High energy solid state battery and method for making same

Abstract

A solid-state battery comprising an electrolyte comprising an electrolyte material and a positive electrode in contact with the electrolyte, wherein at least a portion of the electrolyte material is solid, the solid portion of the electrolyte material comprising a first chloride compound, and the positive electrode comprising an active cathode material comprising a second chloride compound, the battery being economically deployable and capable of producing a high energy density.

Description

[Technical Field]

[0001] This disclosure generally relates to high energy solid state batteries and methods of making the same, which include an electrolyte comprising a solid electrolyte material and a positive electrode comprising an active positive electrode material. [Background technology]

[0002] Batteries are ubiquitous in modern technology, used in a wide range of applications, from small batteries for industrial and medical equipment to larger 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 an intercalated lithium compound as one electrode material and relies on the shuttle of lithium ions between a positive electrode and a negative electrode in an electrolyte solution. While lithium-ion batteries have many advantages, they can produce relatively low energy densities and require expensive materials for manufacture.

[0003] Solid-state batteries are often considered the next generation of lithium-ion battery technology. At least theoretically, solid-state batteries have the potential to outperform current lithium-ion batteries in many respects, including safety and energy density. However, in practice, such batteries are still too expensive to manufacture to achieve better safety and greater energy density than conventional lithium-ion batteries. First-generation all-solid-state batteries contain solid electrolytes. Despite the high ionic conductivity and low grain boundary resistance of such solid electrolytes, they can require high stack pressures (i.e., greater than 10 MPas) and extremely dry manufacturing environments (i.e., dew points below -60°C), and the properties of the solid electrolyte material itself can be difficult to convert into freestanding thin films with thicknesses of less than 20 μm.

[0004] What is needed are improved solid-state batteries that contain highly compatible cathode and electrolyte materials, that can achieve higher energy densities (>500 Wh / kg), more economical manufacturing costs, and lower material costs, while also exhibiting greater electrochemical reversibility, extended cycle life, and reduced risk of fire and explosion. Summary of the Invention

[0005] The present disclosure focuses on a solid-state battery having an electrolyte and a positive electrode, the electrolyte including an electrolyte material, at least a portion of which is solid, and the solid portion of the electrolyte material including a first chlorine compound, the positive electrode in contact with the electrolyte, and the positive electrode including an active cathode material including a second chlorine compound.

[0006] The disclosed features, functions, and advantages of the disclosed batteries, cathodes, and cathode active materials can be realized independently in various embodiments of the present disclosure or can be combined in further embodiments, further details of which can be understood with reference to the following description and drawings. [Brief explanation of the drawings]

[0007] FIG. 1 is a schematic diagram of an exemplary solid-state battery according to the present disclosure.

[0008] FIG. 2 is a flow chart of an exemplary method for making a cathode active material according to the present disclosure.

[0009] FIG. 3 is a flow chart of an exemplary method for fabricating a positive electrode according to the present disclosure.

[0010] FIG. 4 is a semi-schematic diagram of an exemplary anode-free battery according to the present disclosure.

[0011] FIG. 5 is a semi-schematic diagram of an alternative exemplary anode-free battery according to the present disclosure.

[0012] FIG. 6 is a schematic diagram illustrating the fabrication of a solid-state battery including an electrolyte and a positive electrode fabricated in accordance with the present disclosure.

[0013] FIG. 7 is a schematic diagram illustrating selected details of an exemplary solid-state battery fabricated in accordance with the present disclosure.

[0014] FIG. 8 is a graph demonstrating the advantageously high rechargeability of an exemplary battery according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present disclosure provides batteries that exhibit high energy density, extended cycle life, and reduced risk of fire and explosion. In some embodiments, the disclosed batteries are substantially rechargeable. In some embodiments, the disclosed batteries are operable at room temperature.

[0016] "Positive electrode active material" refers to the portion of the positive electrode that participates in the supply of ions through the electrolyte and the supply of electrons through the external circuit during charging of the battery, and that participates in the acceptance of ions through the electrolyte and the acceptance of electrons through the external circuit during discharging of the battery. "Negative electrode active material" refers to the portion of the negative electrode that participates in the supply of ions through the electrolyte and the supply of electrons through the external circuit during discharging of the battery, and that participates in the acceptance of ions through the electrolyte and the acceptance of electrons through the external circuit during charging of the battery. Both the positive electrode active material and the negative electrode active material participate in electrochemical redox reactions by transporting ions through the electrolyte and / or transporting electrons through the external circuit.

[0017] Any coating, natural or artificial layer, protective layer of any kind on the surface of the positive or negative electrode active material, if present, that does not participate in the electrochemical redox reaction during charging and discharging of the battery, is not considered part of the respective active material.

[0018] A "solid-state battery" refers to a type of battery having an electrolyte comprising an electrolyte material, at least a portion of which is solid. An "all-solid-state battery" refers to a solid-state battery having an electrolyte comprising an electrolyte material, all of which is solid. The solid portion of the electrolyte material of the solid-state battery of the present disclosure can be more than 50 wt% of the electrolyte material, preferably more than 75 wt% of the electrolyte material, and more preferably 100 wt% of the electrolyte material.

[0019] "Inverse vulcanization" refers to a solvent-free polymerization process that produces polymers containing chains of sulfur atoms. The polymers produced by inverse vulcanization consist of long, linear sulfur chains interspersed with organic linkers. Utilizing the inverse vulcanization polymerization method of sulfur allows for the production of solid electrolyte materials with physical properties that allow them to form freestanding thin films.

[0020] "Redox reaction" refers to a class of chemical reactions in which the oxidation state of participating atoms, molecules, radicals, or ions changes by gaining or losing electrons. Redox reactions are most often characterized by the actual or formal transfer of electrons between chemical species, with one species becoming oxidized and the other species becoming reduced.

[0021] "Current collector" refers to a component adjacent to an electrode (positive or negative) configured to carry current from a fixed portion to a moving portion of an electrochemical cell circuit, or vice versa. A current collector is a bridge component that collects current generated at an electrode and forms a connection to an external circuit. The current collector is typically adjacent to the positive or negative electrode. A bipolar current collector can be adjacent to both the positive and negative electrodes, or both the positive and negative electrodes can be coated on one or both sides of the bipolar current collector. In some embodiments, the current collector comprises a conductive material, i.e., a porous carbon material. The porous carbon material can be selected from, for example, carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, reduced graphene oxide, and graphene nanoribbons.

[0022] "Electrolyte" or "electrolyte solution" refers to a material that transports ions 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 positive electrode to the negative electrode during charging of the electrochemical cell, and from the negative electrode to the positive electrode during discharge.

[0023] The term "room temperature," as used herein, refers to any temperature within a range that most people prefer for an indoor environment and that they find comfortable when wearing typical indoor clothing. More specifically, room temperature includes temperatures between 15°C and 30°C (i.e., 59°F and 86°F).

[0024] The term "solubility," as used herein, refers to the maximum amount by weight of a material that dissolves in a given amount by weight of solvent at a given temperature. As used herein, the term "at least slightly soluble" means that less than 1,000 parts by weight of electrolytic solvent is required per weight of active cathode material at a given temperature. As used herein, the term "substantially insoluble" means that more than 10,000 parts by weight of electrolytic solvent is required per weight of active cathode material at a given temperature.

[0025] The term "semi-solid," as used herein, refers to a material whose state is between that of a solid and a liquid. While similar to solids in some respects, such as the ability to support its own weight and retain its shape, semi-solids also share certain properties, such as the ability to conform to a shape under applied pressure and to flow under pressure. The terms "quasi-solid," "semi-solid," and "semi-liquid" can be used interchangeably to refer to semi-solid materials. Typically, the viscosity of a semi-solid is in the range of 10 mPas to 100,000 mPas.

[0026] The term "substantially" means to conform substantially to a particular size, area, shape, concept, or other situation modified by the term, so that features or components do not necessarily 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] The terms "comprising," "including," and "having" (and their conjugations) are open-ended terms that are used interchangeably to mean inclusion, but not necessarily limitation, and are not intended to exclude additional, unrecited elements or method steps.

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

[0029] All specifications regarding amounts and portions, particularly amounts and portions intended to define the scope of the present disclosure, unless they relate to a specific embodiment, indicate a tolerance of ±10%, e.g., 11% average, i.e., 9.9% to 12.1%. In the case of terms such as "solvent," the word "a" should not be considered a numerical word, but rather as an indefinite article or pronoun unless the context requires otherwise.

[0030] The term "combination," unless otherwise specified, means any kind of combination of two of the associated elements, up to a plurality or all of such elements.

[0031] 1, a solid-state battery 10 of the present disclosure includes at least one solid-state electrochemical cell 12 including a positive electrode 14 with an active positive electrode material 16 and an electrolyte 30. Each solid-state electrochemical cell 12 may further include an anode 18 including an active anode material 20.

[0032] The electrolyte 30 and cathode active material 16 of the electrochemical cell 12 are selected such that at least a portion of the electrolyte material 36 of the electrolyte 30 is solid, the solid portion of the electrolyte includes a first chlorine compound, and the cathode active material 16 includes a second chlorine compound. The first chlorine compound and the second chlorine compound can be the same. When the first chlorine compound and the second chlorine compound are the same, the chlorine compound can function as both the cathode active material and the electrolyte material. In some embodiments, the solid-state battery can be configured such that the first chlorine compound is electrochemically converted to the second chlorine compound, and the second chlorine compound is converted to the first chlorine compound.

[0033] The solid-state electrochemical cell 12 can further include a separator 32 that separates the positive electrode from the negative electrode or the positive electrode from the negative electrode current collector. In some embodiments, the electrolyte itself can also function as such a separator. The electrolyte 30 and / or separator 32 can be configured to be wider and / or longer than one or both of the positive electrode current collector 24 and the negative electrode current collector 26 to avoid contact between the negative electrode 18 and the positive electrode 14.

[0034] In some cases, the disclosed solid-state electrochemical cell 12 includes a negative electrode current collector 26 but does not initially include an active negative electrode material 20. In such cases, the active negative electrode material 20 can be deposited on or interposed with the negative electrode current collector 26 during initial charging of the solid-state battery 10 including the electrochemical cell 12. In such cases, an electrolyte 30 can be disposed within the positive electrode 14 and / or between the negative electrode current collector 26 and the positive electrode 14. In some embodiments, the negative electrode current collector 26 and / or the positive electrode current collector 24 correspond to the cell housing 34 of the self-charging electrochemical cell 10.

[0035] In some embodiments, the first chlorine compound of the solid-state battery has a melting point of less than 700°C. Preferably, the first chlorine compound has a melting point of less than 600°C. More preferably, the first chlorine compound has a melting point of less than 500°C. Solid electrolytes exhibiting low melting points can be advantageous in the fabrication of the solid-state batteries of the present disclosure. For example, electrolyte materials having relatively low melting points can be stored in separate containers under a controlled atmosphere and introduced into electrochemical cells as needed, with less energy consumption and lower manufacturing costs.

[0036] In some embodiments, the first chlorine compound has 3% or more by weight of chlorine. Preferably, the first chlorine compound may have 6% or more by weight of chlorine. More preferably, the first chlorine compound may have 9% or more by weight of chlorine.

[0037] In some embodiments, the active cathode material of the solid-state battery comprises one or more metals selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, or aluminum. Preferably, the active cathode material can comprise one or more metals selected from lithium, sodium, potassium, magnesium, calcium, vanadium, copper, zinc, or aluminum. More preferably, the active cathode material can comprise one or more metals selected from lithium, sodium, potassium, magnesium, zinc, or aluminum. In some embodiments, the solid-state battery is configured such that charging the solid-state battery oxidizes the metal of the active cathode material to metal ions, thereby transporting the metal ions through the electrolyte.

[0038] In some embodiments, the solid portion of the electrolyte material 36 of the solid-state battery 10 comprises sulfur. When the solid portion of the electrolyte material 36 comprises sulfur, the solid portion can be produced by inverse vulcanization of sulfur.

[0039] In one embodiment of the present disclosure, a disclosed solid-state battery includes an electrolyte 30 including an electrolyte material 36, at least a portion of which is solid, the solid portion of which is formed by reverse vulcanization of sulfur, and a cathode 14 in contact with the electrolyte 30, the cathode including an active cathode material 16.

[0040] Preparation of positive electrode active material

[0041] An exemplary method for making a high-energy active cathode material according to the present disclosure is shown in Flowchart 40 of Figure 2. The method includes providing a solution comprising a hygroscopic species and an active oxygen species in step 42 of Flowchart 40, heating the solution at a temperature less than about 800°C for a time sufficient to produce a precipitate of the active cathode material in step 44 of Flowchart 40, recovering the precipitated active cathode material in step 46 of Flowchart 40, and drying the recovered active cathode material at a temperature less than about 800°C in step 48 of Flowchart 40. The precipitate can be an active oxygen species derivative, an active oxygen species derivative combined with a hygroscopic species, or an active oxygen species combined with a hygroscopic species.

[0042] The hygroscopic species used to prepare the positive electrode active material can be any hygroscopic species that forms a precipitate when heated with the appropriate reactive oxygen species in solution. Typically, the hygroscopic species is a compound or substance that attracts water from its environment by chemical reaction, by containing water of hydration, or by physical adsorption. Specifically, the hygroscopic species can be substantially free of transition metals. Particularly useful hygroscopic materials can include one or more ionic and / or organic materials.

[0043] When the hygroscopic species includes one or more ionic substances, the ionic substances may include one or more ionic compounds, which are typically salts, and more typically chlorides, bromides, pentoxides, sulfides, and / or sulfates. The ionic substances may also be acids capable of donating protons.

[0044] When the hygroscopic species comprises one or more organic materials, the organic materials can be selected from any suitable organic compound or fragment of an organic compound containing one or more nitrogen or oxygen atoms, for example, the one or more organic materials or compounds can be selected from among toluxenone, toluxenone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives, quinone, quinone derivatives, benzoquinone, benzoquinone derivatives, diamine derivatives, phenazine, phenazine derivatives, quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, triazine, triazine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropenium derivatives, and amide derivatives.

[0045] Selected examples of hygroscopic species for the present disclosure include, inter alia, CH 14 Cl4N4 (benzenetetraamine tetrahydrochloride), C6H6O4 (hexaketocyclohexane octahydrate), C8H6O4 (terephthalic acid), LiOH (lithium hydroxide), NaOH (sodium hydroxide), C 13 H 22 NO3 (tetramethylpiperidin-1-oxyl-4-yl methacrylate), LiCl (lithium chloride), NaCl (sodium chloride), HCl (hydrogen chloride), HBr (hydrogen bromide), LiBr (lithium bromide), NaClO3 (sodium chlorate), P2O5 (diphosphorus pentoxide), H2S (hydrogen sulfide), H2SO4 (hydrogen sulfate), HClO3 (chloric acid), C7H6O2 (benzoic acid), C2HF3O2 (trifluoroacetic acid), HBO (metaboric acid), C7H6O3 (salicylic acid), C2H4O2 (acetic acid), C 16 H 32 O2 (palmitic acid), HSCN (thiocyanic acid), C3H6O3 (lactic acid), H3PO4 (phosphoric acid), CH2O2 (formic acid), C 12 H 23 N (dicyclohexylamine), C2H6N (dimethylamine), C6H5SH (thiophenol), C6H2O6 (rhodizonic acid), C 16 H8O6 (anthraquinone-2-3-dicarboxylic acid), C6H2Cl2O4 (chloranilic acid) and C22 H 24 It may contain N4O4 (naphthalene diimide).

[0046] The reactive oxygen species can be any species that includes one or more reactive oxygen species moieties. For example, the reactive oxygen species can include one or more reactive oxygen moieties such as peroxide, superoxide, superoxide radical, hydroxyl radical, peroxyl radical, hydroxyl radical, alkoxyl radical, singlet oxygen, hypochlorous acid, and alpha oxygen. In one embodiment of the present disclosure, the reactive oxygen species includes at least one peroxide moiety. The reactive oxygen species can be, among others, Li2O2 (lithium peroxide), HO2 (hydrogen peroxide), HOCl (hypochlorous acid), O2 *- (superoxide radical), NaO2 (sodium superoxide), NO * (nitroxyl radical), C6H5O * (phenoxyl radical) and 1 O2 (singlet oxygen) or O2 (singlet oxygen).

[0047] During reaction, reactive oxygen species is typically converted into reactive oxygen species derivative.This reactive oxygen species derivative can be any species derived from this reactive oxygen species, and this reactive oxygen species derivative can be distinguished from this reactive oxygen species in that it no longer contains active oxygen moieties such as peroxide, superoxide, superoxide radical, hydroxyl radical, peroxyl radical, hydroxyl radical, alkoxyl radical, singlet oxygen, hypochlorous acid and alpha oxygen.

[0048] Any method of preparing a solution comprising hygroscopic species and reactive oxygen species is suitable for purposes of the method of Flowchart 40. For example, preparing a solution comprising one or more hygroscopic species and one or more reactive oxygen species can include adding the desired hygroscopic species and reactive oxygen species to a single solution to produce the desired mixed solution. Alternatively, one or both of the hygroscopic species and reactive oxygen species can be first dissolved in a single solution, and then the hygroscopic species solution and the reactive oxygen species solution can be mixed to produce the mixed solution, or both can be added to an existing solution to produce the mixed solution.

[0049] The resulting solution is then heated to a temperature less than about 800°C but high enough to cause the formation of a precipitate of the desired positive electrode active material. The heating temperature is preferably less than about 600°C, and more preferably less than about 400°C. It should be appreciated that, because it is usually not possible to heat the solution to a temperature higher than the melting point of the solution, the mixed solution should be transferred to a sealed container or autoclave for heating under elevated pressure. The atmosphere of the sealed container or autoclave can be replaced with high-purity oxygen gas during the heating process.

[0050] When the mixed solution has been heated for a time sufficient to precipitate the positive electrode active material, the positive electrode active material can be recovered. Any suitable separation method can be used to recover the precipitated positive electrode active material, but typically, the precipitation mixture is filtered and washed. As part of the step of recovering the positive electrode active material, the filtered and washed positive electrode active material can be dried under vacuum or in an inert gas atmosphere, typically at a temperature less than about 800°C. The drying temperature is preferably less than about 600°C, and more preferably less than about 400°C.

[0051] Inspection or further processing of the recovered and dried positive electrode active material should be carried out under dry conditions, for example, in a sealed container or glove box with a dew point below −60° C. Such processing can be carried out in a dry room.

[0052] positive electrode active material

[0053] During preparation of the active cathode material, the hygroscopic species and the reactive oxygen species typically react to produce an active cathode material that includes one or more new materials. In one embodiment, the active cathode material includes at least a first active cathode material and a second active cathode material, where the first active cathode material and the second active cathode material are different materials.

[0054] When the positive electrode active material includes a first positive electrode active material and a second positive electrode active material, the first positive electrode active material and the second positive electrode active material may be in contact with each other on or in the positive electrode. The first positive electrode active material and the second positive electrode active material may have different solubilities in the electrolyte solution present in the battery's electrolyte. In some embodiments, when one of the first positive electrode active material and the second positive electrode active material may be at least slightly soluble in the electrolyte solution, the other positive electrode active material may be substantially insoluble in the electrolyte solution.

[0055] In one embodiment, the ratio of the solubility of the first positive electrode active material in the electrolyte solution to the solubility of the second positive electrode active material in the electrolyte solution is less than 0.5 at a given temperature. In another embodiment, the ratio of the solubility of the first positive electrode active material in the electrolyte solution to the solubility of the second positive electrode active material in the electrolyte solution is less than 0.2. In another embodiment, the ratio of the solubility of the first positive electrode active material in the electrolyte solution to the solubility of the second positive electrode active material in the electrolyte solution is less than 0.1. In another embodiment, the ratio of the solubility of the first positive electrode active material in the electrolyte solution to the solubility of the second positive electrode active material in the electrolyte solution is less than 0.01.

[0056] In one aspect of the present disclosure, the combination of the hygroscopic species 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 may be separate components of the cathode active material; for example, the cathode active material may include a heterogeneous mixture. Alternatively or additionally, the metal compound and the metal oxide may be related to each other within a complex, within a cluster, or within a crystal, a quasicrystal, or an amorphous matrix. In one embodiment, one or more of the hygroscopic species are metal compounds. Typically, the cathode active material includes the metal compound and the metal oxide such that the metal compound and the metal oxide are in contact with each other.

[0057] The metal compound of the cathode active material has an empirical formula M a R b which can be represented, where M is a metal, and each R moiety is independently selected from any suitable atom, molecule or radical such that M a R b is an inorganic or organometallic compound or complex. Each R moiety can 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 independent non-zero positive real numbers, provided that 0 < a < 7 and 0 < b < 7. Each R may be a fragment or substituent of a larger compound.

[0058] In one embodiment, one or more of the R moieties may independently be one or more of hydrogen, nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus and boron, or may include one or more thereof. Alternatively or additionally, each R can independently be an inorganic or organic group.

[0059] [[ID=二十]]Alternatively or additionally, the metal compound of the cathode active material has an empirical formula MR xIt can be represented by, provided that M is a metal, and R is a moiety that is an atom, molecule, or radical. R can have a formal oxidation state of -1, -2, or -3. Typically, R has a formal oxidation state of -1. The value of x is a non-zero positive real number, provided that 0 < x < 7. Each R moiety can be an organic group or a halogen. Typically, when R is an organic group, R is an organic group containing one or more heteroatoms independently selected from nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and boron.

[0060] Each R moiety that is an inorganic group can be selected particularly from hydrides, halides, oxides, hydroxides, chlorates, sulfides, metaborates, thiocyanates, amides, nitrides, and azides.

[0061] Each R moiety that is an organic group can contain one or more of carbon and hydrogen and can be a fragment or substituent of a larger substance. In some embodiments, the organic group is derived from a suitable organometallic or organic compound. In some embodiments, the organic group can be, by way of non-limiting examples, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkylamino group, an aryl group, an aromatic group, or any combination thereof, or can contain these. In some embodiments, the organic group can particularly contain heteroatoms such as boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine, bromine, etc., or combinations thereof. In some embodiments, the organic group can contain one or more aromatic groups. As used herein in the specification, the term "aromatic group" is intended to mean a functional group containing one or more aromatic rings. In some embodiments, the R moiety can contain carbon, hydrogen, or oxygen. In some embodiments, the R moiety is an organic group having 1 to 6 carbons.

[0062] In some embodiments, each R that is an organic group excludes alkali metals, alkaline earth metals, or transition metals.

[0063] In some embodiments, when the positive electrode active material includes first and second positive electrode active materials, at least one of the first and second positive electrode active materials includes an organic group. In some embodiments, the positive electrode active material includes an organic compound and / or an organic group.

[0064] Non-exclusive examples of suitable R moieties for the present disclosure include, among others, -H (hydride), -OH (hydroxyl), -COOH (carboxyl), -CH (alkyne), -CH2 (alkene), -CHO (aldehyde), -CO- (carbonyl), -COO- (ester), -O- (ether), -NH2 (amine), -CN (nitrile), alkyl halide, oxyhalide, alkane, alkene, alkyne, arene, phenyl, thiol, thial, sulfide, sulfoxide, sulfone, ketone, amide, alkyl halide, methoxide, ethoxide, epoxide, phenolic, nitride, nitrate, nitroso, quinone, imine, imide, azide, lactate, phosphate, formate, and cyanate.

[0065] Selected examples of metal compounds of the positive electrode active material include, among others, MOH, MCl, MBr, MClO3, M2S, M2SO4, MC7H5O, MC2F3O2, MCH3O, MBO2, MC7H5O3, MC2H3O2, MC 16 H 31 O2, MSCN, MC9H 18 N, MC3H5O, M3PO4, MCHO2, MBH4, MC 12 H 22 N, MNH2, MH, MC2H5S, MCH3O, MC2H6N, MC6H5O, MC6H5S, M3N, MN3, MC3H7O, M2C8H4O4, M2C6O6, MC 16 H8O6, M2C6H4O4, MC3H2O2, M2C6Cl4O2, MC6Cl4O2, MC3Cl2O, MC6H4O2, M2C6H4O2, MC3H2O and MC 22 H 24 N4O4, where M is a metal.

[0066] The metal compound of the positive electrode active material is represented by the empirical formula M' x Oy It can be represented by M′Ox / y, where M′ is a metal that may be the same as or different from M of the metal compound, x and y are positive real numbers other than zero, 0 < x < 7 and 0 < y < 7, and they may be the same or different. The metal oxide may be a metal superoxide, a metal superoxide radical, and / or a metal peroxide, or may contain them.

[0067] The positive electrode active material can contain a second chlorine compound. In some embodiments, the second chlorine compound contains a metal complex composed of chlorine. When the second chlorine compound contains a metal complex composed of chlorine, the metal complex composed of chlorine can be a metal chloride. The metal chloride can be represented by the empirical formula M″ c Cl d where M″ is a metal, and c and d are positive real numbers other than zero. In some embodiments, the second chlorine compound has 5% by mass or more of chlorine. Preferably, the second chlorine compound may have 10% by mass or more of chlorine. More preferably, the second chlorine compound may have 15% by mass or more of chlorine.

[0068] When the positive electrode active material contains a second chlorine compound, non-exclusive examples of the second chlorine compound are M″Cl, M″3ClO, M″3ClO2, M″Mn<00^00032>Ni 0.5 O 4-x Cl x (0 < x < 4), M″2FeSiO 4-x Cl x (0 < x < 4), M″2FeMn3O 8-0.5x Cl x (0 < x < 16), M″Ni 0.7 Co 0.3 O 2-x Cl x [[ID=^37]](0 < x < 2), M″Ni 0.33 Co<00000^45>Mnx 0.33 O 2-x Cl x (0 < x < 2), M″<^ 1+x Ni 0.33 Co 0.33 Mn 0.33 O2-x Cl x (0 < x < 2), M″3V2(PO4) 3-x Cl x (0 < x < 3), M″ 1.11 Ni 0.89 O 2-x Cl x (0 < x < 2), M″ 1.2 Mn 0.585 Ni 0.185 Fe 0.03 O 2-x Cl x (0 < x < 2), and M″Fe(PO4) 1-x Cl 3x can include (0 < x < 1).

[0069] Each of M, M’ and M″ may be the same or different. In one embodiment, one or more of M, M’ and M″ are selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc or aluminum.

[0070] The resulting cathode active material can include at least a portion of a metal compound and at least a portion of a metal oxide that are thought to form clusters together. In one aspect of the present disclosure, the resulting cluster has the empirical formula MaM’ b R c O d and can be represented by, where each of a, b, c and d is a non-zero real number that may be the same or different, and 0 < a < 7, 0 < b < 7, 0 < c < 7 and 0 < d < 7. In one embodiment, when M and M’ are the same, the resulting cluster has the empirical formula M a R b O c and can be represented by, where each of a, b and c is a non-zero real number that may be the same or different, provided that 0 < a < 7, 0 < b < 7 and 0 < c < 7.

[0071] The resulting positive electrode active material composition can include a ratio of metal compound to metal oxide that can range from 5:95 to 75:25 by weight. a R b :M' x O y The composition ratio of the positive electrode active material 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 positive electrode active material is at least about 25 wt% metal oxide. Preferably, the positive electrode active material is at least about 50 wt% metal oxide. More preferably, the positive electrode active material is at least about 75 wt% metal oxide.

[0072] In one embodiment, the active cathode material includes a first active cathode material and a second active cathode material, and as described above, one of the first and second active cathode materials can include a metal compound and the other active cathode material can include a metal oxide. In this embodiment, the first active cathode material can be a metal oxide and the second active cathode material can be a metal compound, and the metal compound exhibits higher solubility in the electrolyte solution than the metal oxide.

[0073] When the active cathode material includes a first active cathode material and a second active cathode material, at least one of the first and second active cathode materials can include one or more of hydrogen, nitrogen, chlorine, bromine, fluorine, sulfur, phosphorus, and / or boron.

[0074] In one embodiment, at least one of the first and second positive electrode active materials can include one or more of hydrogen, nitrogen, chlorine, sulfur, and / or phosphorus. Preferably, at least one of the first and second positive electrode active materials can include one or more of chlorine and / or sulfur. More preferably, at least one of the first and second positive electrode active materials can include chlorine for compatibility with the solid electrolyte.

[0075] When the positive electrode active material includes a first positive electrode active material and a second positive electrode active material, at least one of the first and second positive electrode active materials can include one or more metals. In one embodiment, the first positive electrode active material and the second positive electrode active material each independently include one or more metals. In another embodiment, the first and second positive electrode active materials both include at least one metal. In some embodiments, the metal or metals can be selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, or aluminum. In some embodiments, the metal or metals can be selected from lithium, sodium, potassium, magnesium, calcium, vanadium, zinc, or aluminum. In some embodiments, the metal or metals can be selected from lithium, sodium, magnesium, vanadium, or zinc, which are more easily oxidized and transported in the electrolyte.

[0076] If at least one of the first and second positive electrode active materials includes one or more metals, when a battery including the resulting positive electrode is charged, the metals in the first and second positive electrode active materials are oxidized and converted to metal ions and transported through the electrolyte.

[0077] When the first and second active cathode materials each independently comprise one or more metals, the metals in the first and second active cathode materials are oxidized and converted to metal ions and transported through the electrolyte when a battery including the resulting cathode is charged. When the first and second active cathode materials both comprise at least one metal, the metals in the first and second active cathode materials are oxidized and converted to metal ions and transported through the electrolyte when a battery including the resulting cathode is charged.

[0078] The average particle size of the positive electrode active material can be from about 5 nm to about 50 μm, and exhibits average pores of from about 0.1 nm to about 1 μm. Typically, the average particle size of the positive electrode active material is less than about 50 μm. Preferably, the average particle size of the positive electrode active material is greater than about 50 nm and less than about 40 μm. More preferably, the average particle size of the positive electrode active material is greater than about 200 nm and less than about 30 μm. Typically, the average pore size of the positive electrode active material is less than about 1 μm. Preferably, the average pore size of the positive electrode active material is greater than about 1 nm and less than about 500 nm. More preferably, the average pore size of the positive electrode active material is greater than about 5 nm and less than about 200 nm.

[0079] In some embodiments, the positive electrode active material is at least partially surrounded by a protective coating layer on its outer surface. The coating layer may have a thickness of about 1 nm to about 1 μm. More preferably, the protective coating layer has a thickness of about 5 nm to about 200 nm. If present, the protective coating layer may contain one or more of carbon and / or oxygen, each of which may exist as a compound or complex. The elements contained in the protective coating layer may be generated from a reactive gas that contacts the electrolyte. When the reactive gas is carbon monoxide and / or carbon dioxide, the elements contained in the protective coating layer on the positive electrode surface preferably contain one or more of carbon and / or oxygen. In some embodiments, the protective coating layer includes a metal oxide such as LiNbO3 or Li2CO3, and / or a metal halide such as LiCl or LiF. The purpose of the protective coating layer on the positive electrode active material is to avoid partial direct contact with the solid electrolyte material and prevent any potential parasitic reactions and / or interdiffusion of the solid electrolyte material into the positive electrode active material. The protective surface coating layer, if present, is optionally electrically insulating. "Electrically insulating" means that the protective coating on the positive electrode surface is -3 Preferably, the protective coating on the positive electrode surface has a conductivity of 10 S / cm or less. -5 More preferably, the protective coating on the positive electrode surface exhibits a conductivity of 10 S / cm or less. -7It has a conductivity of less than S / cm.

[0080] High-energy cathode

[0081] The active cathode materials disclosed herein can be used to prepare high-energy cathodes, as presented in Flowchart 50 of Figure 3. As shown, a method for manufacturing a cathode for use in a battery includes providing a solution comprising a hygroscopic species and an active oxygen species in step 51 of Flowchart 50, heating the solution at a temperature less than about 800°C for a time sufficient to form a precipitate of the active cathode material in step 52 of Flowchart 50, recovering the active cathode material in step 54 of Flowchart 50, drying the recovered active cathode material at a temperature less than about 800°C in step 56 of Flowchart 50, combining the recovered active cathode material with one or more of a conductive material, a polymer binder, a plasticizer, and a carboxylic acid in step 58 of Flowchart 50, and depositing the combined cathode material onto a current collector to form a cathode in step 60 of Flowchart 50.

[0082] Steps 51, 52, 54 and 56 of flowchart 50 are very similar to the corresponding steps 42, 44, 46 and 48 of flowchart 40 described above.

[0083] As shown in step 58 of flowchart 60, the active cathode material can be mixed with one or more of a conductive material, a polymer binder, a plasticizer, and a carboxylic acid. Typically, the active cathode material is mixed with a conductive material. Additionally, the active cathode material may be further mixed with one or more of a polymer binder, a plasticizer, and a carboxylic acid.

[0084] If the positive electrode includes a conductive material, it can be added to one of the hygroscopic species and the active oxygen species before preparing the positive electrode active material, or one or more positive electrode active materials can be mixed with the conductive material after the positive electrode active material is formed. Generally, the positive electrode active material is in contact with the conductive material. If the positive electrode includes a first positive electrode active material and a second positive electrode active material, at least one of the first and second positive electrode active materials is in contact with the conductive material.

[0085] When the positive electrode active material includes a metal compound and a metal oxide, the metal compound and the metal oxide are in contact with each other, and one or both of the metal compound and the metal oxide are in contact with the conductive material.

[0086] When the positive electrode includes an active positive electrode material and a conductive material, the positive electrode composition may include a ratio of active positive electrode material to conductive material that can range from 20:80 to 99:1 by weight. The ratio of active positive electrode material to conductive material can be approximately 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, or 99:1. Typically, the positive electrode composition is at least 20 wt% active positive electrode material. Preferably, the positive electrode composition is at least 40 wt% active positive electrode material. More preferably, the positive electrode composition is at least 60 wt% active positive electrode material.

[0087] Any conductive material that facilitates operation of the resulting positive electrode is a suitable conductive material for purposes of the present disclosure. In some embodiments, the conductive material comprises a porous carbon material, i.e., 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, 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 one embodiment, the conductive material comprises a porous carbon material selected from carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and / or graphene nanoribbons. When the positive electrode comprises a porous carbon material, carbon nanotubes and / or carbon nanofibers, and carbon nanotubes, are particularly preferred due to their high aspect ratio and durability.

[0088] In one embodiment, the conductive material comprises a porous carbon material having particles with an average particle size or diameter of about 50 nm to about 50 μm and an average pore size of about 0.1 nm to about 1 μm. Typically, the average particle size or diameter of the conductive material is less than 50 μm. Preferably, the average particle size of the conductive material is greater than about 10 nm and less than about 40 μm. More preferably, the average particle size of the conductive material is greater than about 50 nm and less than about 30 μm. Typically, the average pore size of the conductive material is less than 1 μm. Preferably, the average pore size of the conductive material is greater than about 1 nm and less than about 500 nm. More preferably, the average pore size of the conductive material is greater than about 5 nm and less than about 200 nm.

[0089] In some embodiments, the average particle size or diameter of the positive electrode active material and the conductive material are inversely related. In such embodiments, when the average particle size of the positive electrode 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, or vice versa. Typically, one or more of the positive electrode active material and the conductive material comprise 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.

[0090] In one embodiment, the step of mixing the positive electrode active material and the conductive material includes mixing the positive electrode 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. Positive electrodes containing porous carbon materials doped with nitrogen and / or fluorine are preferred, and nitrogen is particularly preferred because it enables lower charge transfer resistance. When present, the porous carbon material may include one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

[0091] In some embodiments, the conductive material is at least partially surrounded by a protective coating layer on the outer surface. The coating layer can have a thickness of about 1 nm to about 1 μm. Preferably, the protective coating layer has a thickness of about 2 nm to about 500 nm. More preferably, the protective coating layer has a thickness of about 5 nm to about 200 nm. When present, the protective coating layer can contain one or more of carbon and / or oxygen, each element of which can exist as a compound or complex. The elements contained in the protective coating layer can be generated from a reactive gas that is liquefied, dissolved, or contacted with an electrolyte. When the reactive gas is carbon monoxide and / or carbon dioxide, the elements contained in the protective coating layer on the positive electrode surface preferably include one or more of carbon and / or oxygen. In some embodiments, the protective coating layer contains a metal oxide, such as LiNbO3 or Li2CO3, and / or a metal halide, such as LiCl or LiF. The purpose of the protective coating layer of conductive material is to avoid any direct partial contact with the solid electrolyte material to prevent any potential parasitic reactions.

[0092] Any suitable conductive material, which may have the same or different formulation, can be used in the positive electrode of the present disclosure. The positive electrode active material and / or conductive material can be flat and / or particulate solid. When the positive electrode active material, conductive material, and / or electrolyte are particulate, the particles can have any suitable shape, including, among others, spherical, cubic, rectangular, conical, pyramidal, cylindrical, rectangular prism, hexagonal prism, hemispherical, triangular prism, pentagonal prism, octagonal prism, toroidal, octahedral, and dodecahedral.

[0093] If the positive electrode includes a polymer binder, it can be added to either the hygroscopic species or the active oxygen species before preparation of the positive electrode active material, or the positive electrode active material can be mixed with the polymer binder after it is formed.

[0094] The polymer binder can be added to facilitate the formation of a solid cathode from the cathode active material. Suitable polymer binders for purposes of this disclosure can include one or more of polycaprolactone, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinylpyrrolidone, poly(4-vinylpyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, and polycarbonate, among others. In certain embodiments, the polymer binder includes one or more of polyethylene glycol or polyvinylidene fluoride.

[0095] Alternatively, or in addition, the positive electrode can incorporate a plasticizer that can be used to make the resulting positive electrode softer and more flexible. The plasticizer can include one or more of succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, sulfonates, 3-methyl-oxazolidine, butylene carbonate, phthalic acid derivatives, trimellitic acid, adipates, sebacates, and maleates, among others. In certain embodiments, the plasticizer can include succinonitrile.

[0096] Alternatively, or additionally, the positive electrode can incorporate one or more carboxylic acids. The carboxylic acids, when present, can be monocarboxylic or polycarboxylic acids. When the carboxylic acid is a polycarboxylic acid, it is optionally oxalic acid.

[0097] As presented in step 60 of flowchart 50, a mixed cathode material including an active cathode material, and optionally one or more of a conductive material, a polymeric binder, a plasticizer, and a carboxylic acid, is deposited onto a current collector to form the desired cathode.

[0098] The current collector may comprise any suitable conductive material. In some embodiments, the positive electrode current collector comprises one or more metals, such as alkaline earth metals, transition metals, rare earth elements, post-transition metals, and alkali metals. In some embodiments, the positive electrode current collector comprises at least one of aluminum, aluminum alloys, nickel, nickel alloys, duplex stainless steel, and stainless steel. In one embodiment, the positive electrode current collector is a metallic current collector comprising a metal or metal alloy that also comprises one or more of molybdenum, titanium, and zirconium. In another embodiment, the positive electrode current collector comprises a metal or metal alloy that includes molybdenum. Molybdenum is particularly suitable for inclusion in the positive electrode current collector due to its high corrosion resistance. In an alternative embodiment, the positive electrode current collector is a conductive material comprising porous carbon in electrical contact with the positive electrode active material.

[0099] The positive electrode current collector can be solid or perforated. If perforated, the pore size of the positive electrode current collector can be from about 500 nm to about 1 mm with a pore spacing of from about 10 μm to about 100 mm.

[0100] The positive electrode material with additional conductive material, polymeric binder, and plasticizer, if present, can be applied to the current collector using any suitable application technique. For example, the mixed positive electrode material can be cast into a film and deposited onto the desired current collector.

[0101] The resulting positive electrode can be incorporated into a battery 10, as shown in FIG. 1. The positive and negative electrode current collectors can be the same and can be referred to as bipolar current collectors. The bipolar current collectors of the present disclosure can include alloys of one or more of molybdenum, titanium, and zirconium. Molybdenum is particularly suitable for inclusion in the positive electrode current collector due to its high corrosion resistance. The positive and negative electrodes are typically separated by an electrolyte separator 32. The battery components are typically held in a battery case or housing that surrounds the battery components and can maintain the battery components under a desired gas composition or atmosphere. The positive and / or negative electrodes can be in contact with an electrolyte 30. Regardless of how a battery is illustrated herein, it should be appreciated that the batteries of the present disclosure can take any conventional or suitable battery configuration, for example, by being formed as a button cell, pouch cell, prismatic cell, cylindrical cell, flow cell, alternating plate, or jelly roll, among others.

[0102] negative electrode active material

[0103] The negative electrode 18 can include an active negative electrode material. In some embodiments, the negative electrode includes one or more of lithium, sodium, potassium, magnesium, calcium, vanadium, aluminum, zinc, silicon, graphite, graphene, porous carbon, activated carbon, silicon compounds, metal oxides, and combinations thereof. The active negative electrode material can be present as a coating, foil, mesh or screen, or other separate negative electrode component. Alternatively, or additionally, the active negative electrode material can be incorporated into the negative electrode as a component or component compound. In some embodiments, the negative electrode includes a non-metal oxide as the active negative electrode material. In some embodiments, the negative electrode can include graphite. In some embodiments, the negative electrode can include silicon, graphite, graphene, activated carbon, or a metal, or a combination thereof. When the negative electrode includes a metal, the metal can be an alkali metal or an alkaline earth metal. In some embodiments, the negative electrode includes a metal oxide. In some embodiments, the negative electrode includes Li4Ti5O 12 , TiO2, TiNb2O7, Nb 16 W5O 55 , Nb 18 W 16 O 93 , Nb2O5, Li3VO4, H2Ti6O 13 , LiMnBO3, LiV 0.5 Ti 0.5 S2, Li3V2O5, Li x Metal oxides include V2O5, Li3MoO4, Li5W2O7, or any combination thereof.

[0104] The negative electrode active material can be generated in situ by carefully selecting components of the electrochemical cell, such as the electrolyte and / or additional components thereof, and, if necessary, applying a negative electrode current collector to the electrochemical cell. The selection of the negative electrode active material is not particularly limited, provided that the selected material is capable of storing and releasing ions. For example, the negative electrode active material can be selected from alkali metals (such as lithium, sodium, and / or potassium), alkaline earth metals (such as magnesium and / or calcium), amphoteric metals (such as aluminum and / or zinc), semimetals (such as boron, germanium, arsenic, antimony, tin, tellurium, polonium, and / or silicon), metal complexes, inorganic carbon (such as graphite, graphene, graphene oxide, reduced graphene oxide, activated carbon, carbon nanotubes, and carbon dots), sulfur, sulfides (such as titanium disulfide MV), and the like. 0.5 Ti 0.5 S2, where M is a metal, metal sulfide (M2S), metal polysulfide (e.g., M2S2, M2S4, M2S6, M2S8)), sulfur-containing compounds or substances (e.g., sulfates or organic sulfur compounds (e.g., polysulfur-random-(1,3-diisopropenylbenzene), sulfurized polyacrylonitrile)), oxides (e.g., M x Ti5O 12 , TiO2, TiNb2O7, Nb2O5, M x VO4, H2Ti6O 13 , M x MnBO3, M x V2O5, M x MoO4, M x W2O7, M' 1-x M″O2, M' 1-w (M″ x M'″ y)O2 and / or metal titanates), organic substances or compounds (e.g., truxenone, truxenone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives (e.g., 10-acetylphenothiazine, 10-[2-(2-methoxyethoxy)ethyl]-10H-phenothiazine), quinone, quinone derivatives (e.g., 2,2'-(2-vinylanthracene-9,10-diylidene)dimalononitrile, 2-vinylanthraquinone, anthraquinone-2,6-disulfonate, anthraquinone-1 ,8-disulfonate, anthraquinone-1-sulfonate, anthraquinone-1,5-disulfonic acid, 2,2'-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol)), diamine derivatives, phenazine, phenazine derivatives, quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, cyclohexane, cyclohexane derivatives, triazine, triazine derivatives, melamine, melamine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropenium derivatives, amide derivatives, amino acids, amino acid derivatives, biphenyls, phenylalanine ... viologens, viologen derivatives (e.g., ethyl viologen), nitrogen oxide derivatives), organic radicals (e.g., piperidine derivatives (e.g., 4-isothiocyanato-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-(2-iodoacetamido)-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6 ,6-tetramethylpiperidine 1-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-(2-chloroacetamido)-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6,6-tetramethyl-4-(2-propynyloxy)piperidine 1-oxyl, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-glycidyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl)sebacic acid, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl), pyrrolidine derivatives (e.g., 3-carboxy-2,2,5,5-tetramethylpiperidine ethylpyrrolidine 1-oxyl, 16-doxylstearic 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), or any combination thereof.

[0105] In some embodiments, the negative electrode active material can include one or more organic materials, as described above. When the negative electrode active material includes an organic material, the organic material can be selected from any suitable organic compound or fragment of an organic compound, as described above. In one aspect, the negative electrode active material includes an organic compound containing heteroatoms, such as boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine, and bromine, among others. Alternatively, or additionally, the negative electrode active material can include an organic group containing one or more aromatic groups.

[0106] Materials used as part of the positive electrode, excluding the positive electrode active material, such as conductive material, polymer binder, plasticizer, carboxylic acid, etc., can also be part of the negative electrode. When the negative electrode includes one or more additional materials, polymer binder, and plasticizer in addition to the conductive material, 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 applied to the desired current collector.

[0107] The negative electrode 18 can include a negative electrode material, which is a negative electrode active material. The particles of the negative electrode active material can be at least partially surrounded on their outer surfaces by a protective coating layer. The protective coating layer can have a thickness of about 1 nm to about 1 μm. Preferably, the protective coating layer has a thickness of about 2 nm to about 500 nm. More preferably, the protective coating layer has a thickness of about 5 nm to about 200 nm. In one embodiment, the protective coating layer on the negative electrode surface includes one or more of carbon and / or oxygen, and each element can exist as a compound or complex. The elements included in the protective coating layer on the negative electrode surface can be generated from a reactive gas. When the reactive gas is carbon monoxide and / or carbon dioxide, the elements included in the coating layer on the negative electrode surface preferably include one or more of carbon and / or oxygen. In some embodiments, the protective coating layer includes a metal oxide, such as LiNbO3 or Li2CO3, and / or a metal halide, such as LiCl or LiF. The purpose of the protective coating layer on the negative electrode active material is to avoid any direct partial contact with the solid electrolyte material to prevent any potential parasitic reactions and / or interdiffusion of the solid electrolyte material into the positive electrode active material. The protective surface coating layer, if present, is optionally electrically insulating. "Electrically insulating" means that the protective coating on the negative electrode surface is -3 Preferably, the protective coating on the negative electrode surface has a conductivity of 10 S / cm or less. -5 More preferably, the protective coating layer on the positive electrode surface has a conductivity of 10 S / cm or less. -7 It has a conductivity of less than S / cm.

[0108] The negative electrode current collector 26 can include a metal or metal alloy, such as copper, copper alloy, nickel, nickel alloy, duplex stainless steel, stainless steel, silver, silver alloy, or any combination thereof. In one embodiment, the negative electrode current collector is a metallic current collector including a metal or metal alloy that also includes one or more of molybdenum, titanium, and zirconium. In another embodiment, the negative electrode current collector includes a metal or metal alloy that includes molybdenum. Molybdenum is particularly suitable for inclusion in the negative electrode current collector due to its high corrosion resistance. In some embodiments, the negative electrode current collector can be a conductive material such as a porous carbon material that is or includes carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, microporous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, graphene nanoribbons, nitrogen-doped carbon, nitrogen-doped graphene, nitrogen-doped graphene oxide, and combinations thereof. In some embodiments, the conductive material is in the form of particles, powder, paper, foam, fiber, sheet, disc, rod, foil, or any combination thereof.

[0109] In some embodiments, batteries of the present disclosure can be so-called "anode-free" batteries. For example, an anode-free battery is shown schematically in FIG. 4. Battery 70 includes a cathode 72 according to the present disclosure, including a mixed cathode material 76, as described above, which can include one or more different cathode active materials, applied to a cathode current collector 74. Battery 70 does not include a cathode, but does incorporate an anode current collector 78, with the cathode and anode current collector separated by an electrolyte separator 80. The anode-free battery is held within a battery case or housing 82 that encloses the battery components and can maintain them under a desired gas composition or atmosphere. During charging, metal ions oxidized by the cathode are transported through the electrolyte and deposited on the anode current collector.

[0110] An alternative embodiment of an anode-free battery is shown schematically in FIG. 5 , where the anode-free battery 84 includes a cathode 72 according to the present disclosure, including a mixed cathode material 76, as described above, which may include one or more different cathode active materials, applied to a cathode current collector 74. The battery 84 does not include an anode and does not include an anode current collector. The anode-free battery is held within a battery case or housing 82 that encloses the battery components and can maintain the battery components under a desired gas composition or atmosphere. In this embodiment, during charging, metal ions oxidized by the cathode are transported through the electrolyte and deposited on the interior surface of the battery housing 82.

[0111] electrolyte

[0112] As mentioned above, the electrolyte 30 can include an electrolyte separator 32, which can be in contact with the positive electrode 14, or the separator 30 can be in contact with the electrolyte 30. If the electrochemical cell 12 includes a negative electrode, the electrolyte separator 32 can be disposed between the positive electrode 14 and the negative electrode 18. The separator 32 can be larger in either width or length than either or both of the positive and negative current collectors 24 and 26 to avoid contact between the positive and negative electrodes, between the positive and negative current collectors, between the positive and negative current collectors, or between the positive and negative current collectors.

[0113] An electrolyte separator 32 may be disposed between the positive electrode 14 and the negative electrode 18 and typically contains an electrolyte to provide for ion transport within the battery and acts as a conduit for ion transport through its interaction with the negative and positive electrode materials. The electrolyte separator may be in contact with the electrolyte. The separator may comprise an electrically insulating material. "Electrically insulating" means that the separator is electrically insulating. -5 This means that the separator has a conductivity of 10 S / cm or less. -7 More preferably, the separator has a conductivity of 10 S / cm or less. -9The separator has a conductivity of 0.1 S / cm or less. In some embodiments, the separator's electrically insulating material has a melting point greater than 200°C. Preferably, the separator's electrically insulating material may have a melting point greater than 300°C. More preferably, the separator's electrically insulating material may have a melting point greater than 400°C. In some embodiments, the separator's electrically insulating material has a porosity greater than 50%. Preferably, the separator's electrically insulating material may have a porosity greater than 70%. More preferably, the separator's electrically insulating material may have a porosity greater than 90%. The separator can include a polymeric material, such as a thin polymer film, such as polyethylene, polypropylene, polytetrafluoroethylene, or polyvinyl chloride, among others. Typically, the thin polymer film, when present, includes polypropylene and / or polyethylene. Alternatively, or additionally, the electrolyte separator can include nonwoven fibers (such as nylon, polyester, and glass, among others), glass, ceramic, or any combination thereof. In some embodiments, the separator comprises glass fiber, hi some embodiments, the separator comprises a surfactant coating or treatment to improve wettability with liquid electrolyte.

[0114] The electrolyte 30 is a material that can act as a route for ion transport within an electrochemical cell of a battery through interaction with the electrodes of the cell. The electrolyte 30 can be a liquid, solid, gel, or liquefied gas that includes an electrolyte material that is ionically conductive. The electrolyte 30 can include an electrolyte solvent. The electrolyte 30 may include water as the electrolyte solvent. The electrolyte material 36 is a 10 -10 S / cm or more and ionic conductivity of 10 -1 Preferably, the electrolyte material 36 is selected to have a conductivity of 10 S / cm or less. -8 S / cm or more and ionic conductivity of 10 -3 More preferably, the electrolyte material has a conductivity of 10 S / cm or less. -6 S / cm or more and ionic conductivity of 10 -5It has a conductivity of less than S / cm.

[0115] When the battery's positive electrode active material includes a first positive electrode active material and a second positive electrode active material, the electrolyte can include an electrolytic solvent. In one embodiment, the electrolyte and / or the electrolytic solvent can be a solid or semi-solid. In another embodiment, such an electrolyte further includes an additional solid or semi-solid. In another embodiment, such a battery includes a separator including a polymer material. When the electrolyte 30 includes a solid electrolyte material 36, the solid electrolyte material may be one or more of a polymer, a glass, a phosphate, a fluorophosphate, a carbonate, an amine, a borate, a fluoroborate, a halide, a halogenate, an oxohalide, an oxide (e.g., MO, MO, MO, MOH, MO, MO, MO, PO, MPO, MMO, where M is a metal or a metalloid), a perovskite, an inverse perovskite (e.g., MOBr, MOCl, MOHBr, MOHCl, where M is a metal or a metalloid), a LISICON-type electrolyte (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+3y M' x M” 2-x (Si y PO4)3, M 14 M'M”4O 16 , M 4-x M' x V xO4, provided that M is a metal or a semi-metal), 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 O 12 , provided that M is a metal or a semi-metal), sulfide (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, M2S, P2S5, M3PS4, MS2, M7M’PS8, M6PS5Br, M6PS5I, M3PO4, M3P7S 11 , M2M’S3, M4M’S4, M 4-2x M’ x M”S4, MM’S, M5M’S4, M 11-x M’ 2-x P 1+x S 12 , M 4-x M’ 1-x P x S4, M 10 M’P2S 12 , provided that 0 < x < 1, and M is a metal or a semi-metal), thio-LISICON type electrolyte (e.g., M (4-x) M’ (1-x) P xS4, where M is a metal or metalloid), oxynitride, or nitride, etc. (LISICON is an acronym for Lithium Super Ionic Conductor). The solid or semi-solid electrolyte material can be an electrolytic solvent or electrolyte, and can optionally include one or more electrolytic solvents and / or one or more salts dissolved in the electrolytic solvent.

[0116] When the electrolyte 30 is present in the electrochemical cell as a solid or semi-solid, the electrolyte 30 is optionally present in the form of a thin film, foil, tape, paper, sheet, layer, etc. The electrolytes of the present disclosure can be selected to include an electrolyte material 36 that is solid, the solid portion of the electrolyte material including a first chlorine compound. Selected, non-limiting examples of suitable first chlorine compounds for purposes of the present disclosure include MCl, M 7-x PS 6-x Cl x (0 <x<6)、M6PS5Cl、M7M’ x P 3-x S 11-y Cl y (0 <x<3、0<y<11)、M 11-x M' 2-x P 1+x S 12-y Cl y (0 <x<2、0<y<12)、M 4-x M' 1-x P x S 4-y Cl y (0 <x<1、0<y<4)、M 6+x M' x P 1-x S5Cl(0 <x<1)、M 2-x OHCl 1-x (0 <x<1)、M 3-x OH xContaining Cl(0 < x < 1), M3ClO, M4CL(OH)3, M5Cl3(OH)2, where M is a metal or a metalloid. Each M, M’, or M″ in the present disclosure can be selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, magnesium, zinc, boron, silicon, tin, gallium, germanium, and aluminum. M, M’, or M″ in the present disclosure can be an alkali metal because the inclusion of an alkali metal brings high energy density. When present, it may be preferable to use the same metal or metalloid of the electrolyte material in the positive electrode active material and / or the negative electrode active material.

[0117] When the electrolyte 30 exists as a solid within the electrochemical cell, the electrolyte 30 may optionally exist as a composition of solid particles. The average particle size of a suitable electrolyte material 36 can be from about 5 nm to about 30 μm and can exhibit an average pore size from 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. When the electrolyte 30 exists as a composition of solid particles, the average pore size of the electrolyte material can 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.

[0118] When electrolyte 30 includes a liquefied gas, the liquefied gas can include one or more of methane (e.g., methane, fluoromethane, difluoromethane), ethane (e.g., ethane, fluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane), propane (e.g., propane, 2-fluoropropane), butane (e.g., butane, fluorobutane), ethylene, acetylene, propylene, carbon monoxide, and carbon dioxide. The liquefied gas can be generated from a gas below its condensation temperature at its critical pressure or above its vapor pressure at its critical temperature.

[0119] When electrolyte 30 includes an organic liquid, the organic liquid can include one or more organic carbonates, ethers, esters, amides, halogenated liquids, nitriles, or ionic liquids.

[0120] When electrolyte 30 includes an organic carbonate, the organic carbonate can be, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, dipropyl carbonate, 4-vinyl-1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, diethyl 2,5-dioxahexanedioate, bis(2,2,2-trifluoroethyl)carbonate, 4-fluoro-1,3-dioxolan-2-one, dimethyl 2,5-dioxahexanedioate, or dibutyl carbonate, among others.

[0121] When electrolyte 30 comprises an ether, the ether can be, for example, dimethoxyethane, dimethoxymethane, dimethyl ether, diethyl ether, ethylene glycol, ethylene glycol derivatives (diglyme, triglyme, tetraglyme), tetrahydrofuran, dioxolane, or dioxane, among others.

[0122] When electrolyte 30 includes an ester, the ester can be, for example, triethyl borate, trimethyl borate, tris(2,2,2-trifluoroethyl) borate, 2,4,6-trimethoxyboroxine, tributyl borate, tributyl borate, trihexyl borate, or tripropyl borate, among others.

[0123] When electrolyte 30 includes an amide, the amide can be, for example, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylpropionamide, diethylpropionamide, 2,2,2-trifluorodimethylacetamide, or dipropylacetamide, among others.

[0124] When electrolyte 30 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).

[0125] When electrolyte 30 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-hexanetricarbonitrile, 1,2,2,3-propanetetracarbonitrile, malononitrile, fumaronitrile, valeronitrile, acrylonitrile, tolunitrile, methoxybenzonitrile, or 3-butoxypropionitrile, among others.

[0126] When the electrolyte 30 includes an ionic liquid, the ionic liquid may be, for example, an imidazolium derivative (e.g., 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 2,3-dimethyl-1-propylimidazolium bis(trifluoromethanesulfonyl)imide, imide, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-vinylimidazole bis(trifluoromethane sulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazolium trifluoromethanesulfonate, 3-ethyl-1-vinylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-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-methylimidazole bis(trifluoromethanesulfonyl)imide, 1-methyl-1H-imidazol-3-ium hexafluorophosphate, or 3,3'-(butane-1,4-diyl)bis(1-vinyl-3-imidazolium)bis(trifluoromethanesulfonyl)imide, etc.

[0127] When electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, a pyrrolidinium derivative, among others (e.g., 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium hexafluorophosphate, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, or 1-allyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, among others).

[0128] When the electrolyte 30 includes an ionic liquid, the ionic liquid may be, for example, a pyridinium derivative (e.g., 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-hexylpyridinium hexafluorophosphate, 1-ethyl-3-(hydroxymethyl)pyridinium ethyl sulfate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methyl ... The fluorophosphate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyrrolidinium tetrafluoroborate, 1-ethyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-methylpyridinium bis(trifluoromethanesulfonyl)imide, or 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium, etc.

[0129] When electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, a piperidinium derivative such as 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide or 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide.

[0130] When electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, an ammonium derivative such as methyltri-n-octylammonium bis(trifluoromethanefluorosulfonyl)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, among others.

[0131] When electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, a phosphonium derivative such as tributylmethylphosphonium bis(trifluoromethanesulfonyl)imide, tributyl(2-methoxyethyl)-phosphonium bis(trifluoromethanesulfonyl)imide, tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium hexafluorophosphate, or tributylmethyl-phosphonium bis(trifluoromethanesulfonyl)imide, among others.

[0132] When the electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, a morpholinium derivative or a sulfonium derivative (such as triethylsulfonium bis(trifluoromethanesulfonyl)imide).

[0133] When electrolyte 30 is present in the electrochemical cell as a solution including a solvent and a solute dissolved in the solvent, the solute may include, for example, one or more ionic metal complexes such as 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 tricyanomethanide, metal nitrate, metal halide, metal bis(oxalato)borate, metal difluoro(oxalato)borate, or metal perchlorate, among others.

[0134] Electrolyte 30 may optionally include one or more additives, which may be polymeric materials, plasticizers, phosphazenes, phosphates, sulfonyl ions, and carboxylic acids. When present, the polymeric materials may include, for example, one or more of polycaprolactone, polyacrylic acid, polymethylmethacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinylpyrrolidone, poly(4-vinylpyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, styrene butadiene rubber, and sodium carboxymethyl cellulose, in any combination. In one embodiment, the polymeric material specifically includes one of polyethylene oxide or polyvinylidene fluoride.

[0135] When the additive comprises a plasticizer, the plasticizer can include, for example, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, gamma butyrolactone, sulfolane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalic acid derivatives, trimellitic acid, adipate, sebacate, maleate, or any combination thereof, among others.

[0136] When the additive includes a phosphazene, the phosphazene can include, for example, one or more of pentafluoro(phenoxy)cyclotriphosphazene, phosphorus(trimer)nitride chloride, ethoxy(pentafluoro)cyclotriphosphazene, hexaphenoxycyclotriphosphazene, or hexafluorocyclotriphosphazene, among others.

[0137] When the additive includes a phosphate, the phosphate 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-ethylhexyldiphenyl phosphate, triamyl 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.

[0138] When the additive comprises a sulfonyl, the sulfonyl may comprise, for example, one or more of isopropyl methyl sulfone, dimethyl sulfone, dimethyl sulfite, dipropyl sulfone, 1,3-propane sultone, 3-methyl sulfolane, 1,4-butane sultone, tetrahydrothiophene 1,1-dioxide, 1,3,2-dioxathiolane 2,2-dioxide, 1,3,2 dioxathiolane 2-oxide.

[0139] When the additive includes a carboxylic acid, the additive 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 percent 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 %.

[0140] When electrolyte 30 is or includes a gel, the gel is typically obtained by mixing a suitable liquid electrolyte material (as described above) with a suitable solid electrolyte material (as described above). By "suitable," we mean that the liquid and solid electrolyte materials are physically and chemically compatible and, when mixed together in a selected ratio, provide an electrolyte gel exhibiting the desired viscosity and electrolytic properties.

[0141] In some embodiments, the battery may be referred to as a "mono-material" battery, in which the active cathode material disclosed herein may also serve as the electrolyte and / or separator. In such embodiments, the active cathode material that is not in contact with a conductive material or current collector functions as the electrolyte and / or separator.

[0142] When the battery 10 includes a cathode 14 and an electrolyte 30, the composition can include a cathode:electrolyte ratio that can range from 15:85 to 95:5 by weight. The cathode:electrolyte composition ratio can be approximately 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, or 95:5. Typically, the cathode to 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.

[0143] A solid-state battery refers to a compound that is a gas at any given temperature or pressure and can further include a reactive gas that chemically or electrochemically reacts with the solid electrolyte material or the electrode (cathode or anode) active material. In one embodiment of the present disclosure, the reactive gas can include a compound having at least one oxygen atom (e.g., CO, CO, O, N, O, N, and SO), at least one sulfur atom (e.g., S, COS, CS, SF, H, S, SO, CH, SH, (CH)S, and CHSH), and / or at least one chlorine atom (e.g., Cl, CCl, CH, CCl, CHClF, ClO).

[0144] By reacting with the solid electrolyte or electrode active materials, the reactive gas can chemically or electrochemically form a protective coating layer on the outer surface of one or more of the positive electrode active material, the negative electrode active material, and / or the conductive material. In some embodiments, the reactive gas is removed from the solid-state battery using a vacuum source after one or more formation cycles involving exposure to the reactive gas or after producing the desired protective coating layer on the surface of the cell components. The formation cycles can include applying a current or voltage to the battery either from the negative electrode to the positive electrode or from the positive electrode to the negative electrode. The resulting protective coating layer is expected to reduce charge transfer resistance between the electrode and the solid electrolyte material by preventing some direct contact with the solid electrolyte material and maximizing the contact area for ion transport without applying a significant amount of stack pressure. The reactive gas itself is not a positive or negative electrode active material, and the reactive gas should not participate in the redox reactions of the electrochemical cell during battery operation.

[0145] Although the description of various embodiments herein is written in terms of batteries having a single cell, it should be appreciated that the same or similar principles can be applied to battery assemblies including two or more battery cells (i.e., battery packs, etc.), and such multi-battery assemblies should be understood to be within the scope of the present disclosure.

[0146] Example 1: Fabrication of a high-energy positive electrode

[0147] Positive electrodes according to the present disclosure were fabricated and tested using the following procedure.

[0148] To prepare a 0.1M LiOH / 0.1M LiCl solution, lithium hydroxide (LiOH) monohydrate and lithium chloride (LiCl) hydrate were dissolved in a 1:4 oxalic acid (OA)-methanol (MeOH) mixture with vigorous stirring. 100 mg of carbon nanotubes (CNTs) were added to the solution with stirring, and the resulting mixture was sonicated for 10 minutes to interweave the carbon nanotubes. A solution consisting of hydrogen peroxide (H2O2) and urea peroxide (CH6N2O3) was added dropwise to the reaction mixture with vigorous stirring at a temperature of 65 °C.

[0149] 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, washing with acetone, and drying under vacuum at 110°C for 24 hours. The recovered material was then quickly transferred to an argon-filled glovebox with minimal exposure to air. The composition of the as-prepared active cathode material is expected to be one or more of LiCl-LiO and LiCl-LiO composites, and the resulting clusters can be empirically described as LiClO and LiClO, respectively.

[0150] Example 2: Preparation of solid electrolyte

[0151] The first solid electrolyte was prepared using inverse vulcanization of elemental sulfur. Predried elemental sulfur and 1,3-diisopropenylbenzene (DIB) were mixed in a 50:50 weight ratio and stirred on a hot plate in a glove box filled with argon at 180 °C for about 4 hours. During the inverse vulcanization, after the color changed from yellow to red, the mixture was cooled to room temperature overnight. Next, the resulting material was dissolved in chloroform together with predried LiCl and polyethylene oxide. The composition of the first solid electrolyte is expected to be a composite polymer material consisting of poly(S-r-DIB)-LiCl-PEO. Then, a polybenzimidazole (PBI) nanofiber sheet with a high porosity (90%) (thickness less than 15 μm) was immersed in the resulting solution, dried for about 1 hour, and repeated at least three times to ensure complete coverage of the surface of the separator. The resulting independent thin film can have a thickness of about 18 μm.

[0152] The second solid electrolyte precursor contains predried LiCl and LiOH. A few drops of methanol were added to the mixture consisting of LiCl and LiOH to form a paste, and the resulting paste was introduced into a TEFLON reactor and sealed. The reactor was heated at 250 °C for 48 hours before opening. Next, the reactor was cooled to room temperature and a vacuum pump was used to remove water from the reactor. The composition of the prepared second solid electrolyte is expected to be Li 2-x OHCl 1-x 、Li 3-x OH x Cl and Li3ClO, where 0 < x < 1. It was found that the melting point of the solid electrolyte is less than 270 °C. Next, the resulting solid electrolyte was placed on the outer surface of a stainless steel drum container surrounded by a heating element and connected to a stainless steel tube, and the inside of the container was filled with a predried mixed gas consisting of CO2 and Ar. The concept of the solid electrolyte reservoir is expected to maintain a manufacturing cost reduction to minimize the manufacturing space volume at a dew point of less than -60 °C.

[0153] Example 3 Fabrication of a Solid-State Electrochemical Cell

[0154] The positive electrode active material was mixed with Li2C6Cl4O2 as an additional positive electrode active material, carbon black as a conductive material, succinonitrile as a plasticizer, and polytetrafluoroethylene as a polymer binder. The resulting mixture was poured onto a 316L stainless steel bipolar current collector to form a positive electrode 90 for a battery cell 92. The prepared positive electrode was placed in a cylindrical cell with a PBI nanofiber separator 94 coated with a first solid electrolyte, as shown in FIG. 7. After assembly, a second solid electrolyte 96 in an external reservoir 98 was heated to above 300°C and liquefied, then introduced into the assembled cell 92 using a pump 100. The liquefied electrolyte 96 penetrated the pores of the separator and electrode, then cooled to room temperature and converted back to a solid phase. Inert CO2 is added to a reservoir 98 and introduced into the cell 90 along with the second solid electrolyte 96, where it is expected to form a protective layer on the outer surface of the electrode material to avoid some direct contact with the solid electrode material and to reduce charge transfer resistance between the electrode and the solid electrolyte material. Any remaining CO2 can be removed from the housing after one or more formation cycles of applying a current or voltage to the cell, for example, using a vacuum source (e.g., a vacuum pump) coupled to a port through the cell housing.

[0155] A close-up portion of the structure of cell 92 is shown in Figure 7. Sample portion 102 includes, from left to right, anode current collector 104, anode 106, electrolyte separator 108, cathode 110, and cathode current collector 112. Similarly, close-up portion 114 of electrolyte separator 108 shows the structure including solid glass electrolyte 116 surrounding high-temperature polymer 118 but separated from polymer 118 by solid polymer electrolyte 120.

[0156] Similarly, an enlarged portion 122 of the positive electrode 110 shows particles of electrode material 124 surrounded by a protective layer 126 disposed within a solid electrolyte 128 .

[0157] Example 4 Determination of the rechargeability of high energy batteries

[0158] The high-energy battery prepared in Example 3 was repeatedly discharged and recharged. As shown in Figure 8, the battery had a current of 0.1 mA / cm 2 The high capacity was maintained for 15 cycles at a current density of 0.1.

[0159] Example 5 Additional Selected Embodiments

[0160] This section describes additional aspects and features of the disclosed cathode active materials, cathodes, and batteries, presented without limitation as a series of headings, some or all of which may be presented in alphanumeric order for clarity and efficiency. Each of these headings can be combined in any suitable manner with one or more of the other headings and / or with the disclosure elsewhere in this specification. Some of the following headings explicitly refer to and further limit other headings, describing without limitation some examples of suitable combinations.

[0161] A1. A solid-state battery comprising an electrolyte comprising an electrolyte material and a positive electrode in contact with the electrolyte, wherein at least a portion of the electrolyte material is solid, the solid portion of the electrolyte material comprises a first chlorine compound, and the positive electrode comprises an active cathode material comprising a second chlorine compound.

[0162] A2. The solid-state battery of paragraph A1, wherein the solid-state battery is configured such that the first chlorine compound and the second chlorine compound are the same.

[0163] A3. The solid-state battery of paragraph A1, wherein the solid-state battery is configured such that the first chlorine compound is electrochemically converted to the second chlorine compound and the second chlorine compound is electrochemically converted to the first chlorine compound.

[0164] A4. The solid-state battery of paragraph A1, wherein the solid portion of the electrolyte material includes sulfur.

[0165] A5. The solid-state battery of paragraph A4, wherein the solid portion of the electrolyte material is formed by inverse vulcanization of sulfur.

[0166] A6. The solid-state battery of paragraph A1, wherein the first chlorine compound has a melting point of less than 700°C.

[0167] A7. The solid-state battery of paragraph A1, wherein the second chlorine compound includes a metal complex of chlorine.

[0168] A8. The solid-state battery of paragraph A1, wherein the positive electrode active material includes one or more metals selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, or aluminum.

[0169] A9. The solid-state battery of paragraph A8, wherein the solid-state battery is configured such that, upon charging of the solid-state battery, the metal of the positive electrode active material is oxidized to metal ions, and then the metal ions are transported through the electrolyte.

[0170] A10. The solid-state battery according to paragraph A1, wherein the positive electrode active material includes an organic compound and / or an organic group.

[0171] A11. The solid-state battery of paragraph A1, wherein the positive electrode further includes a conductive material in contact with the positive electrode active material.

[0172] A12. The solid-state battery of paragraph A11, wherein the conductive material and / or the positive electrode active material includes a protective coating layer.

[0173] A13. The solid-state battery of paragraph A11, wherein the conductive material comprises a porous carbon material selected from carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons.

[0174] A14. The solid-state battery according to paragraph A13, wherein the porous carbon material is doped with one or more heteroatoms independently selected from boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine, and bromine.

[0175] A15. The solid-state battery of paragraph A1, wherein the positive electrode further comprises one or more of a polymer binder, a plasticizer, or a carboxylic acid.

[0176] A16. The solid-state battery of paragraph A1, further comprising a negative electrode including a negative electrode active material.

[0177] A17. The solid-state battery of paragraph A1, further comprising a reactive gas in contact with or dissolved in the electrolyte.

[0178] A18. The solid-state battery of paragraph A17, wherein the reactive gas comprises oxygen, chlorine, and / or sulfur.

[0179] A19. The solid-state battery of paragraph A17, wherein the reactive gas comprises one or more of CO2, CO, Cl2, CCl4, CH3CCl3, CHClF2, ClO2, O2, N2O, NO2, SO2, S8, COS, CS2, SF6, H2S, SO2, CH3SH, (CH3)2S, and C2H5SH.

[0180] A20. The solid-state battery of paragraph A1, further comprising a bipolar current collector, the bipolar current collector comprising an alloy of one or more of molybdenum, titanium, and zirconium.

[0181] A21. The solid-state battery of paragraph A1, further comprising a separator, the separator comprising an electrically insulating material.

[0182] A22. The solid-state battery of paragraph A21, wherein the electrically insulating material of the separator has a melting point greater than 200°C.

[0183] A23. The solid-state battery of paragraph A21, wherein the electrically insulating material of the separator has a porosity of greater than 50%.

[0184] A24. The solid-state battery of paragraph A1, wherein the solid electrolyte material contains more than 3% by mass of chlorine.

[0185] A25. The solid-state battery of paragraph A1, wherein the second chlorine compound contains more than 5% by mass of chlorine.

[0186] A26. A solid-state battery comprising an electrolyte comprising an electrolyte material and a positive electrode in contact with the electrolyte, wherein at least a portion of the electrolyte material is solid, the solid portion of the electrolyte material being formed by inverse vulcanization of sulfur, and the positive electrode comprising a positive electrode active material.

[0187] Advantages, Features, and Benefits

[0188] Solid-state batteries comprising the cathode active materials and solid electrolyte materials of the present disclosure are economical and enable the fabrication of high-energy cells with high discharge capacities and high discharge potentials.

[0189] Selected batteries of the present disclosure have a 0.1 mA / cm 2 At the above current densities, the ratio of Li / Li + The electrode can produce an average working discharge potential of at least 2.0 V.

[0190] Selected batteries of the present disclosure have a 0.1 mA / cm 2 At the above current density, the battery exhibits a discharge specific capacity of at least 200 mAh / g based on the amounts of the first and second positive electrode active materials.

[0191] In some embodiments, the batteries of the present disclosure have a current density of 0.1 mA / cm 2 At the above current densities, the positive electrode can exhibit a discharge specific capacity of greater than 200 mAh / g, greater than 300 mAh / g, and greater than 400 mAh / g, based on the amount of the positive electrode active material.

[0192] Selected batteries of the present disclosure have a Li / Li ratio + In some embodiments, the batteries of the present disclosure can exhibit an average working discharge potential greater than 1.0 V vs. Li / Li+ Such batteries can exhibit average operating discharge potentials of greater than 2.0 V, greater than 3.0 V, or greater than 4.0 V at 0.1 mA / cm. 2 At the above current densities, the ratio of Li / Li + The electrode is capable of producing an average working discharge potential of at least 3.0 V.

[0193] Selected batteries of the present disclosure can produce high cell-level energy densities of greater than 500 Wh / kg, along with high discharge capacities and high discharge potentials, at low cell-level costs of less than $50 / kWh.

[0194] Selected batteries of the present disclosure, including batteries having a first active cathode material and a second active cathode material, can be substantially rechargeable. In one embodiment of the present disclosure, a battery can be considered substantially rechargeable if the battery exhibits a cycle count greater than 100. Alternatively, or additionally, selected batteries of the present disclosure, including batteries having a first active cathode material and a second active cathode material, can operate efficiently at room temperature, which in one embodiment can be defined as 15°C to 30°C. The active cathode materials of the present disclosure have a Li / Li + It exhibits a typical redox potential of over 3.0 V at 1000 kJ / cm².

[0195] "Combination" or "combinations" means any and all combinations of two related components to a plurality or all of such components, unless otherwise specified.

[0196] The description of method steps, whether shown in the drawings or described in the description, should not be considered to indicate a specific order of the method steps unless the order is specifically stated. The order of such steps may be different from that shown and described, and / or two or more steps may be performed concurrently or with partial concurrence unless otherwise specified.

[0197] The features and variations detailed in individual embodiments and examples may be freely combined with the features and variations of other examples and embodiments and may be used to characterize the invention as claimed without necessarily implying other details of the respective embodiments or examples.

[0198] The present disclosure described above may encompass numerous different embodiments having independent utility. While each of these embodiments has been disclosed in one or more exemplary forms, many variations are possible, and therefore the specific embodiments of the present disclosure disclosed and described herein should not be considered limiting. To the extent that section headings are used within this disclosure, such headings are for organizational purposes only. The subject matter of the present disclosure includes all novel and unobvious combinations and subcombinations of the various elements, features, functions, and / or properties disclosed herein. The following claims specifically set forth certain combinations and subcombinations that are believed to be novel and unobvious. Other combinations and subcombinations of features, functions, elements, and / or properties may be claimed in applications claiming priority from this or a related application. Such claims, whether broader, narrower, equal, or different in scope from the original claims, are also considered to be within the scope of the subject matter of the present disclosure.

Claims

1. an electrolyte comprising an electrolyte material; a solid-state battery comprising a positive electrode in contact with the electrolyte, at least a portion of the electrolyte material is solid, and the solid portion of the electrolyte material comprises a first chlorine compound; The solid-state battery, wherein the positive electrode includes a positive electrode active material including a second chlorine compound.

2. 2. The solid-state battery of claim 1, wherein the solid-state battery is configured such that the first chlorine compound and the second chlorine compound are the same.

3. 10. The solid-state battery of claim 1, wherein the solid-state battery is configured such that the first chlorine compound is electrochemically converted to the second chlorine compound, and the second chlorine compound is electrochemically converted to the first chlorine compound.

4. 10. The solid-state battery of claim 1, wherein the solid portion of the electrolyte material comprises sulfur.

5. 5. The solid-state battery of claim 4, wherein the solid portion of the electrolyte material is formed by inverse vulcanization of sulfur.

6. 10. The solid-state battery of claim 1, wherein the first chlorine compound has a melting point of less than 700°C.

7. 2. The solid-state battery according to claim 1, wherein the positive electrode active material comprises one or more metals selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc, or aluminum.

8. 8. The solid-state battery according to claim 7, wherein the solid-state battery is configured such that, upon charging of the solid-state battery, a metal of the positive electrode active material is oxidized to metal ions, and then the metal ions are transported through the electrolyte.

9. The solid-state battery according to claim 1 , wherein the positive electrode active material comprises an organic compound and / or an organic group.

10. 10. The solid-state battery of claim 1, wherein the positive electrode further comprises a conductive material in contact with the positive electrode active material.

11. 11. The solid-state battery of claim 10, wherein at least one of the conductive material or the positive electrode active material includes a protective coating layer.

12. The solid-state battery of claim 1 , further comprising a negative electrode comprising a negative electrode active material.

13. 10. The solid-state battery of claim 1, further comprising a reactive gas in contact with or dissolved in the electrolyte.

14. 10. The solid-state battery of claim 1, further comprising a bipolar current collector, the bipolar current collector comprising an alloy of one or more of molybdenum, titanium, and zirconium.

15. 10. The solid-state battery of claim 1, further comprising a separator, said separator comprising an electrically insulating material.

16. 16. The solid-state battery of claim 15, wherein the electrically insulating material of the separator has a melting point greater than 200°C.

17. 16. The solid-state battery of claim 15, wherein the electrically insulating material of the separator has a porosity greater than 50%.

18. 10. The solid-state battery according to claim 1, wherein the solid electrolyte material contains more than 3% by mass of chlorine.

19. 10. The solid-state battery of claim 1, wherein the second chlorine compound contains more than 5% by weight of chlorine.

20. an electrolyte comprising an electrolyte material; a solid-state battery comprising a positive electrode in contact with the electrolyte, at least a portion of the electrolyte material is solid, the solid portion of the electrolyte material being formed by inverse vulcanization of sulfur; The positive electrode comprises a positive electrode active material.

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