyl-3-imidazolium)bis(trifluoromethanesulfonyl)imide, etc.

[0089] When electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a pyrrolidinium derivative (such as 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium hexafluorophosphate, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium, bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoro-methanesulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, or 1-allyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, among others).

[0090] When the electrolyte 32 includes an ionic liquid, the ionic liquid may be, for example, a pyridinium derivative (e.g., 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium bis(trifluoro-methanesulfonyl)imide, 1-hexylpyridinium hexafluorophosphate, 1-ethyl-3-(hydroxymethyl-)pyridinium ethyl sulfate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium tetrafluoroborate ... The pyridinium hexafluorophosphate may be 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylpyridinium bis(trifluoro-methanesulfonyl)imide, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-methylpyridinium bis(trifluoromethanesulfonyl)imide, or 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium, etc.

[0091] When electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a piperidinium derivative, such as, for example, 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, or 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)-imide, among others.

[0092] When the electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, an ammonium derivative, such as, for example, methyltri-n-octylammonium bis(trifluoromethanesulfonyl)imide, ethyl(3-methoxypropyl)dimethylammonium bis(trifluoro-methanesulfonyl)imide, ethyl(2-methoxyethyl)dimethylammonium bis(trifluoromethane-sulfonyl)imide, butyltrimethylammonium bis(trifluoro-methane-sulfonyl)imide, tetrabutyl-ammonium trifluoromethanesulfonate, methyltri-n-octylammonium bis(trifluoro-methane-sulfonyl)imide, trimethyl-propylammonium bis(trifluoromethanesulfonyl)imide, tributyl-methylammonium bis(trifluoromethanesulfonyl)imide, butyltrimethylammonium bis(trifluoro-methanesulfonyl)imide, or tetrabutylammonium hexafluorophosphate, among others.

[0093] When the electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a phosphonium derivative, such as, for example, tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide, tributyl(2-methoxyethyl)-phosphonium bis(trifluoro-methane-sulfonyl)imide, tetrabutylphosphonium tetrafluoroborate, tetrabutyl-phosphonium hexafluorophosphate, or tributylmethyl-phosphonium bis(trifluoromethane-sulfonyl)imide, among others.

[0094] When electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a morpholinium derivative, or a sulfonium derivative (eg, triethylsulfonium bis(trifluoromethanesulfonyl)imide, etc.).

[0095] When electrolyte 32 is present in electrochemical cell 10 as a solution including a solvent and a solute dissolved in the solvent, the solute can include one or more ionic metal complexes, such as, among others, bis(nonafluorobutanesulfonyl)imides, metal (fluorosulfonyl)(trifluoro-methanesulfonyl)imides, metal trifluoromethanesulfonates, metal tetrafluoroborates, metal hexafluorophosphates, metal bis(fluorosulfonyl)imides, metal nonafluoro-1-butanesulfonates, metal bis(trifluoromethanesulfonyl)imides, metal tricyanomethanides, metal nitrates, metal halides, metal bis(oxalato)borates, metal difluoro(oxalato)borates, or metal perchlorates.

[0096] The electrolyte 32 may optionally include one or more additives, where the additives may be polymeric materials, plasticizers, phosphazenes, phosphates, sulfonyls, and carboxylic acids. When present, the polymeric materials may include, for example, one or more of polycaprolactone, poly(acrylic acid), poly(methyl methacrylate), polytetrafluoroethylene, poly(vinylidene fluoride), polyacrylonitrile, poly(ethylene terephthalate), polyvinylpyrrolidone, poly(4-vinylpyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, styrene-butadiene-rubber, sodium carboxymethyl cellulose, in any combination. In one embodiment, the polymeric materials include one of poly(ethylene oxide) or poly(vinylidene fluoride), among others.

[0097] When the additive includes a plasticizer, the plasticizer can include, for example, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, gamma-butyrolactone, sulfolane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitates, adipates, sebacates, maleates, or any combination thereof, among others.

[0098] When the additive includes a phosphazene, the phosphazene can include, for example, one or more of pentafluoro(phenoxy)cyclotriphosphazene, phosphorus nitrile chloride trimer, ethoxy(pentafluoro)cyclotriphosphazene, hexaphenoxycyclo-triphosphazene, or hexafluorocyclotriphosphazene, among others.

[0099] When the additive includes a phosphate, the phosphate can include, for example, one or more of tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphate, tris(2-butoxyethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(1H,1H,5H-octafluoropentyl) phosphate, 2-ethylhexyldiphenyl phosphate, triamyl phosphate, tri-o-cresyl phosphate, triallyl phosphate, tri-m-cresyl phosphate, triethyl phosphate, tri-p-cresyl phosphate, triphenyl phosphate, trimethyl phosphate, tris(2,2,2-trifluoroethyl) phosphate.

[0100] When the additive comprises a sulfonyl, the sulfonyl can comprise, for example, one or more of isopropyl methyl sulfone, dimethyl sulfone, dimethyl sulfite, dipropyl sulfone, 1,3-propane sultone, 3-methyl sulfolane, 1,4-butane sultone, tetrahydrothiophene 1,1-dioxide, 1,3,2-dioxathiolane 2,2-dioxide, 1,3,2-dioxathiolane 2-oxide.

[0101] When the additive includes a carboxylic acid, the carboxylic acid can be, for example, a monocarboxylic acid or a polycarboxylic acid. When the carboxylic acid is a polycarboxylic acid, it can be oxalic acid. When present, the carboxylic acid can be present in the electrolyte at a weight percentage between about 0.01% and about 30% by weight, preferably between about 0.1% and about 20% by weight, and more preferably between about 1% and about 10% by weight.

[0102] When electrolyte 32 is or includes a gel, the gel is typically obtained by mixing a suitable liquid electrolyte material (as described above) with a suitable solid electrolyte material (as described above). By suitable, it is meant that the liquid and solid electrolyte materials are physically and chemically compatible and, when mixed together in a selected ratio, are capable of obtaining an electrolyte gel that exhibits the desired consistency and electrolytic properties.

[0103] The electrolyte 32 preferably comprises a liquid, liquefied gas, and / or gel, since the discharge products 28 are typically easily dissolved by such electrolytes. In one embodiment, the electrolyte 30 comprises a solvent having a molecular weight that is less than about 300 g / mol, preferably less than about 200 g / mol, and more preferably less than about 100 g / mol, with solvents having smaller molecular weights being able to provide higher energy densities for the resulting electrochemical cell. For example, water has a molecular weight of 18.01 g / mol, dimethylacetamide 87.12 g / mol, dimethoxyethane 90.12 g / mol, dimethylcarbonate 90.08 g / mol, ethylene carbonate 88.06 g / mol, and dioxolane 74.08 g / mol.

[0104] In some embodiments, battery 32 can be referred to as a "mono-material" battery, in which the cathode active material disclosed herein can also be used as the electrolyte and / or separator. In such embodiments, the cathode active material that is not in contact with an electrically conductive material or current collector functions as the electrolyte and / or separator.

[0105] When the battery comprises a cathode and an electrolyte, the composition can have a weight ratio of cathode:electrolyte that can vary from 15:85 to 95:5. The composition ratio of cathode:electrolyte can be about 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5. Typically, the cathode electrolyte ratio is at least 15% by weight cathode. Preferably, the cathode electrolyte ratio is at least 30% by weight cathode. More preferably, the cathode electrolyte ratio is at least 45% by weight cathode.

[0106] When the battery includes a cathode and an electrolyte, the electrolyte can include an electrolytic solvent. In some embodiments, the solubility of the metal oxide of the cathode active material of the present disclosure in the electrolytic solvent is less than the solubility of the metal compound of the cathode active material of the present disclosure. In some embodiments, the ratio of the solubility of the metal oxide in the electrolytic solvent to the solubility of the metal compound in the electrolytic solvent is less than 0.5. Preferably, the solubility ratio is less than 0.3. More preferably, the solubility ratio is less than 0.1. In some embodiments, a portion or the total amount of the metal compound is dissolved in the electrolytic solvent before the operation of the battery, and the metal oxide is not dissolved in the electrolytic solvent. In some embodiments, when the metal compound is dissolved in the electrolytic solvent, the metal compound can also act as part of the electrolyte. In some embodiments, when the metal compound is dissolved in the electrolytic solvent, the electrolyte can flow by and through the cathode anyway.

[0107] Additionally, the electrolyte and / or atmosphere 50 of the electrolytic separator 46 may include a greenhouse gas. When present in the electrolyte, the greenhouse gas may be dissolved or liquefied greenhouse gas. The term "greenhouse gas" typically refers to a gas that absorbs and emits radiant energy in the thermal infrared range. Non-limiting examples of greenhouse gases include carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O), ozone (O3), sulfur hexafluoride (SF6), nitrogen trifluoride (NF3), hydrofluorocarbons, chlorofluorocarbons, and perfluorocarbons, among others. When the greenhouse gas is a halocarbon compound, it may include, for example, carbon tetrachloride (CCl4), tetrafluoromethane (CF4), or hexafluoroethane (C2F6), among others.

[0108] If the greenhouse gas is dissolved in the liquid electrolyte, the greenhouse gas can be introduced by a device comprising a pressure gauge, a gas inlet, a gas outlet, and a chemically resistant frit or foam immersed in the liquid electrolyte. The liquid electrolyte can be maintained under a greenhouse gas atmosphere at a pressure above standard atmospheric pressure for at least 10 seconds to at least 100 seconds, or longer.

[0109] Although the description of various embodiments herein is written in the context of a battery having a single cell, it should be understood that the same or similar principles may be applied to battery assemblies including two or more battery cells (i.e., battery packs, etc.), and such multiple battery assemblies should be understood to be within the scope of the present disclosure. EXAMPLES

[0110] Example 1. Fabrication of a high energy cathode Cathodes according to the present disclosure are fabricated and tested using the following procedure.

[0111] A 0.1MLiOH / 0.1MLiCl solution was prepared by dissolving lithium hydroxide (LiOH) monohydrate and lithium chloride (LiCl) hydrate in a 1:4 oxalic acid (OA)-methanol (MeOH) mixture under vigorous stirring. 100mg of carbon nanotubes (CNTs) were added to this solution under stirring, and the resulting mixture was sonicated for 10 minutes to interweave the carbon nanotubes. A solution of hydrogen peroxide (H2O2) and carbamide peroxide (CH6N2O3) was added dropwise to the reaction mixture at a temperature of 65°C under vigorous stirring. The molar ratio of the components of the reaction mixture was Н2O2:CH6N2O3:LiОН:LiCl=1:1:1:1.

[0112] The reaction mixture was then transferred to a Teflon-lined stainless steel autoclave and heated to 130° C. for 12 hours. The resulting precipitate was separated from the mother liquor by filtration, washed with acetone, and dried under vacuum at 110° C. for 24 hours. The collected material was then quickly transferred to an argon-filled glove box with minimal air exposure and mixed with porous carbon, succinonitrile as a plasticizer, and polytetrafluoroethylene as a polymer binder. The resulting mixture was cast onto a 316L stainless steel mesh current collector with a wire diameter of 0.05 mm and an aperture of 0.08 mm to yield a high-energy cathode.

[0113] The prepared cathode was placed in a coin cell (CR2032) with lithium metal foil as the anode and a polypropylene separator wetted with an electrolyte solution of 0.5 M bistrifluoro-methanesulfonimidate (LiTFSI) / 0.5 M lithium nitrate (LiNO3) in FEC-DMAC (1:1 volume ratio). The electrolyte solution was stored under a CO2 atmosphere at a pressure of over 5 bar for 7 days before use.

[0114] Example 2. Measurement of charge-discharge profile of a high energy battery The high energy battery prepared in Example 1 is subjected to charge-discharge cycles by applying a constant current to the battery. The high capacity performance of the battery is demonstrated in the plot of Figure 4, which is a plot of the charge-discharge profile of voltage (V vs. Li / Li+) versus specific capacity (mAh / g).

[0115] As shown in the figure, the battery of Example 1 has a current of 1 mA / cm 2 A specific capacity of over 500 mAh / g based on the weight of the cathode active material is achieved at a current density of 1.5 V. The plot also shows a high operating average discharge voltage of 3.41 V, with a clear discharge plateau at about 3.48 V. Furthermore, there is no sign of any oxygen reduction reaction at about 2.5 V, indicating that the cathode active material does not evolve gaseous oxygen during charging.

[0116] Example 3. Measurement of rechargeability of high energy batteries The high energy battery prepared in Example 1 is subjected to repeated discharge and recharge. As shown in FIG. 5, the battery has a current of 1 mA / cm 2 The high capacity was maintained for more than 15 cycles at a current density of 1.

[0117] Example 4. Comparison of specific capacitance The specific capacity of the cathode material prepared in Example 1 is compared with that of a conventional lithium-ion battery having a metal oxide cathode. As shown in FIG. 6, the cathode prepared as in Example 1 has a specific capacity of 100%. x Mn y Al z O2(B), LiNi x Co y Al z The results show that the lithium-ion batteries exhibit higher practical specific capacity than conventional lithium-ion batteries having metal oxide cathodes selected from LiO2 (C), LiCoO2 (D), LiNiO2 (E), LiMnO2 (F), LiMnPO4 (G), LiTiS2 (H), and Li2MnO3 (I) (values ​​for conventional battery compositions shown in graph taken from published literature) (see https: / / doi.org / 10.1016 / j.mattod.2014.10.040).

[0118] Example 5. Additional Selected Embodiments This section describes further aspects and features of the disclosed cathode active materials, cathodes, and batteries, presented without limitation as a series of paragraphs, some or all of which may be designated by alphanumeric characters for clarity and efficiency. Each of these paragraphs may be combined in any suitable manner with one or more of the other paragraphs and / or with the disclosure from elsewhere in this application. Some of the paragraphs below explicitly refer to and further qualify other paragraphs, and provide, without limitation, examples of some suitable combinations.

[0119] A1. M a R b wherein M is a metal, R is an atom, molecule, or radical, and a and b are independently non-zero positive real numbers; and M' x O y where M′ is a metal, and x and y are independently positive real numbers other than zero, and a metal oxide having an empirical formula of:

[0120] A2. The cathode active material of paragraph A1, wherein M and M' may be the same or different and are selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum.

[0121] A3. The cathode active material of paragraph A1, wherein at least a portion of the metal compound and a portion of the metal oxide, in combination, are M a M' b R c O d (wherein a, b, c, and d are each a non-zero positive real number and may be the same or different).

[0122] A4. The cathode active material of paragraph A1, wherein each R is independently an organic moiety or a heteroatom independently selected from nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron.

[0123] A5. The cathode active material of paragraph A4, wherein when R is an organic moiety, R is an organic moiety that contains one or more heteroatoms independently selected from nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron.

[0124] A6. The cathode active material of paragraph A1, wherein the metal oxide comprises a metal superoxide, a metal superoxide radical, and / or a metal peroxide.

[0125] B1. A cathode active material comprising a metal compound and a metal oxide, wherein the metal compound is M a R b wherein M is a metal, R is an atom, molecule, or radical, and a and b are independently non-zero positive real numbers, and the metal oxide has an empirical formula of M' x O y wherein M' is a metal, and x and y are independently non-zero positive real numbers, and wherein a metal compound and a metal oxide are in contact with each other; and an electrically conductive material, wherein one or both of the metal compound and the metal oxide are in contact with the electrically conductive material.

[0126] B2. The cathode material of paragraph B1, wherein M and M' may be the same or different and are selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum.

[0127] B3. The cathode material of paragraph B1, wherein the electrically conductive material comprises a porous carbon material.

[0128] B4. The cathode material of paragraph B3, wherein the porous carbon material is doped with one or more heteroatoms selected from boron, nitrogen, sulfur, phosphorus, fluorine, chlorine, and bromine.

[0129] B5. The cathode material of paragraph B1, wherein the electrically conductive material comprises one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

[0130] B6. The cathode material of paragraph B1, further comprising one or more of a polymeric binder, a plasticizer, and a carboxylic acid.

[0131] C1. A battery having a cathode, where the cathode is M a R b wherein M is a metal, R is an atom, molecule, or radical, and a and b are independently non-zero positive real numbers; and M' x O y and a metal oxide having an empirical formula of: where M' is a metal, and x and y are independently positive real numbers other than zero, wherein the metal compound and the metal oxide are in contact.

[0132] C2. The cell of paragraph C1, wherein the cathode evolves substantially zero gaseous oxygen during operation of the cell.

[0133] C3. The battery of paragraph C1, wherein the battery has a current density of 0.1 mA / cm 2 At or above that current density, the cathode exhibits a discharge specific capacity of at least 500 mAh / g based on the amount of cathode active material.

[0134] C4. The battery of paragraph C1, wherein the battery has a current density of 0.1 mA / cm 2 At current densities above Li / Li + The device can produce an average operating discharge potential of at least 3.0 V relative to the discharge potential of the battery.

[0135] C5. The battery of paragraph C1, wherein the battery is substantially rechargeable.

[0136] C6. The battery of paragraph C1, wherein the battery is operable at room temperature.

[0137] C7. The battery of paragraph C1, further comprising an anode, wherein the anode comprises an anode active material at least partially encapsulated by a coating layer on an exterior surface of the anode material, the coating layer comprising carbon and oxygen.

[0138] C8. The battery of paragraph C1, further comprising a liquid, solid, or semi-solid electrolyte, wherein the electrolyte comprises an electrolytic solvent.

[0139] C9. The battery of paragraph C8, wherein the solubility of the metal oxide in the electrolyte solvent is less than the solubility of the metal compound.

[0140] C10. The battery of paragraph C9, wherein the ratio of the solubility of the metal oxide in the electrolytic solvent to the solubility of the metal compound in the electrolytic solvent is less than 0.5.

[0141] C11. The battery of paragraph C1, further comprising a greenhouse gas that is liquefied and in contact with or dissolved in the electrolyte.

[0142] C12. The battery of paragraph C11, wherein the greenhouse gases include one or more of carbon dioxide (CO2), methane (CH4), sulfur hexafluoride (SF6), perfluorocarbon compounds, chlorofluorocarbon compounds, and hydrofluorocarbon compounds.

[0143] C13. The battery of paragraph C1, further comprising a separator, wherein the separator comprises a polymeric material.

[0144] C14. The battery of paragraph C1, further comprising a current collector comprising an alloy of one or more of molybdenum, titanium, and zirconium.

[0145] Advantages, Features, Benefits The cathode active materials of the present disclosure enable the fabrication of high energy cathodes for batteries that are economical, provide high discharge capacity, high discharge potential, and do not evolve oxygen during operation.

[0146] Selected batteries of the present disclosure have a 0.1 mA / cm 2 At current densities of 0.1 mA / cm or greater, the batteries of the present disclosure exhibit a discharge specific capacity of at least 100 mAh / g based on the amount of cathode active material. 2 At these current densities, discharge specific capacities of greater than 200 mAh / g, greater than 300 mAh / g, and greater than 500 mAh / g can be exhibited based on the amount of cathode active material.

[0147] The selected battery of the present disclosure is Li / Li + In some embodiments, the batteries of the present disclosure can exhibit an average operating discharge potential of greater than 1.0 V vs. Li / Li + Such cells can exhibit average operating discharge potentials of greater than 2.0 V, greater than 3.0 V, or even greater than 4.0 V vs. 0.1 mA / cm. 2 At current densities above Li / Li + The device can produce an average operating discharge potential of at least 3.0 V relative to the discharge potential of the battery.

[0148] All current densities presented in this disclosure are normalized by the planar area of ​​the cathode.

[0149] Selected batteries of the present disclosure may be substantially rechargeable. In one aspect of the present disclosure, a battery may be considered substantially rechargeable if it exhibits a cycle count greater than 100. Alternatively, or in addition, selected batteries of the present disclosure may be capable of operating efficiently at room temperature, which in one embodiment may be defined as 15°C to 30°C.

[0150] Cathodes made according to the methods of the present disclosure can operate with less than 1 mg / 1 mAh of gaseous oxygen evolution during the entire life of a battery containing the cathode. In some cases, the cathodes of the present disclosure exhibit substantially zero evolution of gaseous oxygen during operation.

[0151] The cathode active material of the present disclosure is Li / Li + It exhibits a standard redox potential of over 3.0 V relative to

[0152] The term "combination" or "combinations" means all types of combinations, starting from two of the elements, up to a plurality or all of such elements, unless otherwise specified.

[0153] The description of method steps, whether shown in the drawings or described in the specification, should not be considered as describing a particular order of method steps, unless an order is specifically provided. The order of such steps may differ from that shown and described, and / or two or more steps may occur simultaneously or with partial concurrence, unless otherwise noted.

[0154] The features and alternatives described in individual embodiments and examples can be freely combined with the features and alternatives of other examples and embodiments and can be specifically used to characterize the invention in the claims without necessarily implying other details of each embodiment or each example.

[0155] The disclosure disclosed above can encompass a number of different embodiments having independent utility. Although each of these has been disclosed in one or more exemplary forms, the specific embodiments disclosed and described herein should not be considered in a limiting sense, as numerous alternative forms are possible. To the extent that section headings are used within this disclosure, such headings are for organizational purposes only. The subject matter of the present disclosure includes all novel and unobvious combinations and subcombinations of the various elements, features, functions, and / or properties disclosed herein. The following claims specifically set forth certain combinations and subcombinations that are deemed novel and unobvious. Other combinations and subcombinations of features, functions, elements, and / or properties may be claimed in applications claiming priority from this or related applications. Such claims are also considered to be within the subject matter of the present disclosure, whether broader, narrower, equal, or different in scope than the original claims.

Claims

1. M a R b wherein M is a metal and each R is independently a R b is selected to be an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers; M x O y wherein M is the same metal in said metal compound, and x and y are independently positive real numbers other than zero; and a metal oxide having an empirical formula of: a cathode active material, the metal compound and the metal oxide being in contact with each other;

2. 2. The cathode active material of claim 1, wherein at least one R comprises one or more of hydrogen, nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron.

3. 2. The cathode active material of claim 1, wherein M is selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum.

4. 10. The cathode active material of claim 1, wherein at least one R is an organic moiety.

5. A cathode active material comprising a metal compound and a metal oxide, The metal compound is M a R b wherein M is a metal and each R is independently a R b is selected to be an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers, The metal oxide is M x O y wherein M is the same metal in said metal compound, and x and y are independently non-zero positive real numbers; a cathode active material in contact with the metal compound and the metal oxide; 1. An electrically conductive material comprising: an electrically conductive material, such that one or both of said metal compound and said metal oxide are in contact with said electrically conductive material.

6. 6. The cathode material of claim 5, wherein M is selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum.

7. 6. The cathode material of claim 5, wherein the electrically conductive material comprises a porous carbon material.

8. 8. The cathode material of claim 7, wherein the porous carbon material is doped with one or more heteroatoms selected from boron, nitrogen, sulfur, phosphorus, fluorine, chlorine, and bromine.

9. 8. The cathode material of claim 7, wherein the electrically conductive material comprises one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

10. 6. The cathode material of claim 5, further comprising one or more of a polymeric binder, a plasticizer, and a carboxylic acid.

11. M a R b wherein M is a metal and each R is independently a R b is selected to be an inorganic or organometallic compound or complex, and a and b are independently non-zero positive real numbers; M x O y wherein M is the same metal in said metal compound, and x and y are independently positive real numbers other than zero; and a metal oxide having an empirical formula of: A battery having a cathode comprising an active cathode material in contact with said metal compound and said metal oxide.

12. 0.1mA / cm 2 12. The battery of claim 11, exhibiting a discharge specific capacity of at least 500 mAh / g based on the amount of said cathode active material at or above a current density.

13. 0.1mA / cm 2 At a current density of Li / Li + 12. The battery of claim 11, capable of producing an average operating discharge potential of at least 3.0 V vs.

14. 12. The battery of claim 11, which is substantially rechargeable.

15. 12. The battery of claim 11, capable of operating at room temperature.

16. 12. The battery of claim 11 further comprising an anode, the anode comprising an active anode material that is at least partially encapsulated by a coating layer on an exterior surface of the anode material.

17. 12. The battery of claim 11, further comprising a liquid, solid, or semi-solid electrolyte, the electrolyte comprising an electrolytic solvent.

18. 20. The battery of claim 17, wherein the solubility of the metal oxide in the electrolytic solvent is less than the solubility of the metal compound.

19. 20. The battery of claim 18, wherein the ratio of the solubility of the metal oxide in the electrolytic solvent to the solubility of the metal compound in the electrolytic solvent is less than 0.

5.

20. 12. The battery of claim 11, further comprising a greenhouse gas that is liquefied and in contact with or dissolved in the electrolyte.

21. The greenhouse gas is carbon dioxide (CO 2 ), methane (CH 4 ), sulfur hexafluoride (SF 6 21. The battery of claim 20 comprising one or more of a perfluorocarbon compound, a chlorofluorocarbon compound, and a hydrofluorocarbon compound.

22. 12. The battery of claim 11, further comprising a separator, wherein the separator comprises a polymeric material.

23. 12. The battery of claim 11, further comprising a current collector comprising an alloy of one or more of molybdenum, titanium, and zirconium.

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