High energy cathodes and methods of making same

Abstract

A cathode active material includes a metal compound having the formula MaRb wherein M is a metal, each R is independently selected such that MaRb is an inorganic or organometallic compound or complex, and a and b are independent positive non-zero 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 independent positive non-zero real numbers; with the proviso that the metal compound and the metal oxide are contacted. The cathode can be economically incorporated into a battery that can provide high energy density.

Description

[0001] This application is a divisional application of a patent application with an international application date of February 11, 2022, entitled “High Energy Cathode and Its Manufacturing Method”, and national application number 202280014760.0 (international application number PCT / US2022 / 070632). Technical Field

[0002] The present disclosure relates to cathode active materials, methods of making cathode active materials, cathodes containing cathode active materials, and batteries incorporating such cathodes.

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application is a continuation-in-part of U.S. patent application serial number 17 / 175,267 filed on February 12, 2021, under 35 U.S.C. §120, and a continuation-in-part of U.S. patent application serial number 17 / 220,823 filed on April 1, 2021, under 35 U.S.C. §120, each of which is incorporated herein by reference for all purposes. Background Art

[0005] Batteries are ubiquitous in modern technology, used in a wide range of applications, from small batteries for industrial and medical devices to large batteries for electric vehicles and grid energy storage systems. Perhaps the most well-known and widely used battery technology today is the lithium-ion battery, which uses intercalated lithium compounds as an electrode material and employs lithium ions that shuttle between a cathode and an anode in an electrolyte pool. While lithium-ion batteries offer many advantages, they offer relatively low energy density and can require expensive materials to manufacture.

[0006] Lithium-air or lithium-oxygen batteries are considered the "next generation" lithium-ion battery technology and are known to outperform current lithium-ion batteries in many aspects, such as energy density and material cost. These batteries consume oxygen and produce reactive oxygen species that serve as cathode active materials. However, such batteries are prone to oxygen desorption at relatively low temperatures during operation and produce electrochemically irreversible byproducts that severely hinder the rechargeability of the battery. This oxygen desorption or dissociation of reactive oxygen species can also cause thermal runaway reactions in the battery.

[0007] There is a need for an improved cathode that incorporates improved cathode active materials and that can provide greater energy density, more economical manufacturing costs, and lower material costs while exhibiting better electrochemical reversibility and resistance to oxygen gas generation during use. Summary of the Invention

[0008] The present disclosure relates to cathode active materials and methods of making the same, as well as cathodes incorporating the cathode active materials, and batteries incorporating such cathodes.

[0009] In one example, the present disclosure relates to a cathode active material comprising a cathode active material having the empirical formula M a R b A metal compound wherein M is a metal; each R is independently selected such that M a R b is an inorganic or organometallic compound or complex; a and b are independent positive non-zero real numbers; and has the empirical formula M x O y wherein M is the same metal as in the metal compound, and x and y are independent positive non-zero real numbers; provided that the metal compound and the metal oxide are in contact.

[0010] In another example, the present disclosure relates to a cathode material comprising a cathode having the empirical formula M a R b A cathode active material of a metal compound of wherein M is a metal; each R is independently selected so that M a R b is an inorganic or organometallic compound or complex; and a and b are independent positive non-zero real numbers; and has the empirical formula M x O y wherein M is the same metal in the metal compound, and x and y are independent positive non-zero real numbers; such that the metal compound and the metal oxide are in contact; and a conductive material; such that one or both of the metal compound and the metal oxide are in contact with the conductive material.

[0011] In another example, the present disclosure relates to a battery comprising a cathode and an electrolyte, wherein the cathode comprises a cathode active material comprising a cathode having the empirical formula M a R b A metal compound wherein M is a metal; each R is independently selected such that M a R b is an inorganic or organometallic compound or complex; and a and b are independent positive non-zero real numbers; and has the empirical formula M x O y A metal oxide of , wherein M is the same metal in the metal compound, and x and y are independent positive non-zero real numbers; wherein the metal compound is in contact with the metal oxide.

[0012] 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 may be combined in yet other embodiments, further details of which can be seen with reference to the following description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is a flow chart of an illustrative method of making a cathode active material according to the present disclosure.

[0014] Figure 2 is a flow chart of an illustrative method of making a cathode according to the present disclosure.

[0015] Figure 3 is a semi-schematic diagram of an illustrative battery including a cathode made according to the present disclosure.

[0016] Figure 4 is a graph demonstrating the high specific capacity and high voltage performance of an illustrative battery incorporating cathode active materials according to the present disclosure, as described in Example 2.

[0017] Figure 5 is a graph illustrating the advantageous high rechargeability of an illustrative battery including a cathode active material according to the present disclosure, as described in Example 3.

[0018] Figure 6 is a bar graph comparing the specific capacity of selected battery cathode materials with cathodes prepared according to the present disclosure, as described in Example 4. DETAILED DESCRIPTION

[0019] The present disclosure provides high energy density cathode active materials that can be produced inexpensively and can be used to prepare cathodes for use in batteries. Selected cathodes prepared according to the present disclosure do not evolve substantially gaseous oxygen during operation of a battery including the cathode. In some aspects, a cathode prepared according to the present disclosure evolves gaseous oxygen at a rate of less than about 1 mg / 1 mAh during the complete life cycle of a battery including the cathode. As used herein, the term "complete life cycle of a battery" is intended to mean the life of a battery that is considered to have exceeded its normal useful life, which is assumed herein to be the point at which the battery first exhibits 80% of its original capacity.

[0020] When constructing the positive electrode of a battery cell, the cathode active material determines the difference in composition, and therefore the cathode active material determines the type of battery. For example, an LFP battery (deevs.com / news / 563506 / tesla-transition-ess-lfp-batteries) is a battery that includes LFP (lithium iron phosphate, LiFePO4) as its cathode active material. The cathode active material is responsible for supplying ions through the electrolyte and supplying electrons through an external circuit when the battery is charging, and is responsible for accepting ions through the electrolyte and accepting electrons through an external circuit when the battery is discharging. On the other hand, the anode active material is responsible for supplying ions through the electrolyte and supplying electrons through an external circuit when the battery is discharging, and is responsible for accepting ions through the electrolyte and accepting electrons through an external circuit when the battery is charging. Both the cathode active material and the anode active material participate in the electrochemical redox reaction by transporting ions through the electrolyte and / or transmitting electrons through an external circuit.

[0021] Any coating, natural or artificial layer, protective layer of any kind on the surface of the cathode active material or the anode active material that does not participate in the electrochemical redox reaction during charge and discharge of the battery should not be considered as part of the corresponding active material.

[0022] "Redox reaction" refers to a type of chemical reaction in which the oxidation state of participating atoms, molecules, free 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 commonly with one species undergoing oxidation and the other undergoing reduction.

[0023] "Current collector" refers to a component adjacent to an electrode that is configured to transfer electrical current from a fixed portion to a mobile portion of an electrochemical cell circuit, or vice versa. A current collector is a bridging component that collects the 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 a conductive material, i.e., a porous carbon material, which can be selected from carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, reduced graphene oxide, and graphene nanoribbons.

[0024] "Electrolyte" or "electrolyte solution" refers to a material that facilitates ion transport within an electrochemical cell. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes. Specifically, the electrolyte facilitates the movement of ions from the cathode to the anode during charging of the electrochemical cell and from the anode to the cathode during discharge.

[0025] As used herein, "room temperature" is any temperature within the range of air temperatures that most people prefer for indoor settings and feel comfortable wearing typical indoor clothing. More specifically, room temperature includes temperatures between 15°C and 30°C (or 59°F and 86°F).

[0026] "Substantially" means conforming more or less to a particular size, range, shape, concept, or other aspect modified by the term, such that the feature or component does not need to conform exactly. For example, an object that is "substantially cylindrical" means that the object resembles a cylinder, but may have one or more deviations from a true cylinder.

[0027] "Comprise," "include," and "have" (and variations thereof) are used interchangeably to mean inclusion but not necessarily limitation, and are open-ended terms that are not intended to exclude additional, non-recited elements or method steps.

[0028] Terms such as "first," "second," and "third" may be used to distinguish or identify various members of a group, etc., and are not intended to indicate sequential or numerical limitations.

[0029] All specifications regarding quantities and parts, particularly those used to define the present invention, indicate a tolerance of ±10%, for example: 11% means: from 9.9% to 12.1%, unless they refer to specific examples. For terms such as "a solvent", the word "a" should not be considered a numerical term, but rather as a general reference or pronoun, unless the context indicates otherwise.

[0030] Unless otherwise indicated, the term "combination" or "combinations" refers to all types of combinations starting from two of the relevant elements to a plurality or all of such elements.

[0031] Preparation of cathode active materials

[0032] Figure 1 Flowchart 10 of FIG. 1 illustrates an illustrative method for making a high-energy cathode active material according to the present disclosure. The method includes: preparing a solution of a hygroscopic substance and a reactive oxygen species at step 12 of flowchart 10; heating the solution at a temperature below about 400° C. for a time sufficient to form a precipitate of the cathode active material at step 14 of flowchart 10; collecting the precipitated cathode active material at step 16 of flowchart 10; and drying the collected cathode active material at a temperature below about 400° C. at step 18 of flowchart 10. The precipitate can be a derivative of the reactive oxygen species, a derivative of the reactive oxygen species combined with a hygroscopic substance, or a reactive oxygen species combined with a hygroscopic substance.

[0033] The hygroscopic material used to prepare the cathode active material can be any hygroscopic material that forms a precipitate when heated in solution with an appropriate reactive oxygen species. Typically, a hygroscopic material is a compound or substance that attracts water from its environment by chemical reaction, by binding water of hydration, or by physical adsorption. In particular, the hygroscopic material can be substantially free of transition metals. Particularly useful hygroscopic materials may include one or more ionic materials and / or one or more organic materials.

[0034] Where the hygroscopic substance comprises one or more ionic materials, the ionic materials may comprise one or more ionic compounds, wherein the ionic compounds are typically salts, and more typically chlorides, bromides, pentoxides, sulfides and / or sulfates. The ionic material may also be an acid capable of donating protons.

[0035] In the case where the hygroscopic substance comprises 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 the group consisting of: trimerized indanone, trimerized indanone 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, cyclopropene derivatives, and amide derivatives.

[0036] Examples of the selection of hygroscopic materials for use in the present disclosure may include CH 14 Cl4N4 (benzenetetramine tetrahydrochloride), C6H 16 O 14 (hexaketocyclohexane octahydrate), C8H6O4 (terephthalic acid), LiOH (lithium hydroxide), NaOH (sodium hydroxide), C 13 H 22 NO3 (tetramethylpiperidin-1-oxy-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 (bisulfate), HClO3 (chloric acid), C7H6O2 (benzoic acid), C2HF3O2 (trifluoroacetic acid), HBO (boric 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 23N (dicyclohexylamine), C2H6N (dimethylamine), C6H5SH (thiophenol), C6H2O6 (rose bengal acid dihydrate), C 16 H8O6 (anthraquinone-2,3-dicarboxylic acid), C6H2Cl2O4 (chloroaniline) and C 22 H 24 N4O4 (naphthalene diimide), etc.

[0037] The reactive oxygen species may be any species that includes one or more reactive oxygen moieties. For example, the reactive oxygen species may include one or more reactive oxygen moieties such as peroxides, superoxides, superoxide radicals, hydroxyl radicals, peroxyl radicals, perhydroxyl radicals, hydroperoxyl radicals, alkoxyl radicals, singlet oxygen, hypochlorous acid, and α-oxygen. In one embodiment of the present disclosure, the reactive oxygen species includes at least one peroxide moiety. The reactive oxygen species may be selected from Li2O2 (lithium peroxide), H2O2 (hydrogen peroxide), HOCl (hypochlorous acid), O2* - (superoxide radical), NaO2 (sodium superoxide), NO* (nitroxyl radical), C6H5O* (phenoxyl radical) and 1 One or more of O2 (singlet oxygen), etc.

[0038] Upon reaction, the reactive oxygen species is typically converted to a reactive oxygen species derivative. A reactive oxygen species derivative can be any substance derived from the reactive oxygen species and is distinguished from the reactive oxygen species in that the reactive oxygen species derivative no longer includes a reactive oxygen moiety, such as peroxide, superoxide, superoxide radical, hydroxyl radical, peroxyl radical, perhydroxyl radical, hydroperoxyl radical, alkoxyl radical, singlet oxygen, hypochlorous acid, and α-oxygen.

[0039] Any method for preparing a solution of a hygroscopic substance and a reactive oxygen species is a suitable method for the purposes of the method of Scheme 10. For example, preparing a solution of one or more hygroscopic substances and one or more reactive oxygen species may include adding each of the desired hygroscopic substances and reactive oxygen species to a single solution to form the desired combined solution. Alternatively, one or both of the hygroscopic substance and the reactive oxygen species may be first dissolved in a solvent, and then the hygroscopic substance solution and the reactive oxygen species solution may be mixed to form the combined solution, or both may be added to an existing solution to form the combined solution.

[0040] The resulting solution is then heated at a temperature below about 400°C but high enough to cause the formation of a precipitate of the desired cathode active material. The heating temperature is preferably less than about 300°C, and more preferably less than about 200°C. It should be understood that it is generally not possible to heat the solution to a temperature above the boiling point of the solution under standard conditions, so the combined solution should be transferred to a sealed container or autoclave for heating under elevated pressure. During the heating process, the atmosphere of the sealed container or autoclave can be replaced with high-purity oxygen.

[0041] When the combined solution has been heated for a sufficient period of time to form a precipitate of the cathode active material, the cathode active material can be collected. The cathode active material precipitate can be collected using any suitable separation method, but the precipitate mixture is typically 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 under an inert gas atmosphere, typically at a temperature below about 400°C. The drying temperature is preferably less than about 300°C, and more preferably less than about 200°C.

[0042] The collected and dried cathode active material should be tested or further processed under dry conditions, such as at a relative humidity of less than about 25%. Preferably, such processing will be carried out in a drying chamber.

[0043] cathode active material

[0044] In the preparation process of the cathode active material, the hygroscopic substance and the reactive oxygen species typically undergo a reaction to produce a cathode active material comprising one or more new materials. In one aspect of the present disclosure, the combination of the hygroscopic substance and the reactive oxygen species produces a cathode active material comprising 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 in the case where the cathode active material comprises a heterogeneous mixture. Alternatively or additionally, the metal compound and the metal oxide can be combined with each other in a complex, cluster or crystalline, quasi-crystalline or amorphous matrix. In one embodiment, the one or more hygroscopic substances are metal compounds. Typically, the cathode active material comprises a metal compound and a metal oxide such that the metal compound and the metal oxide are in contact.

[0045] The metal compound of the cathode active material can be represented by the empirical formula M a R b Description, wherein M is a metal, and each R moiety is independently selected from any suitable atom, molecule or radical such that M a R bis an inorganic or organometallic compound or complex. Each R moiety may independently have a formal oxidation state of -1, -2, or -3. Typically, each R moiety has a formal oxidation state of -1. The values ​​of a and b are independently positive non-zero real numbers. Each R may be a fragment or substituent of a larger compound.

[0046] In one embodiment, one or more R moieties may independently be or include one or more of hydrogen, nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron. Alternatively or additionally, each R may independently be an inorganic moiety or an organic moiety.

[0047] Each R moiety that is an inorganic moiety can be selected from hydrides, halides, oxides, hydroxides, chlorates, sulfides, sulfates, metaborate, thiocyanates, amides, nitrides, azides, and the like.

[0048] Each R part as organic moiety optionally also includes one or more heteroatoms independently selected from nitrogen, chlorine, bromine, fluorine, sulphur, phosphorus and boron.In certain embodiments, each R as organic moiety does not include alkali metal, alkaline earth metal or transition metal.In certain embodiments, R part can comprise carbon, hydrogen or oxygen.In certain embodiments, R part is an organic moiety with 1-6 carbon.

[0049] Non-exclusive examples of suitable R moieties for use in the present disclosure can include -H (hydride), -OH (hydroxyl), -COOH (carboxyl), -CH (alkyne), -CH2 (alkene), -CHO (aldehyde), -CO- (carbonyl), -COO- (ester), -O- (ether), NH2- (amine), -CN (nitrile), alkyl halides, oxyhalides, alkanes, alkenes, alkynes, arenes, phenyls, thiols, thialdehydes, sulfides, sulfoxides, sulfones, ketones, amides, alkyl halides, methoxides, ethoxides, epoxides, phenolates, nitrides, nitrosos, quinones, imines, imides, azides, lactates, phosphates, formates, and cyanates, among others.

[0050] Examples of the metal compound of the cathode active material may include 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 18N (2,2,6,6-tetramethylpiperidinium lithium), LiC3H5O (lithium lactate), Li3PO4 (lithium phosphate), LiCHO2 (lithium formate), LiBH4 (lithium borohydride) LiC 12 H 22 N (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 rhodonate), LiC 16 H8O6 (lithium anthraquinone dicarboxylate), Li2C6H4O4 (lithium dihydroxybenzoquinone) and LiC 22 H 24 N4O4 (lithium naphthalimide), etc.

[0051] The metal oxide of the cathode active material can be represented by the empirical formula M′ x O y wherein M' is a metal which may be the same as or different from M of the metal compound, and wherein x and y are each a positive non-zero 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.

[0052] 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.

[0053] The resulting cathode active material may include at least a portion of a metal compound and at least a portion of a metal oxide, which form clusters from a combination perspective. In one aspect of the present disclosure, the resulting clusters may be represented by the empirical formula M a M′ b R c O d , to describe, where each of a, b, c and d is a positive non-zero real number that can be the same or different.

[0054] The resulting cathode active material composition may include a ratio of metal compound:metal oxide that may vary from 5:95 to 75:25 by weight. a R bThe 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 contains at least 25 wt% of the metal oxide. Preferably, the cathode active material contains at least about 50 wt% of the metal oxide. More preferably, the cathode active material contains at least about 75 wt% of the metal oxide.

[0055] The average particle size of the cathode active material can vary from about 5 nm to about 50 μm, exhibiting 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.

[0056] In some embodiments, the cathode active material is at least partially surrounded by a coating on its outer surface. The thickness of the coating can vary between about 1 nm and about 1 μm. Preferably, the coating has a thickness of about 2 nm to about 500 nm. More preferably, the coating has a thickness of about 5 nm to about 200 nm. When present, the coating may comprise carbon and oxygen.

[0057] High-energy cathode

[0058] The cathode active materials disclosed herein can be used to prepare high energy cathodes, such as Figure 2 As shown in flowchart 20, the method for manufacturing a cathode for a battery includes: preparing a solution of a hygroscopic material and a reactive oxygen material 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 a 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 a conductive material, a polymer binder, a plasticizer, and a carboxylic acid in step 28 of flowchart 20; and depositing the combined cathode material on a current collector to produce a cathode in step 30 of flowchart 20.

[0059] Steps 21 , 22 , 24 and 26 of flowchart 20 are directly analogous to corresponding steps 12 , 14 , 16 and 18 of flowchart 10 described above.

[0060] As described in step 28 of flow chart 20, the cathode active material can be combined with one or more of a conductive material, a polymer binder, a plasticizer, and a carboxylic acid. Typically, the cathode active material is combined with the conductive material. Alternatively, the cathode active material can be further combined with one or more of a polymer binder, a plasticizer, and a carboxylic acid.

[0061] Where the cathode comprises a conductive material, it may be added to one of the hygroscopic species or reactive oxygen species prior to preparation of the cathode active material, or the cathode active material may be combined with the conductive material after its formation. Typically, the cathode active material is in contact with the conductive material.

[0062] In the case where 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 are in contact with a conductive material.

[0063] In the case where the cathode includes a cathode active material and a conductive material, the cathode composition can include a ratio of cathode active material to conductive material that can vary from 20:80 to 99:1 by weight. The composition ratio of cathode active material to 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 contains at least 20 wt% cathode active material. Preferably, the cathode composition can contain at least 40 wt% cathode active material. More preferably, the cathode composition can contain at least 60 wt% cathode active material.

[0064] Any conductive material that promotes the cathode performance of the result is a suitable conductive material for the purpose of the present invention. In certain embodiments, the conductive material includes a porous carbon material, which 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 conductive material can have any suitable and compatible physical form, such as particles, powder, paper, foam, fiber, sheet, disk, rod, foil or any combination thereof. In the case where the cathode includes a porous carbon material, carbon nanotubes and / or carbon nanofibers, carbon nanotubes are particularly preferred due to their high aspect ratio and durability.

[0065] In one embodiment, the conductive material comprises a porous carbon material having particles having 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 conductive material has an average particle size or diameter of less than about 50 μm. Preferably, the conductive material has an average particle size greater than about 50 nm and less than about 50 μm. More preferably, the conductive material has an average particle size greater than about 500 nm and less than about 50 μm. Typically, the conductive material has an average pore size less than about 1 μm. Preferably, the conductive material has an average particle size greater than about 1 nm and less than about 500 nm. More preferably, the conductive material has an average particle size greater than about 5 nm and less than about 200 nm.

[0066] In some embodiments, the average particle size or diameter of the cathode active material and the conductive material are inversely related. 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 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 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.

[0067] In one embodiment, the step of combining the cathode active material with the 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. It is preferred that the cathode comprises a porous carbon material doped with nitrogen and / or fluorine, and nitrogen is particularly preferred because they allow lower charge transfer resistance. When present, the porous carbon material can include one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide and graphene nanoribbons.

[0068] Any suitable conductive material can be used for the cathode disclosed in the present invention, and it can have the same or different formulas.Cathode active material and / or conductive material can be shaped as a flat surface, and / or a granular solid.When cathode active material, conductive material and / or electrolyte are particles, the particles can have any suitable shape, including sphere, cube, cuboid, cone, pyramid, cylinder, rectangular prism, hexagonal prism, hemisphere, triangular prism, pentagonal prism, octagonal prism, ring, octahedron and dodecahedron etc.

[0069] Where the cathode includes a polymeric binder, it can be added to one of the hygroscopic species or the reactive oxygen species prior to preparation of the cathode active material, or it can be combined with the polymeric binder after the cathode active material is formed.

[0070] A polymer binder may be added to assist in forming a solid cathode from the cathode active material. Suitable polymer binders for the purposes of the present disclosure may include one or more of polycaprolactone, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinyl pyrrolidone, poly-4-vinyl pyridine, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, and the like. In a particular embodiment, the polymer binder includes one of polyethylene oxide or polyvinylidene fluoride.

[0071] Alternatively or additionally, the cathode can be combined with 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, trimellitate, adipate, sebacate, and maleate, etc. In a particular embodiment, the plasticizer can include succinonitrile.

[0072] Alternatively or additionally, 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 may optionally be oxalic acid.

[0073] As depicted in step 30 of flow chart 20, a combined cathode material comprising a cathode active material and optionally one or more of a conductive material, a polymer binder, a plasticizer, and a carboxylic acid is deposited on a current collector to form the desired cathode.

[0074] 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 steel, and stainless steel. In one embodiment, the cathode current collector is a metal current collector comprising a metal or metal alloy comprising one or more of molybdenum, titanium, and zirconium. In another embodiment, the cathode current collector is a conductive material comprising porous carbon in electrical contact with the cathode active material.

[0075] The cathode current collector can be solid or perforated. When perforated, the cathode current collector can have a pore size ranging from about 500 nm to about 1 mm, with the pores spaced apart by a distance of about 10 μm to about 100 mm.

[0076] The cathode material, along with the additional conductive material, polymer 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.

[0077] The resulting cathode can be incorporated into a battery 32, such as Figure 3 . The battery 32 generally includes a cathode 34 according to the present disclosure. The cathode 34 may include a combined cathode material 36 as described above, which includes a 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 anode 40 are generally separated by an electrolytic separator 46. The battery components are generally retained within a battery casing 48, which surrounds the battery components and can maintain the battery components under a desired gas composition or atmosphere 50. It should be understood that regardless of how the battery 32 is illustrated herein, the batteries of the present disclosure can be configured in any conventional or suitable battery configuration, such as by being formed as a button cell, a pouch cell, a prismatic cell, a cylindrical cell, a flow cell, an alternating plate format, an egg roll format, or the like.

[0078] Anode 40 may include an anode active 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 anode active material may be present as a coating, foil, mesh or grid, or other discrete anode component. Alternatively or additionally, the anode active material may be incorporated into the anode as a component element or component compound. In some embodiments, anode 40 includes a non-metallic oxide as the anode active material. In some embodiments, the anode may include graphite. In some embodiments, the anode may include silicon, graphite, graphene, activated carbon, or a metal, or a combination thereof. In the case where the anode includes a metal, the metal may be an alkali metal or an alkaline earth metal. In some embodiments, the anode includes a metal oxide. In some embodiments, the anode includes a metal oxide, such as Li4Ti5O 12 , TiO2, TiNb2O7, Nb2O5, Li3VO4, H2Ti6O 13 、LiMnBO3、LiV 0.5 Ti 0.5 S2, Li3V2O5, Li3+xV2O5, Li3MoO4, Li5W2O7 or any combination thereof.

[0079] The anode active material 20 can be generated in situ by carefully selecting components of the electrochemical cell 10, such as the electrolyte 30 and / or additional components thereof, and optionally by applying the anode current collector 26 to the electrochemical cell 10. The choice of the anode active material 20 is not particularly limited, as long as the selected material can store and release ions. For example, the anode active material 20 can be an alkali metal (such as lithium, sodium and / or potassium), an alkaline earth metal (such as magnesium and / or calcium), an amphoteric metal (such as aluminum and / or zinc), a metalloid (such as boron, germanium, arsenic, antimony, tin, tellurium, polonium and / or silicon), a metal complex, an inorganic carbon (such as graphite, graphene, graphene oxide, reduced graphene oxide, activated carbon, carbon nanotubes and / or carbon dots), sulfur, a sulfide (such as metal titanium disulfide MV 0.5 Ti 0.5 S2, wherein M is a metal, a metal sulfide (M2S), a metal polysulfide (e.g., M2S2, M2S4, M2S6, M2S8)), a sulfur-containing compound or material (such as a sulfate or an organosulfur compound (e.g., poly(sulfur-random-(1,3-diisopropenylbenzene)), sulfurized polyacrylonitrile)), an oxide (e.g., in the form of 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 materials and / or metal titanates), organic materials or compounds (e.g., trimerized indanone, trimerized indanone 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)dicarbonitrile, 2-vinylanthraquinone, anthraquinone-2,6-disulfonate, anthraquinone-1,8-disulfonate, anthraquinone-1-sulfonate, anthraquinone-1,5-disulfonic acid, 2,2′-(2-vinylanthracene-9,10-diylidene)bis(1,3-disulfide)), diamine derivatives, phenazine, phenazine derivatives , quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, cyclohexane, cyclohexane derivatives, triazine, triazine derivatives, melamine, melamine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropene derivatives, amide derivatives, amino acids, amino acid derivatives, viologen, viologen derivatives (e.g., ethyl viologen), nitrogen oxide derivatives), organic free radicals (e.g., piperidine derivatives (e.g., 4-isothiocyanato-2,2,6,6-tetramethylpiperidinyl-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidinyl-1-oxyl, 4-(2-iodoacetylamino)-2,2,6,6-tetramethylpiperidinyl-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidinyl-1-oxyl, 4- Methacryloxy-2,2,6,6-tetramethylpiperidine-1-oxy, 2,2,6,6-tetramethylpiperidine-1-oxy, 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxy, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxy, 4-(2-chloroacetylamino)-2,2,6,6-tetramethylpiperidine-1-oxy, 2,2,6,6-tetramethyl-4-(2-propynyloxy)piperidine-1-oxy, 2,2,6,6-tetramethylpiperidine-1-oxy, 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-oxyglycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxy, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidinyl-1-oxyl, bis(2,2,6,6-tetramethyl-4-piperidinyl-1-oxy)sebacate, 4-methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl), pyrrolidine derivatives (e.g., 3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl, 16-DOXYL stearic acid), imidazoline derivatives (e.g., 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl, 2-(4-nitrophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl), 1,1-diphenyl-2-picrylhydrazyl, galvinoxyl free radical), or any combination thereof.

[0080] In certain embodiments, the anode active material may include one or more organic materials as described above. In the case where the anode active material includes an organic material, the organic material may be selected from any suitable organic compound as described above or a fragment of an organic compound. 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. Alternatively or additionally, the anode active material may include an organic material containing one or more aromatic groups.

[0081] Materials used as part of the cathode other than the cathode active material, such as conductive materials, polymer binders, plasticizers, carboxylic acids, can also be part of the anode. In the case where the anode includes a conductive material and one or more additional materials, a polymer binder, and a plasticizer, the conductive material can be applied to the current collector using any suitable application technique. For example, the conductive material can be cast into a film and then deposited onto the desired current collector.

[0082] Anode 40 may include an anode material 42 as the anode active material, wherein the anode active material is at least partially surrounded by a coating on the outer surface. The thickness of the coating may vary from about 1 nm to about 1 μm. Preferably, the coating has a thickness of about 2 nm to about 500 nm. More preferably, the coating has a thickness of about 5 nm to about 200 nm. When present, the surface coating may optionally be electrically insulating. "Electrically insulating" means that the anode surface coating exhibits a resistance of less than or equal to 10 -3 S / cm. Preferably, the anode surface coating exhibits an electrical conductivity less than or equal to 10 -5 More preferably, the anode surface coating has an electrical conductivity of less than or equal to 10 -7 In one embodiment, the anode surface coating comprises one or more of carbon, oxygen, nitrogen, boron, sulfur, silicon, tin, and selenium, wherein each element may be present as a compound or a complex.

[0083] Anode current collector 44 may 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, anode current collector 44 may be in contact with a conductive material (e.g., coated with a conductive material), with the bottom material being a porous carbon material, which 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 conductive material is in the form of particles, powder, paper, foam, fiber, sheet, disk, rod, foil, or any combination thereof.

[0084] In some embodiments, the battery 32 may be a so-called "anode-less" battery, in which the anode 40 includes an anode current collector 44, but is devoid of anode material 42. In such embodiments, the anode current collector 44 may be disposed on or in the electrolyte and / or separator such that the electrolyte and / or separator is between the cathode 34 and the anode current collector 44. Alternatively or additionally, the anode current collector 44 may be or include the housing of the battery (i.e., battery housing 48).

[0085] The electrolytic separator 46 may be in contact with the cathode 34, or the separator 46 may be in contact with the electrolyte. In the case where the electrochemical cell includes an anode, the separator 46 may 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, one or both of the width and length of the separator 46 may be greater than one or both of the cathode current collector and the anode current collector.

[0086] Electrolysis separator 46 can be arranged between cathode 34 and anode 40, and generally includes electrolyte to provide ion transport in battery 32, and acts as a conduit for ion transport by its interaction with anode material 42 and cathode material 36. Electrolysis separator 46 can be in contact with electrolyte, and can include polymer material, such as polymer film, such as polyethylene, polypropylene, polytetrafluoroethylene or polyvinyl chloride etc. Usually, when present, polymer film includes polypropylene and / or polyethylene. Alternatively or additionally, electrolysis separator 46 can include non-woven fibers (such as nylon, polyester and glass etc.), glass, ceramic or its any combination. In some embodiments, separator includes glass fiber. In some embodiments, separator includes surfactant coating or treatment layer, to enhance the wettability of liquid-based electrolyte.

[0087] The electrolyte 32 is a material that can act as a conduit for ion transport within the electrochemical cell of the battery through its interaction with the electrodes of the cell. The electrolyte 32 can be a liquid, solid, gel, or liquefied gas comprising an ionically conductive electrolyte material. The electrolyte can include an electrolytic solvent. The electrolyte can include water as an electrolytic solvent. The electrolyte material can be selected to have a conductivity greater than or equal to 10 -10 S / cm and an ionic conductivity less than or equal to 10 -1 S / cm. Preferably, the electrolyte material has a conductivity greater than or equal to 10 -8 S / cm and the ionic conductivity is less than or equal to 10 -3 More preferably, the electrolyte material has a conductivity greater than or equal to 10 -6 S / cm and the ionic conductivity is less than or equal to 10 -5The conductivity is S / cm.

[0088] Where the electrolyte 32 is present in the electrochemical cell as a solid, the electrolyte 32 may optionally be present in the form of a film, foil, tape, paper, sheet, layer, etc. The solid electrolyte material may include one or more polymers, glasses, phosphates, fluorophosphates, carbonates, amines, borates, fluoroborates, halides, halogenates, oxyhalides, oxides (e.g., MO2, M2O3, M2B2O5, M2O, MOH, M2O2, M2CO3, P2O5, MPO4, M2M'3O7, where M is a metal or metalloid), perovskites, antiperovskites (e.g., M3OBr, M3OCl, M2OHBr, M2OHCl, 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 Si y P 3-y O 12 、M 1+x M' x M” y Ti 2-x-y P3O 12 、M 1+x+3 yM' 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), garnet (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 O12 , where M is a metal or metalloid), sulfides (e.g., M6PS5Cl, 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, wherein M is a metal or metalloid), sulfide crystalline lithium superionic conductor (thio-LISICON) (e.g., M (4-x) M' (1-x) P x S4, where M is a metal or metalloid), oxynitride, nitride, etc. (LISICON is the acronym for lithium superionic conductor).

[0089] In the case where the electrolyte 32 is present in the electrochemical cell as a solid, the electrolyte 32 may optionally be present as a composition of solid particles. The average particle size of a suitable electrolyte material may vary from about 5 nm to about 30 μm and may exhibit an average pore size of about 0.1 nm to about 500 nm. Typically, the average particle size or diameter of a suitable electrolyte material is less than about 30 μm. Preferably, the average particle size of the electrolyte material is greater than about 10 nm and less than about 20 μm. More preferably, the average particle size of the electrolyte material is greater than about 20 nm and less than about 10 μm. In the case where the electrolyte 30 is present as a composition of solid particles, the average pore size of the electrolyte material may be less than about 500 nm. Preferably, the average pore size of the electrolyte material is greater than about 0.5 nm and less than about 200 nm. More preferably, the average pore size of the electrolyte material is greater than about 1 nm and less than about 100 nm.

[0090] In the case where the electrolyte 32 includes a liquefied gas, the liquefied gas may 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 may be generated from the gas at or below the condensation temperature of the gas and at the critical pressure, or at or above the vapor pressure of the gas and at the critical temperature.

[0091] Where the electrolyte 32 comprises an organic liquid, the organic liquid may comprise one or more organic carbonates, ethers, esters, amides, halogenated liquids, nitriles, or ionic liquids.

[0092] When the electrolyte 32 includes an organic carbonate, the organic carbonate may be, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, dipropyl carbonate, 4-vinyl-1,3-dioxolane-2-one, 4-chloro-1,3-dioxolane-2-one, diethyl 2,5-dioxadipic acid, bis(2,2,2-trifluoroethyl) carbonate, 4-fluoro-1,3-dioxolane-2-one, dimethyl 2,5-dioxadipic acid, or dibutyl carbonate, among others.

[0093] In the case where the electrolyte 32 includes an ether, the ether may be, for example, dimethoxyethane, dimethoxymethane, dimethyl ether, ethyl ether, ethylene glycol, ethylene glycol derivatives (diglyme, triglyme, tetraglyme), tetrahydrofuran, dioxolane, dioxane, or the like.

[0094] Where the electrolyte 32 includes an ester, the ester may be, for example, triethyl borate, trimethyl borate, tris(2,2,2-trifluoroethyl)borate, 2,4,6-trimethoxyboroxy, tributyl borate, trihexyl borate, or tripropyl borate, among others.

[0095] Where the electrolyte 32 includes an amide, the amide may be, for example, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylpropionamide, diethylpropionamide, 2,2,2-trifluorodimethylacetamide, dipropylacetamide, or the like.

[0096] In the case where the electrolyte 32 includes a halogenated liquid, the halogenated liquid may include, for example, a chlorinated liquid such as dichloromethane or a fluorinated liquid such as 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.

[0097] In the case where the electrolyte 32 includes a solvent that is a nitrile, the nitrile may include, for example, acetonitrile, propionitrile, methoxyacetonitrile, 3-methoxypropionitrile, succinonitrile, glutaronitrile, adiponitrile, tetracyanoethylene, 3,3′-oxydipropionitrile, 3-ethoxypropionitrile, 1,3,6-hexanetrinitrile, 1,2,2,3-propanetetracarbonitrile, malononitrile, fumaronitrile, valeronitrile, acrylonitrile, toluenenitrile, methoxybenzonitrile, or 3-butoxypropionitrile, etc.

[0098] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid may be, for example, an imidazole derivative (such as, for example, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 2,3-dimethyl-1-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-decyl- 3-Methylimidazole bis(trifluoromethanesulfonyl)imide, 1,3-dimethylimidazole bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole trifluoromethanesulfonate, 1-vinylimidazole bis(trifluoromethanesulfonyl)imide, 1-allyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazole trifluoromethanesulfonate, 3-ethyl-1-vinyl Imidazole bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazole tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-Ethyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-(4-sulfobutyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-1H-imidazole-3-hexafluorophosphate or 3,3'-(butane-1,4-diyl)bis(1-vinyl-3-imidazole)bis(trifluoromethanesulfonyl)imide, etc.

[0099] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a pyrrolidine derivative (such as, for example, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 1-methyl-1-pentylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidine, bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-methylpyrrolidine tetrafluoroborate, or 1-allyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, etc.).

[0100] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a pyridine derivative (such as, for example, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-hexylpyridinium hexafluorophosphate, 1-ethyl-3-(hydroxymethyl)pyridinium ethylsulfate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylpyridinium ethylsulfate, 1-methylpyridinium bis(trifluoromethanesulfonyl)imide, or 1,1′-bis[3-(trimethylammonium)propyl]-4,4′-bipyridine, etc.).

[0101] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid may be, for example, a piperidine derivative such as 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide or 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, or the like.

[0102] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, an ammonium derivative, such as methyltri-n-octylammonium bis(trifluoromethanesulfonyl)imide, ethyl(3-methoxypropyl)dimethylammonium bis(trifluoromethanesulfonyl)imide, ethyl(2-methoxyethyl)dimethylammonium bis(trifluoromethanesulfonyl)imide, butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium trifluoromethanesulfonate, methyltri-n-octylammonium bis(trifluoromethanesulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, tributylmethylammonium bis(trifluoromethanesulfonyl)imide, butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, or tetrabutylammonium hexafluorophosphate.

[0103] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid can be, for example, a phosphorus derivative such as tributylmethylphosphorus bis(trifluoromethanesulfonyl)imide, tributyl(2-methoxyethyl)phosphorus bis(trifluoromethanesulfonyl)imide, tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium hexafluorophosphate, or tributylmethylphosphorus bis(trifluoromethanesulfonyl)imide.

[0104] In the case where the electrolyte 32 includes an ionic liquid, the ionic liquid may be, for example, a morpholine derivative, or a sulfonium derivative (such as, for example, triethylsulfonium bis(trifluoromethanesulfonyl)imide).

[0105] In the case where the electrolyte 32 is present in the electrochemical cell 10 as a solution including a solvent and a solute dissolved in the solvent, the solute may include one or more ionic metal complexes, such as, for example, bis(nonafluorobutanesulfonyl)imide, metal (fluorosulfonyl)(trifluoromethanesulfonyl)imide, metal trifluoromethanesulfonate, metal tetrafluoroborate, metal hexafluorophosphate, metal bis(fluorosulfonyl)imide, metal nonafluoro-1-butanesulfonate, metal bis(trifluoromethanesulfonyl)imide, metal tricyanomethane, metal nitrate, metal halide, metal bis(oxalato)borate, metal difluoro(oxalato)borate, or metal perchlorate, among others.

[0106] The electrolyte 32 may optionally include one or more additives, wherein the additives may be polymeric materials, plasticizers, phosphazenes, phosphates, sulfonyl groups, and carboxylic acids. When present, the polymeric materials may include, in any combination, for example, one or more of polycaprolactone, polyacrylic acid, poly(methyl acrylate), polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinyl pyrrolidone, poly(4-vinyl pyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, styrene-butadiene-rubber, and sodium carboxymethyl cellulose. In one embodiment, the polymeric material includes one of polyethylene oxide or polyvinylidene fluoride.

[0107] Where the additive includes a plasticizer, the plasticizer may include, for example, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, γ-butyrolactone, cyclopentane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitates, adipates, sebacates, maleates, or any combination thereof.

[0108] In the case where the additive includes phosphazene, the phosphazene may include, for example, one or more of pentafluoro(phenoxy)cyclotriphosphazene, tripolychlorophosphazene, ethoxy(pentafluoro)cyclotriphosphazene, hexaphenoxycyclotriphosphazene, or hexafluorocyclotriphosphazene.

[0109] In the case where the additive includes a phosphate ester, the phosphate ester may 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-ethylhexyl diphenyl phosphate, tripentyl phosphate, tri-o-cresyl phosphate, triallyl phosphate, tri-m-cresyl phosphate, triethyl phosphate, tri-p-cresyl phosphate, triphenyl phosphate, trimethyl phosphate, and tris(2,2,2-trifluoroethyl) phosphate.

[0110] In the case where the additive includes a sulfonyl group, the sulfonyl group may include, for example, one or more of isopropyl methyl sulfone, dimethyl sulfone, dimethyl sulfite, dipropyl sulfone, 1,3-propane sultone, 3-methylcyclopentane sulfone, 1,4-butane sultone, tetrahydrothiophene 1,1-dioxide, 1,3,2-dioxazolethiophene 2,2-dioxide, and 1,3,2-dioxazolethiophene 2-oxide.

[0111] In the case where 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 of between about 0.01 wt % and about 30 wt %, preferably between about 0.1 wt % and about 20 wt %, and more preferably between about 1 wt % and about 10 wt %.

[0112] In the case where the 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). Suitable means that the liquid and solid electrolyte materials are physically and chemically compatible and, when mixed together in a selected proportion, produce an electrolyte gel exhibiting the desired viscosity and electrolytic properties.

[0113] The electrolyte 32 preferably comprises a liquid, a liquefied gas, and / or a gel because the discharge products 28 are generally more soluble in such electrolytes. In one embodiment, the electrolyte 30 comprises a solvent having a molecular weight of less than about 300 g / mol, preferably less than about 200 g / mol, and more preferably less than about 100 g / mol. Solvents with lower molecular weights can result in higher energy densities in the resulting electrochemical cell. For example, the molecular weight of water is 18.01 g / mol, dimethylacetamide is 87.12 g / mol, dimethoxyethane is 90.12 g / mol, dimethyl carbonate is 90.08 g / mol, ethylene carbonate is 88.06 g / mol, and dioxolane is 74.08 g / mol.

[0114] In some embodiments, the battery 32 may be referred to as a "single-material" battery, in which the cathode active material disclosed herein may also serve as an electrolyte and / or separator. In such embodiments, the cathode active material that is not in contact with the conductive material or current collector serves as the electrolyte and / or separator.

[0115] Where the cell comprises a cathode and an electrolyte, its composition can include a cathode:electrolyte ratio that can vary from 15:85 to 95:5 by weight. The cathode:electrolyte composition ratio 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 wt% cathode. Preferably, the cathode electrolyte ratio is at least 30 wt% cathode. More preferably, the cathode electrolyte ratio is at least 45 wt% cathode.

[0116] In the case where the battery includes a cathode and an electrolyte, the electrolyte may 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 the electrolytic solvent. 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, before the battery is operated, a portion or all of the amount of the metal compound is dissolved in the electrolytic solvent, 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 may also act as part of the electrolyte. In some embodiments, when the metal compound is dissolved in the electrolytic solvent, the electrolyte may flow through and through the cathode at any rate.

[0117] In addition, the electrolyte of electrolytic separator 46 and / or atmosphere 50 may include greenhouse gases. When present in the electrolyte, greenhouse gases may be dissolved or liquefied greenhouse gases. The term "greenhouse gas" generally refers to a gas that absorbs and emits radiant energy in the thermal infrared range. Non-exclusive 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, etc. When the greenhouse gas is a halocarbon compound, it may include, for example, carbon tetrachloride (CCl4), tetrafluoromethane (CF4) or hexafluoroethane (C2F6).

[0118] In the case where the greenhouse gas is dissolved in the liquid electrolyte, the greenhouse gas can be introduced through an apparatus comprising a pressure gauge, a gas inlet, a gas outlet, and a chemically resistant glass frit or foam immersed in the liquid electrolyte. The liquid electrolyte can be maintained in a greenhouse gas atmosphere at a pressure greater than standard atmospheric pressure for at least 10 seconds to at least 100 seconds or longer.

[0119] It should be understood that although the description of various embodiments herein is written in the context of a battery having a single battery cell, the same or similar principles can be applied to battery assemblies including more than one battery cell (i.e., battery packs, etc.). Such multi-battery assemblies should be understood to fall within the scope of the present disclosure.

[0120] Example 1: Fabrication of a high-energy cathode

[0121] Cathodes according to the present disclosure were fabricated and tested using the following procedure.

[0122] Lithium hydroxide (LiOH) monohydrate and lithium chloride (LiCl) hydrate were dissolved in a 1:4 oxalic acid (OA)-methanol (MeOH) mixture under vigorous stirring to prepare a 0.1M LiOH / 0.1M LiCl solution. 100 mg of carbon nanotubes (CNTs) were added to the solution under stirring, and the resulting mixture was sonicated for 10 minutes to intermix the CNTs. A solution of hydrogen peroxide (H2O2) and urea peroxide (CH6N2O3) was added to the reaction mixture under vigorous stirring at 65°C. The molar ratio of the components of the reaction mixture was H2O2:CH6N2O3:LiOH:LiCl = 1:1:1:1.

[0123] 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 in vacuo at 110°C for 24 hours. The collected material was then quickly transferred to an argon-filled glove box with minimal exposure to air 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 a pore size of 0.08 mm to produce a high-energy cathode.

[0124] The prepared cathode was placed in a coin cell (CR2032) along with a lithium metal foil as the anode and a polypropylene separator. The cells were wetted with an electrolyte solution of 0.5 M bistrifluoromethanesulfonimide (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 above 5 bar for 7 days before use.

[0125] Example 2: Determining the charge-discharge curve of a high-energy battery

[0126] The high energy battery prepared in Example 1 was subjected to cyclic charge-discharge by applying a constant current to the battery. Figure 4 As shown in the chart, Figure 4It is a graph of the charge-discharge curves of voltage (V reference Li / Li+) and specific capacity (mAh / g).

[0127] As shown in the figure, the battery of Example 1 has a high current density at 1 mA / cm2 based on the weight of the cathode active material. 2 A specific capacity exceeding 500 mAh / g was achieved at a current density of 1.5 GHz. The graph also shows a high average operating discharge voltage of 3.41 V, with a clear discharge plateau at approximately 3.48 V. Furthermore, there was no evidence of any oxygen reduction reaction at approximately 2.5 V, indicating that the cathode active material did not evolve gaseous oxygen during charging.

[0128] Example 3: Determining the recharge capacity of a high-energy battery

[0129] The high energy battery prepared in Example 1 was subjected to repeated discharge and recharge. Figure 5 As shown, the battery is at 1mA / cm 2 The high capacity was maintained over 15 cycles at a current density of 1.5 GHz.

[0130] Example 4: Comparison of specific capacity

[0131] The specific capacity of the cathode material prepared in Example 1 was compared with that of a conventional lithium-ion battery having a metal oxide cathode. Figure 6 As shown, the cathode prepared in Example 1 exhibits a higher performance than that of the cathode selected from LiFePO4(A), LiNi x Co y Al z O2(C), LiNi x Co y Al z Higher practical specific capacities of conventional lithium-ion batteries with metal oxide cathodes of LiO2(C), LiCOO2(D), LiNiO2(E), LiMnO2(F), LiMnPO4(G), LiTiS2(H) and Li2MnO3(l) (the values ​​shown in the figure for conventional battery compositions are taken from the publicly available literature (see https: / / doi.org / 10.1016 / j.mattod.2014.10.040)).

[0132] Example 5: Alternative Embodiment

[0133] This section describes additional aspects and features of the disclosed cathode active materials, cathodes, and batteries, which are presented as a series of paragraphs without limitation, some or all of which may be represented by alphanumeric characters for clarity and efficiency. Each of these paragraphs may be combined in any suitable manner with one or more other paragraphs and / or with the disclosures elsewhere in this application. Some of the following paragraphs explicitly reference and further limit other paragraphs, thereby providing non-limiting examples of some suitable combinations.

[0134] A1. A cathode active material comprising: a R b A metal compound wherein M is a metal; R is an atom, molecule or free radical; a and b are independently positive non-zero real numbers; and has the empirical formula M′ x O y wherein M′ is a metal, and x and y are independently positive non-zero real numbers; wherein the metal compound is in contact with the metal oxide.

[0135] A2. The cathode active material of paragraph A1, wherein M and M' can be the same or different and are selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum.

[0136] A3. The cathode active material of paragraph A1, wherein at least a portion of the metal compound and a portion of the metal oxide are combined to form a cathode active material having the empirical formula M a M′ b R c O d where each of a, b, c, and d is a positive non-zero real number that may be the same or different.

[0137] 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.

[0138] A5. The cathode active material of paragraph A4, wherein when R is an organic moiety, R is an organic moiety comprising one or more heteroatoms independently selected from nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron.

[0139] 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.

[0140] B1. A cathode material comprising: a cathode active material comprising a metal compound and a metal oxide; wherein the metal compound has an empirical formula M a R b , where M is a metal; R is an atom, molecule or free radical; and a and b are independently positive non-zero real numbers; and the metal oxide has the empirical formula M′x O y , wherein M′ is a metal, and x and y are independently positive non-zero real numbers; bringing the metal compound and the metal oxide into contact; and a conductive material; bringing one or both of the metal compound and the metal oxide into contact with the conductive material.

[0141] B2. The cathode material of paragraph B1, wherein M and M' can be the same or different and are selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc and aluminum.

[0142] B3. The cathode material of paragraph B1, wherein the conductive material comprises a porous carbon material.

[0143] 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.

[0144] B5. The cathode material of paragraph B1, wherein the conductive material comprises one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

[0145] B6. The cathode material of paragraph B1, further comprising one or more of a polymer binder, a plasticizer, and a carboxylic acid.

[0146] C1. A battery having a cathode, wherein the cathode comprises a cathode active material comprising a cathode having the empirical formula M a R b A metal compound wherein M is a metal; R is an atom, molecule or free radical; and a and b are independently positive non-zero real numbers; and has the empirical formula M′ x O y wherein M′ is a metal, and x and y are independently positive non-zero real numbers; wherein the metal compound and the metal oxide are in contact.

[0147] C2. The battery of paragraph C1, wherein the cathode evolves essentially zero gaseous oxygen during operation of the battery.

[0148] C3. The battery of paragraph C1, wherein the battery is greater than or equal to 0.1 mA / cm 2 The cathode active material exhibits a discharge specific capacity of at least 500 mAh / g based on the amount of the cathode active material at a current density of 100 mAh / g.

[0149] C4. The battery of paragraph C1, wherein the battery can be greater than or equal to 0.1 mA / cm 2 The current density of Li / Li + An average operating discharge potential of at least 3.0V.

[0150] C5. The battery of paragraph C1, wherein the battery is substantially rechargeable.

[0151] C6. The battery of paragraph C1, wherein the battery is capable of operating at room temperature.

[0152] C7. The battery of paragraph C1, further comprising an anode, wherein the anode comprises an anode active material, the anode active material being at least partially surrounded by a coating on an outer surface of the anode material, wherein the coating comprises carbon and oxygen.

[0153] C8. The battery of paragraph C1, further comprising a liquid, solid, or semisolid electrolyte, wherein the electrolyte comprises an electrolytic solvent.

[0154] C9. The battery of paragraph C8, wherein the solubility of the metal oxide in the electrolytic solvent is less than the solubility of the metal compound in the electrolytic solvent.

[0155] 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.

[0156] C11. The battery of paragraph C1, further comprising a greenhouse gas that is liquefied, in contact with the electrolyte, or dissolved in the electrolyte.

[0157] C12. The battery of paragraph C11, wherein the greenhouse gas includes one or more of carbon dioxide (CO2), methane (CH4), sulfur hexafluoride (SF6), perfluorocarbons, chlorofluorocarbons, and hydrofluorocarbons.

[0158] C13. The battery of paragraph C1, further comprising a separator, wherein the separator comprises a polymer material.

[0159] C14. The battery of paragraph C1, further comprising a current collector comprising an alloy of one or more of molybdenum, titanium, and zirconium.

[0160] Advantages, features and benefits.

[0161] The cathode active materials of the present disclosure allow for the fabrication of high energy cathodes for batteries that are economical, provide high discharge capacity, high discharge potential, and do not experience oxygen evolution during operation.

[0162] Selected batteries of the present disclosure have a current density greater than or equal to 0.1 mA / cm 2 In some embodiments, the discharge capacity of the cathode active material is greater than or equal to 100 mAh / g at a current density of 0.1 mA / cm 2At a current density of 100 mAh / g, the battery of the present disclosure can exhibit a discharge specific capacity of greater than 200 mAh / g, greater than 300 mAh / g, and greater than 500 mAh / g.

[0163] Selected batteries of the present disclosure may exhibit relative Li / Li + An average operating discharge potential greater than 1.0 V. In some embodiments, the battery of the present disclosure may exhibit a relative Li / Li + The average operating discharge potential is greater than 2.0 V, greater than 3.0 V or even greater than 4.0 V. Typically, at a discharge potential greater than or equal to 0.1 mA / cm 2 At a current density of 2.5 GHz, this battery can produce a relative high current density of Li / Li + An average operating discharge potential of at least 3.0V.

[0164] All current densities presented in this disclosure are normalized by the planar area of ​​the cathode.

[0165] 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 the battery exhibits a cycle count greater than 100. Alternatively or additionally, selected batteries of the present disclosure may operate effectively at room temperature, which in one embodiment may be defined as 15°C-30°C.

[0166] Cathodes prepared according to the methods of the present disclosure can operate with evolution of less than 1 mg / 1 mAh of gaseous oxygen over the entire life cycle of a battery including the cathode. In some cases, cathodes of the present disclosure exhibit essentially zero evolution of gaseous oxygen during operation.

[0167] The cathode active materials of the present disclosure exhibit a relative Li / Li + Above the standard redox potential of 3.0V.

[0168] Unless otherwise stated, the term "combination" or "combinations" refers to all types of combinations starting from two of the relevant elements to a plurality or all of such elements.

[0169] The illustration of method steps, whether shown in the drawings or described in the specification, should not be construed as indicating a specific order of method steps unless an order is specifically provided. The order of the steps may differ from that depicted and described, and / or two or more steps may be performed concurrently or with partial concurrence, unless otherwise indicated.

[0170] Features and variants specified in individual embodiments and examples can be freely combined with features and variants of other examples and embodiments and serve in particular to characterize the invention in the claims, without necessarily implying further details of the respective embodiment or the respective example.

[0171] The above disclosure may include multiple different examples with independent utility. Although each of these has been disclosed in one or more illustrative forms, the specific embodiments thereof as disclosed and shown herein should not be considered restrictive, as many variations are possible. With respect to the section headings used in this disclosure, these headings are for organizational purposes only. The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of the various elements, features, functions and / or performances disclosed herein. The following claims specifically point out certain combinations and sub-combinations that are considered novel and non-obvious. Other combinations and sub-combinations of features, functions, elements and / or performances may be claimed in applications claiming priority to this application or a related application. Such claims, whether broader, narrower, equal or different in scope than the original claims, are also considered to be included in the subject matter of the present disclosure.

Claims

1. A cathode active material comprising: a metal compound having the empirical formula MRx, wherein M is a metal; R is an atom, molecule, or free radical, wherein R has an oxidation state of -1, and x is a positive non-zero real number; and Metal oxides having the empirical formula MyOz, where M is the same metal as found in the metal compound, and y and z are independent positive non-zero real numbers; wherein the metal compound is in contact with the metal oxide; wherein each R is independently an organic moiety or a halogen; wherein when R is an organic moiety, R is an organic moiety comprising one or more heteroatoms independently selected from nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron.

2. A cathode material comprising: a cathode active material comprising a metal compound and a metal oxide; wherein the metal compound has the empirical formula MRx, wherein M is a metal; R is an atom, molecule, or radical, wherein R has an oxidation state of -1, and x is a positive non-zero real number; and the metal oxide has the empirical formula MyOz, wherein M is the same metal as found in the metal compound, and y and z are independently positive non-zero real numbers; such that the metal compound and the metal oxide are in contact; and Conductive materials; One or both of the metal compound and the metal oxide are brought into contact with the conductive material.

3. The cathode material of claim 2, wherein M is selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, and aluminum. The cathode material of claim 2 , wherein the conductive material comprises a porous carbon material. 5 . The cathode material according to claim 4 , wherein the porous carbon material is doped with one or more heteroatoms selected from boron, nitrogen, sulfur, phosphorus, fluorine, chlorine and bromine.

6. The cathode material according to claim 2, wherein the conductive material comprises one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

7. The cathode material according to claim 2, further comprising one or more of a polymer binder, a plasticizer, and a carboxylic acid.

8. A battery having a cathode, wherein the cathode comprises a cathode active material comprising a metal compound having the empirical formula MRx, wherein M is a metal, R is an atom, a molecule, or a free radical, wherein R has an oxidation state of -1, and wherein x is a non-zero positive real number; and a metal oxide having the empirical formula MyOz, wherein M is the same metal as that found in the metal compound, and y and z are independent non-zero positive real numbers; wherein the metal compound and the metal oxide are in contact.

9. The battery of claim 8, wherein the cathode does not evolve substantially gaseous oxygen during operation of the battery.

10. The battery according to claim 8, wherein the 2 The battery exhibits a discharge capacity of at least 500 mAH / g at a current density of .

11. The battery according to claim 8, wherein the 2 The battery is capable of producing an average operating discharge potential of at least 3.0V at a current density of .

12. The battery of claim 8, wherein the battery is substantially rechargeable.

13. The battery according to claim 8, wherein the battery is operable at room temperature.

14. The battery of claim 8, further comprising an anode, wherein the anode comprises an anode active material at least partially surrounded by a coating on an outer surface of the anode material, wherein the coating comprises carbon and oxygen.

15. The battery according to claim 8, further comprising an electrolyte, wherein the electrolyte comprises an organic amide compound.

16. The battery of claim 15, further comprising a greenhouse gas liquefied in contact with or dissolved in the electrolyte.

17. The battery of claim 16, wherein the greenhouse gas comprises one or more of carbon dioxide (CO2), methane (CH4), sulfur hexafluoride (SF6), perfluorocarbons, chlorofluorocarbons, and hydrofluorocarbons.

18. The battery of claim 8, further comprising a separator, wherein the separator comprises a polymer material.

19. The battery of claim 8, further comprising a current collector comprising an alloy of one or more of molybdenum, titanium, and zirconium.

20. A method for producing a cathode active material, comprising: preparing a solution of a hygroscopic substance and a reactive oxygen species, wherein the hygroscopic substance comprises one or more ionic compounds or organic compounds, wherein each ionic compound comprises a chloride, a bromide, a pentoxide, a sulfide, or a sulfate; and wherein the reactive oxygen species comprises one or more peroxides, superoxides, superoxide radicals, hydroxyl radicals, peroxyl radicals, perhydroxyl radicals, hydroperoxyl radicals, alkoxyl radicals, singlet oxygen, hypochlorous acid, and alpha-oxygen; heating the solution at a temperature of less than about 400° C. for a time sufficient to form a precipitate of the cathode active material, wherein the precipitate of the cathode active material comprises a reactive oxygen species derivative, the reactive oxygen species derivative in combination with the hygroscopic species, or the reactive oxygen species in combination with the hygroscopic species; collecting the cathode active material; as well as drying the collected cathode active material; The hygroscopic substance comprises one or more organic compounds selected from the group consisting of trimerized indanone, trimerized indanone 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, cyclopropene derivatives and amide derivatives.

21. The method of claim 20, wherein the hygroscopic substance comprises one or more organic compounds each independently bonding one or more nitrogen atoms or oxygen atoms.

22. A method of manufacturing a cathode for a battery, comprising: preparing a solution of a hygroscopic substance and a reactive oxygen species, wherein the hygroscopic substance comprises one or more ionic compounds or organic compounds, wherein each ionic compound comprises a chloride, a bromide, a pentoxide, a sulfide, or a sulfate; and wherein the reactive oxygen species comprises one or more peroxides, superoxides, superoxide radicals, hydroxyl radicals, peroxyl radicals, perhydroxyl radicals, hydroperoxyl radicals, alkoxyl radicals, singlet oxygen, hypochlorous acid, and alpha-oxygen; heating the solution at a temperature of less than about 400° C. for a time sufficient to form a precipitate of cathode active material, wherein the precipitate of cathode active material comprises a reactive oxygen species derivative, a reactive oxygen species derivative in combination with a hygroscopic species, or a reactive oxygen species derivative in combination with a hygroscopic species; collecting cathode active material; drying the collected cathode active material; combining a cathode active material with one or more conductive materials and a polymer binder; and The combined cathode materials are deposited on a current collector to produce the cathode.

23. The method of claim 22, wherein combining the cathode active material with a conductive material comprises combining the cathode active material with a porous carbon material, the porous carbon material comprising one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphene, graphene oxide, and graphene nanoribbons.

24. The method of claim 22, wherein combining the cathode active material with a conductive material or a polymer binder further comprises combining the cathode active material with a plasticizer.

25. The method of claim 22, wherein depositing a combined cathode material on the current collector comprises depositing a combined cathode material on a metal current collector comprising one or more of molybdenum, titanium, and zirconium.

26. A battery comprising a cathode made according to the method of claim 22, wherein the cathode evolves less than 1 mg / 1 mAh of gaseous oxygen during the complete life cycle of the battery.

27. The battery of claim 26, wherein the cathode evolves essentially zero gaseous oxygen during operation of the battery.

28. The battery according to claim 26, wherein at a temperature greater than or equal to 0.1 mA / cm 2 At a current density of at least 500 mAh / g, the battery exhibits a discharge capacity of at least 500 mAh / g.

29. The battery according to claim 26, wherein at a temperature greater than or equal to 0.1 mA / cm 2 The battery is capable of producing an average operating discharge potential of at least 3.0V at a current density of .

30. The battery of claim 26, further comprising an anode, wherein the anode comprises a coating coating an outer surface of the anode material, wherein the coating comprises carbon and oxygen.

31. The battery of claim 26, further comprising an electrolyte, wherein the greenhouse gas is liquefied, in contact with, and dissolved in the electrolyte.

32. The battery of claim 31 , wherein the greenhouse gas comprises one or more of carbon dioxide (CO2), methane (CH4), tetrafluoromethane (CF4), hexafluoroethane (C2F6), sulfur hexafluoride (SF6), carbon tetrachloride (CCl4), perfluorocarbons, chlorofluorocarbons, and hydrofluorocarbons.

Images