High-energy solid-state battery and manufacturing method thereof

Abstract

A solid state battery includes: an electrolyte having an electrolyte material wherein at least a portion of the electrolyte material is solid and the solid portion of the electrolyte material includes a first chlorine compound; and, a cathode in contact with the electrolyte, the cathode comprising a cathode active material, and wherein the cathode active material comprises a second chlorine compound. These cells can be economically stacked and can provide high energy density.

Description

Technical Field

[0001] The present invention generally relates to high energy solid-state batteries and methods of making solid-state batteries, the batteries comprising an electrolyte comprising a solid electrolytic material and a cathode comprising a cathode active material. Background Art

[0002] Batteries are ubiquitous in modern technology, used in a wide range of applications from small batteries for industrial and medical devices to large batteries for electric vehicles and grid energy storage systems. The most well-known and widely used battery technology today is probably the lithium-ion battery, which uses intercalated lithium compounds as one electrode material and uses lithium ions that shuttle between a cathode and an anode in an electrolyte pool. While lithium-ion batteries have many advantages, they offer relatively low energy density and can require expensive materials to manufacture.

[0003] Solid-state batteries are often considered the future of lithium-ion battery technology. At least in theory, solid-state batteries can outperform today's lithium-ion batteries in many aspects, including safety and energy density. However, in practical applications, such batteries are too expensive to manufacture and cannot achieve better safety and higher energy density than traditional lithium-ion batteries. The first generation of all-solid-state batteries includes solid-state electrolytes. Although such solid-state electrolytes have high ionic conductivity and low grain boundary resistance, they may require a large stacking pressure (i.e., more than 10MPa) and an extremely dry manufacturing environment (i.e., a dew point below -60°C), and the properties of the solid-state electrolyte materials themselves make it difficult to transform them into independent films with a thickness of less than 20 microns.

[0004] Improved solid-state batteries are needed that include highly compatible cathode and electrolyte materials that can provide higher energy density (>500Wh / kg), more economical manufacturing costs, and lower material costs, while exhibiting greater electrochemical reversibility, longer cycle life, and reduced fire and explosion risks. Summary of the invention

[0005] The present invention is directed to a solid-state battery having an electrolyte and a cathode. The electrolyte includes an electrolyte material, wherein at least a portion of the electrolyte material is solid, and the solid portion of the electrolyte material includes a first chlorine compound. The cathode is in contact with the electrolyte, and the cathode includes a cathode active material including a second chlorine compound.

[0006] The disclosed features, functions, and advantages of the disclosed batteries, cathodes, and cathode active materials can be achieved independently in various embodiments of the present disclosure or may be combined together in yet other embodiments, further details of which can be seen with reference to the following description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0009] Figure 3 is a flow chart of an illustrative method of making a cathode according to the present disclosure.

[0010] Figure 4 is a semi-schematic diagram of an illustrative anode-less battery according to the present disclosure.

[0011] Figure 5 is a semi-schematic diagram of another illustrative anode-less battery according to the present disclosure.

[0012] Figure 6 is a schematic illustration showing the fabrication of a solid-state battery including an electrolyte and a cathode fabricated according to the present disclosure.

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

[0014] Figure 8 is a graph demonstrating the advantageously high rechargeability of an illustrative battery according to the present disclosure. Specific embodiments

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

[0016] "Cathode active material" refers to the portion of the cathode that is responsible for supplying ions through the electrolyte and supplying electrons through an external circuit when the battery is charged, and is responsible for accepting ions through the electrolyte and accepting electrons through an external circuit when the battery is discharged. "Anode active material" refers to the portion of the anode that is responsible for supplying ions through the electrolyte and supplying electrons through an external circuit when the battery is discharged, and is responsible for accepting ions through the electrolyte and accepting electrons through an external circuit when the battery is charged. Both cathode active materials and anode active materials participate in electrochemical redox reactions by transporting ions through the electrolyte and / or transporting electrons through an external circuit.

[0017] During charging and discharging of the battery, any coating, natural or artificial layer, any kind of protective layer (when present) on the surface of the cathode active material or the anode active material that does not participate in the electrochemical redox reaction should not be considered as part of the corresponding active material.

[0018] "Solid-state battery" refers to a battery having an electrolyte including an electrolyte material, wherein at least a portion of the electrolyte material is solid. "All-solid-state battery" refers to a solid-state battery having an electrolyte including an electrolyte material, wherein all of the electrolyte material is solid. The solid portion of the electrolyte material of the solid-state battery of the present disclosure may be greater than 50 wt.% of the electrolyte material, preferably greater than 75 wt.% of the electrolyte material, and more preferably 100 wt.% of the electrolyte material.

[0019] "Inverse sulfidation" refers to a solvent-free polymerization process that produces polymers containing chains of sulfur atoms. The polymers produced by inverse sulfidation are composed of long straight chains of sulfur interspersed with organic linkers. The inverse sulfidation polymerization method using sulfur allows the manufacture of solid electrolyte materials with physical properties that enable them to form thin, self-supporting films.

[0020] "Redox reaction" refers to a type of chemical reaction in which the oxidation state of the participating atoms, molecules, free radicals or ions is changed by gaining or losing electrons. Redox reactions are characterized by the actual or formal transfer of electrons between chemical species, most commonly one species undergoing oxidation and the other undergoing reduction.

[0021] "Current collector" refers to a component adjacent to an electrode (cathode or anode) that is configured to transfer current from a fixed portion of a circuit of an electrochemical cell to a mobile portion, or vice versa. A current collector is a bridging component that collects the current generated at an electrode and provides a connection to an external circuit. A current collector is typically adjacent to a cathode or anode. A bipolar current collector may be adjacent to both a cathode and an anode, or both a cathode and an anode may be coated on either or both sides of a bipolar current collector. In some embodiments, the current collector includes a conductive material, i.e., a porous carbon material. The porous carbon material may 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 provides ion transport within an electrochemical cell. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes. In particular, during charging of the electrochemical cell, the electrolyte can facilitate the movement of ions from the cathode to the anode, and during discharge, facilitates the movement of ions from the anode to the cathode.

[0023] As used herein, "room temperature" is any temperature within the range of air temperatures that most people prefer for indoor settings and feel comfortable when wearing typical indoor clothing. More specifically, room temperature includes temperatures of 15°C to 30°C (or 59°F to 86°F).

[0024] As used herein, "solubility" refers to the maximum weight of a material that can be dissolved in a given amount of solvent at a given temperature. "At least slightly soluble" as used herein means that less than 1,000 weight of electrolytic solvent is required per unit weight of cathode active material at a given temperature. "Practically insoluble" as used herein means that more than 10,000 weight of electrolytic solvent is required per unit weight of cathode active material at a given temperature.

[0025] As used herein, "semisolid" refers to a material that is in a state between a solid and a liquid. Although similar to a solid in some respects, such as having the ability to support its own weight and maintain its shape, a semisolid material also has some properties of a liquid, such as deforming when pressure is applied and flowing under pressure. The terms "quasi-solid", "semisolid" and "semi-liquid" may be used interchangeably to refer to a semisolid material. Typically, the viscosity of a semisolid material ranges from 10 mPas to 100,000 mPas.

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

[0027] "Including," "comprising," and "having" (and variations thereof) are used interchangeably to mean including but not necessarily limited to, and are open-ended terms that 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, etc., and are not intended to indicate sequence or numerical limitations.

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

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

[0031] like Figure 1As shown, the solid-state battery 10 of the present disclosure includes at least one solid-state electrochemical cell 12 including a cathode 14 having a cathode active material 16 and an electrolyte 30. Each solid-state electrochemical cell 12 may also include an anode 18 including an anode active material 20.

[0032] The electrolyte 30 and cathode active material 16 of the electrochemical cell 12 are selected so that at least a portion of the electrolyte material 36 of the electrolyte 30 is solid, and 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 serve as both the cathode active material and the electrolyte material. In certain embodiments, the solid-state battery can be configured so 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.

[0033] The solid-state electrochemical cell 12 may also include a separator 32 that separates the cathode from the anode or anode current collector. In certain embodiments, the electrolyte itself may also serve as such a separator. The electrolyte 30 and / or separator 32 may be configured to be larger than one or both of the cathode current collector 24 and the anode current collector 26 in width and / or length to avoid contact between the anode 18 and the cathode 14.

[0034] In some cases, the disclosed solid-state electrochemical cell 12 includes an anode current collector 26 but does not initially contain an anode active material 20. The anode active material 20 may be deposited on or intercalated with the anode current collector 26 during initial charging of the solid-state battery 10 including the electrochemical cell 12. In this case, the electrolyte 30 may be positioned in the cathode 14 and / or positioned between the anode current collector 26 and the cathode 14. In certain embodiments, the anode current collector 26 and / or the cathode current collector 24 corresponds to a battery housing 34 of the self-charging electrochemical cell 10.

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

[0036] In certain embodiments, the chlorine mass percentage of the first chlorine compound is greater than or equal to 3. Preferably, the chlorine mass percentage of the first chlorine compound may be greater than or equal to 6. More preferably, the chlorine mass percentage of the first chlorine compound may be greater than or equal to 9.

[0037] In some embodiments, the cathode active material of the solid-state battery includes one or more metals selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc or aluminum. Preferably, the cathode active material may include one or more metals selected from lithium, sodium, potassium, magnesium, calcium, vanadium, copper, zinc or aluminum. More preferably, the cathode active material may include one or more metals selected from lithium, sodium, potassium, magnesium, zinc or aluminum. In some embodiments, the solid-state battery is configured so that the metal of the cathode active material is oxidized to metal ions when the solid-state battery is charged, so that the metal ions can then be transported via the electrolyte.

[0038] In certain embodiments, the solid portion of the electrolyte material 36 of the solid-state battery 10 includes sulfur. When the solid portion of the electrolyte material 36 includes sulfur, the solid portion may be manufactured by inverse sulfidation of sulfur.

[0039] In one aspect of the present disclosure, the disclosed solid-state battery includes an electrolyte 30 containing an electrolyte material 36 and a cathode 14 in contact with the electrolyte 30, wherein at least a portion of the electrolyte material 36 is solid, and the solid portion of the electrolyte material is produced by reverse sulfidation of sulfur, wherein the cathode includes a cathode active material 16.

[0040] Preparation of cathode active materials

[0041] Figure 2 Flowchart 40 of the present disclosure illustrates an illustrative method for making a high energy cathode active material according to the present disclosure. The method includes: preparing a solution of a hygroscopic substance and a reactive oxygen substance at step 42 of flowchart 40; heating the solution at a temperature below about 800° C. for a sufficient time to form a precipitate of cathode active material at step 44 of flowchart 40; collecting the precipitated cathode active material at step 46 of flowchart 40; and drying the collected cathode active material at a temperature below about 800° C. at step 48 of flowchart 40. The precipitate may be a reactive oxygen substance derivative, a reactive oxygen substance derivative combined with a hygroscopic substance, or a reactive oxygen substance combined with a hygroscopic substance.

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

[0043] In the case where the hygroscopic substance includes one or more ionic materials, the ionic materials may include one or more ionic compounds, wherein the ionic compounds are typically salts, and more typically chlorides, bromides, pentoxides, sulfides and / or sulfates. The ionic material may also be an acid capable of donating protons.

[0044] In the case where the hygroscopic substance comprises one or more organic materials, the organic materials may be selected from any suitable organic compound or fragment of an organic compound incorporating one or more nitrogen or oxygen atoms. For example, the one or more organic materials or organic compounds may be selected from: trimerized indanone, trimerized indanone 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, cyclopropene derivatives and amide derivatives.

[0045] Examples of the selection of hygroscopic materials for use in the present disclosure may include CH 14 Cl4N4 (benzenetetramine tetrahydrochloride), C6H 16 O 14 (hexoketocyclohexane octahydrate), C8H6O4 (terephthalic acid), LiOH (lithium hydroxide), NaOH (sodium hydroxide), C 13 H 22 NO3 (tetramethylpiperidin-1-oxy-4-yl methacrylate), LiCl (lithium chloride), NaCl (sodium chloride), HCl (hydrogen chloride), HBr (hydrogen bromide), LiBr (lithium bromide), NaClO3 (sodium chlorate), P2O5 (phosphorus pentoxide), H2S (hydrogen sulfide), H2SO4 (bisulfate), HClO3 (chloric acid), C7H6O2 (benzoic acid), C2HF3O2 (trifluoroacetic acid), HBO (boric acid), C7H6O3 (salicylic acid), C2H4O2 (acetic acid), C 16 H 32 O2 (palmitic acid), HSCN (thiocyanate), C3H6O3 (lactic acid), H3PO4 (phosphoric acid), CH2O2 (formic acid), C 12 H 23N (dicyclohexylamine), C2H6N (dimethylamine), C6H5SH (benzenethiol), C6H2O6 (rose bengal acid dihydrate), C 16 H8O6 (anthraquinone-2,3-dicarboxylic acid), C6H2Cl2O4 (chloroaniline) and C 22 H 24 N4O4 (naphthalene diimide), etc.

[0046] The reactive oxygen species may be any substance that includes one or more reactive oxygen moieties. For example, the reactive oxygen species may include one or more reactive oxygen moieties such as peroxides, superoxides, superoxide radicals, hydroxyl radicals, peroxyl radicals, perhydroxyl radicals, hydroperoxyl radicals, alkoxyl radicals, singlet oxygen, hypochlorous acid, and α-oxygen. In one embodiment of the present disclosure, the reactive oxygen species includes at least one peroxide moiety. The reactive oxygen species may be selected from Li2O2 (lithium peroxide), H2O2 (hydrogen peroxide), HOCl (hypochlorous acid), O2* - (superoxide radical), NaO2 (sodium superoxide), NO* (nitroxyl radical), C6H5O* (phenoxy radical) and 1 O2 (singlet oxygen), etc.

[0047] Upon reaction, the reactive oxygen species is typically converted to a reactive oxygen species derivative. The reactive oxygen species derivative can be any substance derived from the reactive oxygen species and is distinguished from the reactive oxygen species in that the reactive oxygen species derivative no longer includes a reactive oxygen moiety, such as peroxide, superoxide, superoxide radical, hydroxyl radical, peroxyl radical, perhydroxyl radical, hydroperoxyl radical, alkoxyl radical, singlet oxygen, hypochlorous acid, and alpha-oxygen.

[0048] Any method of preparing a solution of a hygroscopic substance and a reactive oxygen substance is a suitable method for the purpose of the method of flow chart 40. For example, preparing a solution of one or more hygroscopic substances and one or more reactive oxygen substances may include adding each of the desired hygroscopic substances and reactive oxygen substances to a single solution to form the desired combined solution. Alternatively, one or both of the hygroscopic substance and the reactive oxygen substance may first be dissolved in a solvent, and then the hygroscopic substance solution and the reactive oxygen substance solution may be mixed to form the combined solution, or both may be added to an existing solution to form the combined solution.

[0049] The resulting solution is then heated at a temperature less than about 800°C but high enough to cause the formation of a precipitate of the desired cathode active material. The heating temperature is preferably less than about 600°C, and more preferably less than about 400°C. It should be understood that it is generally not possible to heat the solution to a temperature above the boiling point of the solution under standard conditions, so the combined solution should be transferred to a sealed container or autoclave to be heated under elevated pressure. During the heating process, the atmosphere of the sealed container or autoclave can be replaced with high purity oxygen.

[0050] When the combined solution has been heated for a sufficient time to form a precipitate of cathode active material, the cathode active material can be collected. Any suitable separation method can be used to collect the cathode active material precipitate, but the precipitate mixture is generally filtered and washed. Including in the step of collecting the cathode active material, the filtered and washed cathode active material can be dried under vacuum or under an inert gas atmosphere, typically at a temperature below about 800°C. The drying temperature is preferably less than about 600°C, and more preferably less than about 400°C.

[0051] The collected and dried cathode active material should be tested or further processed under dry conditions, such as in a glove box or sealed container with a dew point less than -60° C. Such processing can be performed in a dry room.

[0052] Cathode active material

[0053] During the preparation of the cathode active material, the hygroscopic species and the reactive oxygen species typically undergo a reaction to produce a cathode active material comprising one or more new materials. In one embodiment, the cathode active material comprises at least a first cathode active material and a second cathode active material, wherein the first and second cathode active materials are different materials.

[0054] When the cathode active material comprises a first cathode active material and a second cathode active material, the first cathode active material and the second cathode active material may be in contact with each other on the cathode and / or in the cathode. The first cathode active material and the second cathode active material may have different solubility in the electrolytic solvent present in the electrolyte of the battery. In certain embodiments, one of the first cathode active material and the second cathode active material may be at least slightly soluble in the electrolytic solvent, while the other cathode active material may be substantially insoluble in the electrolytic solvent.

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

[0056] In one aspect of the present disclosure, a combination of a hygroscopic substance and a reactive oxygen substance produces a cathode active material comprising a metal compound and a metal oxide. The metal compound and the metal oxide can be separate components of the cathode active material, such as in the case where the cathode active material comprises a heterogeneous mixture. Alternatively or additionally, the metal compound and the metal oxide can be bound to each other in a complex, cluster, or crystalline, quasi-crystalline, or amorphous matrix. In one embodiment, one or more of the hygroscopic substances are metal compounds. Typically, the cathode active material comprises a metal compound and a metal oxide such that the metal compound and the metal oxide are in contact.

[0057] The metal compound of the cathode active material can be described by the empirical formula M a R b where M is a metal, and each R moiety is independently selected from any suitable atom, molecule, or radical 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 positive non-zero real numbers, where 0 < a < 7 and 0 < b < 7. Each R can be a fragment or substituent of a larger compound.

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

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

[0060] Each R moiety, being an inorganic moiety, may be selected from hydrides, halides, oxides, hydroxides, chlorates, sulfides, sulfates, metaborate, thiocyanates, amides, nitrides, azides, and the like.

[0061] Each R part as an organic part can include one or more carbon and hydrogen, and can be a fragment or substituted part of a larger material. In certain embodiments, the organic part is derived from a suitable organic material or organic compound. In certain embodiments, the organic part can be or include, as a non-limiting example, 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. In certain embodiments, the organic part can include heteroatoms, such as boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine, bromine, etc., or any combination thereof. In certain embodiments, the organic part can include one or more aromatic groups. As used herein, the term "aromatic group" refers to a functional group comprising one or more aromatic rings. In certain embodiments, the R part can include carbon, hydrogen or oxygen. In certain embodiments, the R part is an organic part containing 1-6 carbons.

[0062] In some embodiments, each R as an organic moiety does not include an alkali metal, an alkaline earth metal, or a transition metal.

[0063] In some embodiments, when the cathode active material comprises first and second cathode active materials, at least one of the first and second cathode active materials comprises an organic moiety. In some embodiments, the cathode active material comprises an organic compound and / or an organic moiety.

[0064] Non-exclusive examples of suitable R moieties for use in the present disclosure can include -H (hydride), -OH (hydroxyl), -COOH (carboxyl), -CH (alkyne), -CH2 (alkene), -CHO (aldehyde), -CO- (carbonyl), -COO- (ester), -O- (ether), NH2- (amine), -CN (nitrile), alkyl halides, oxyhalides, alkanes, alkenes, alkynes, arenes, phenyls, thiols, thioaldehydes, sulfides, sulfoxides, sulfones, ketones, amides, alkyl halides, methoxides, ethoxides, epoxides, phenolates, nitrides, nitrates, nitroso, quinones, imines, imides, azides, lactates, phosphates, formates, and cyanates, among others.

[0065] Examples of selected metal compounds of the cathode active material may include 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, etc., where M is a metal.

[0066] The metal oxide of the cathode active material can be represented by the empirical formula M′ x O y Description, wherein M' is a metal which may be the same as or different from M of the metal compound, and wherein x and y are each positive non-zero real numbers which may be the same or different, and wherein 0<x<7, 0<y<7. The metal oxide may be or include a metal superoxide, a metal superoxide radical and / or a metal peroxide.

[0067] The cathode active material may include a second chlorine compound. In some embodiments, the second chlorine compound includes a metal complex of chlorine. When the second chlorine compound includes a metal complex of chlorine, the metal complex of chlorine may be a metal chloride. The metal chloride may be represented by the empirical formula M” c Cl d Description, wherein M" is a metal, c and d are non-zero positive real numbers. In some embodiments, the chlorine mass percentage of the second chlorine compound is greater than or equal to 5. Preferably, the chlorine mass percentage of the second chlorine compound may be greater than or equal to 10. More preferably, the chlorine mass percentage of the second chlorine compound may be greater than or equal to 15.

[0068] When the cathode active material includes a second chlorine compound, non-exclusive examples of the second chlorine compound may include M"Cl, M"3ClO, M"3ClO2, M"Mn 1.5 Ni 0.5 O 4-x Cl x (0 <x<4)、M”2FeSiO4-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 (0 < x < 2), M”Ni 0.33 Co 0.33 Mn 0.33 O 2-x Cl x (0 < x < 2), M” 1+ x Ni 0.33 Co 0.33 Mn 0.33 O 2-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 (0 < x < 1).

[0069] Each of M, M', and M” can be the same or different. In one embodiment, one or more of M, M', and M” can be 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, in combination, form clusters. In one aspect of the present disclosure, the resulting clusters can be described by the empirical formula M a M′ b R c O d , where each of a, b, c, and d is a positive non - zero real number that can be the same or different, and where 0 < a < 7, 0 < b < 7, 0 < c < 7, and 0 < d < 7. In one embodiment, M and M' are the same, and the resulting clusters can be described by the empirical formula M a R b O cTo describe, where each of a, b, c is a positive non-zero real number, they can be the same or different, and where 0<a<7, 0<b<7 and 0<c<7.

[0071] The resulting cathode active material composition may include a ratio of metal compound:metal oxide that may vary between 5:95 and 75:25 by weight. a R b The composition ratio of M'xOy may be about 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30 or 75:25. Typically, the cathode active material contains at least 25 wt% of the metal oxide. Preferably, the cathode active material contains at least about 50 wt% of the metal oxide. More preferably, the cathode active material contains at least about 75 wt% of the metal oxide.

[0072] In one embodiment, the cathode active material includes a first cathode active material and a second cathode active material, as described above, one of the first and second cathode active materials may include a metal compound, and the other may include a metal oxide. In this embodiment, the first cathode active material may be a metal oxide, the second cathode active material may be a metal compound, and the solubility of the metal compound in the electrolytic solvent is higher than that of the metal oxide.

[0073] When the cathode active material includes a first cathode active material and a second cathode active material, at least one of the first and second cathode active materials may 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 cathode active materials may include one or more of hydrogen, nitrogen, chlorine, sulfur and / or phosphorus. Preferably, at least one of the first and second cathode active materials may include one or more of chlorine and / or sulfur. More preferably, at least one of the first and second cathode active materials may include chlorine to make it compatible with the solid electrolyte.

[0075] In the case where the cathode active material includes a first cathode active material and a second cathode active material, at least one of the first and second cathode active materials may include one or more metals. In one embodiment, each of the first cathode active material and the second cathode active material individually includes one or more metals. In another embodiment, the first and second cathode active materials both include at least one metal. In some embodiments, one or more metals may be selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc or aluminum. In some embodiments, one or more metals may be selected from lithium, sodium, potassium, magnesium, calcium, vanadium, zinc or aluminum. In some embodiments, one or more metals may be selected from lithium, sodium, magnesium, vanadium or zinc because they are more easily oxidized and transported in the electrolyte.

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

[0077] In the case where each of the first and second cathode active materials individually includes one or more metals, when a battery including the resulting cathode is charged, the metals of the first and second cathode active materials are oxidized, converted into metal ions, and transported through the electrolyte. In the case where both the first and second cathode active materials include at least one metal, when a battery including the resulting cathode is charged, the metals of the first and second cathode active materials are oxidized, converted into metal ions, and transported through the electrolyte.

[0078] The average particle size of the cathode active material may vary from about 5 nm to about 50 μm, exhibiting an average pore size of about 0.1 nm to about 1 μm. Typically, the average particle size of the cathode active material is less than about 50 μm. Preferably, the average particle size of the cathode active material is greater than about 50 nm and less than about 40 μm. More preferably, the average particle size of the cathode active material is greater than about 200 nm and less than about 30 μm. Typically, the average pore size of the cathode active material is less than about 1 μm. Preferably, the average pore size of the cathode active material is greater than about 1 nm and less than about 500 nm. More preferably, the average pore size of the cathode active material is greater than about 5 nm and less than about 200 nm.

[0079] In some embodiments, the cathode active material is at least partially surrounded by a protective coating on the outer surface. The thickness of the coating can vary between about 1 nm and about 1 μm. Preferably, the thickness of the protective coating is about 2 nm to about 500 nm. More preferably, the thickness of the protective coating is about 5 nm to about 200 nm. When present, the protective coating may include one or more of carbon and / or oxygen, wherein each element may exist as a compound or complex. The elements contained in the protective coating may be generated by a reaction gas, wherein the reaction gas is in contact with the electrolyte. When the reaction gas is carbon monoxide and / or carbon dioxide, the elements contained in the cathode surface protective coating may preferably include one or more of carbon and / or oxygen. In certain embodiments, the protective coating includes metal oxides, such as LiNbO3, Li2CO3 and / or metal halides, such as LiCl, LiF. The purpose of the protective coating of the cathode active material is to partially avoid direct contact with the solid electrolyte material to prevent any potential parasitic reactions and / or interdiffusion of the solid electrolyte material and the cathode active material. When present, the protective surface coating is optionally electrically insulating. "Electrically insulating" means that the conductivity of the cathode surface protective coating is less than or equal to 10 -3 S / cm. Preferably, the conductivity of the cathode surface protective coating is less than or equal to 10 -5 S / cm. More preferably, the conductivity of the cathode surface protective coating is less than or equal to 10 -7 S / cm.

[0080] High energy cathode

[0081] The cathode active materials disclosed herein can be used to prepare high energy cathodes, such as Figure 3 As shown in flowchart 50. As shown in the figure, the method for manufacturing a cathode for a battery includes: in step 51 of flowchart 50, preparing a solution of a hygroscopic substance and a reactive oxygen substance; in step 52 of flowchart 50, heating the solution at a temperature below about 800°C for a sufficient time to form a precipitate of a cathode active material; in step 54 of flowchart 50, collecting the cathode active material; in step 56 of flowchart 50, drying the collected cathode active material at a temperature below about 800°C; in step 58 of flowchart 50, combining the collected cathode active material with one or more of a conductive material, a polymer binder, a plasticizer and a carboxylic acid; and in step 60 of flowchart 50, depositing the combined cathode material on a current collector to produce a cathode.

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

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

[0084] In the case where the cathode includes a conductive material, it can be added to one of the hygroscopic material or the reactive oxygen material before preparing the cathode active material, or one or more cathode active materials can be combined with the conductive material after it is formed. Typically, the cathode active material is in contact with the conductive material. In the case where the cathode includes a first cathode active material and a second cathode active material, at least one of the first and second cathode active materials is in contact with the conductive material.

[0085] In the case where the cathode active material includes a metal compound and a metal oxide, each of the metal compound and the metal oxide is in contact with the other, and one or both of the metal compound and the metal oxide are in contact with a conductive material.

[0086] In the case where the cathode includes a cathode active material and a conductive material, the cathode composition may include a ratio of cathode active material: conductive material that can vary from 20:80 to 99:1 by weight. The composition ratio of cathode active material: conductive material can be about 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 96:4, 97:3, 98:2, 99:1. Typically, the cathode composition contains at least 20 wt% of the cathode active material. Preferably, the cathode composition can contain at least 40 wt% of the cathode active material. More preferably, the cathode composition can contain at least 60 wt% of the cathode active material.

[0087] Any conductive material that promotes the cathode performance of the resultant is a suitable conductive material for the purpose of the present invention. In certain embodiments, the conductive material includes a porous carbon material, which is or includes one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, microporous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, reduced graphene oxide, graphene nanoribbons, nitrogen-doped carbon, nitrogen-doped graphene and nitrogen-doped graphene oxide. The conductive material may have any suitable and compatible physical form, such as particles, powders, paper, foams, fibers, sheets, discs, rods, foils or any combination thereof. In one embodiment, the conductive material includes a porous carbon material selected from carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide, and graphene nanoribbons. In the case where the cathode includes a porous carbon material, carbon nanotubes and / or carbon nanofibers, carbon nanotubes are particularly preferred due to their high aspect ratio and durability.

[0088] In one embodiment, the conductive material comprises a porous carbon material having particles having an average particle size or diameter of about 5 nm to about 50 μm and exhibiting an average pore size of about 0.1 nm to about 1 μm. Typically, the average particle size or diameter of the conductive material is less than about 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 about 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 cathode active material and the conductive material is inversely related. In such embodiments, when the average particle size of the cathode active material is in the range of about 10 μm to about 50 μm, the average particle size of the conductive material can be about 10 nm to about 50 nm, and vice versa. Typically, one or more of the cathode active material and the conductive material include 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, more preferably greater than about 1 μm and less than about 30 μm.

[0090] In one embodiment, the step of combining the cathode active material with the conductive material comprises combining the cathode active material with a porous carbon material. The porous carbon material is optionally doped with one or more heteroatoms selected from boron, oxygen, nitrogen, sulfur, phosphorus, fluorine, chlorine and bromine. A cathode comprising a porous carbon material doped with nitrogen and / or fluorine is preferred, and nitrogen is particularly preferred because they allow lower charge transfer resistance. When present, the porous carbon material can include one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide and graphene nanoribbons.

[0091] In certain embodiments, the conductive material is at least partially coated with a protective coating on the outer surface. The thickness of the coating can vary from about 1 nanometer to about 1 micron. Preferably, the thickness of the protective coating is about 2 nanometers to about 500 nanometers. More preferably, the thickness of the protective coating is about 5 nanometers to about 200 nanometers. When present, the protective coating may include one or more of carbon and / or oxygen, wherein each element may exist in the form of a compound or complex. The elements contained in the protective coating may be generated by a reaction gas, wherein the reaction gas is liquefied, dissolved or in contact with an electrolyte. When the reaction gas is carbon monoxide and / or carbon dioxide, the elements contained in the cathode surface protective coating may preferably include one or more of carbon and / or oxygen. In certain embodiments, the protective coating includes metal oxides, such as LiNbO3, Li2CO3, and / or metal halides, such as LiCl, LiF. The purpose of the protective coating of the conductive material is to partially avoid direct contact with the solid electrolyte material to prevent any potential parasitic reactions.

[0092] Any suitable conductive material can be used for the cathode disclosed in the present invention, and it can have the same or different formulas.Cathode active material and / or conductive material can be shaped as a flat surface, and / or a granular solid.When cathode active material, conductive material and / or electrolyte are particles, particles can have any suitable shape, including sphere, cube, cuboid, cone, pyramid, cylinder, rectangular prism, hexagonal prism, hemisphere, triangular prism, pentagonal prism, octagonal prism, ring, octahedron and dodecahedron etc.

[0093] Where the cathode includes a polymer binder, it may be added to one of the hygroscopic species or the reactive oxygen species prior to preparation of the cathode active material, or it may be combined with the polymer binder after the cathode active material is formed.

[0094] A polymer binder may be added to assist in forming a solid cathode from the cathode active material. Suitable polymer binders for the purposes of the present disclosure may include one or more of polycaprolactone, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinyl pyrrolidone, poly-4-vinyl pyridine, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, etc. In a particular embodiment, the polymer binder includes one of polyethylene oxide or polyvinylidene fluoride.

[0095] Alternatively or additionally, the cathode may incorporate a plasticizer, which may be used to make the resulting cathode softer and more flexible. The plasticizer may include one or more of succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, sulfolane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitate, adipic acid ester, sebacate, and maleate, etc. In a particular embodiment, the plasticizer may include succinonitrile.

[0096] Alternatively or additionally, the cathode may incorporate one or more carboxylic acids. When present, the carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid. When the carboxylic acid is a polycarboxylic acid, it may optionally be oxalic acid.

[0097] As depicted in step 60 of flow chart 50, a combined cathode material including a cathode active material and optionally one or more of a conductive material, a polymer binder, a plasticizer, and a carboxylic acid is deposited on a current collector to form the desired cathode.

[0098] The current collector may include any suitable and compatible conductive material. In some embodiments, the cathode current collector includes one or more metals, such as alkaline earth metals, transition metals, rare earth metals, post-transition metals, and alkali metals. In some embodiments, the cathode current collector includes at least one of aluminum, aluminum alloys, nickel, nickel alloys, duplex steel, and stainless steel. In one embodiment, the cathode current collector is a metal current collector comprising a metal or a metal alloy, which contains one or more of molybdenum, titanium, and zirconium. In another embodiment, the cathode current collector comprises a metal or a metal alloy containing molybdenum. Due to the high corrosion resistance of molybdenum, it is particularly preferred to include it in the cathode current collector. In another embodiment, the cathode current collector is a conductive material comprising porous carbon in electrical contact with the cathode active material.

[0099] The cathode current collector may be solid or perforated. When perforated, the pore size of the cathode current collector may vary from about 500 nm to about 1 mm, with the spacing between pores being about 10 μm to about 100 mm.

[0100] The cathode material, along with the additional conductive material, polymer binder, and plasticizer (if present), may be applied to the current collector using any suitable application technique. For example, the combined cathode material may be cast into a film and deposited onto the desired current collector.

[0101] The resulting cathode can be incorporated into a battery 10, such as Figure 1 As shown. The cathode current collector and the anode current collector may be the same and are described as bipolar current collectors. The bipolar current collectors of the present disclosure may include an alloy of one or more of molybdenum, titanium and zirconium. Molybdenum is particularly preferably contained in the cathode current collector because it has high corrosion resistance. The cathode and anode are typically separated by an electrolytic separator 32. The battery components are typically kept in a battery housing or casing, which surrounds the battery components and can keep the battery components under a desired gas composition or atmosphere. The cathode and / or anode may be in contact with the electrolyte 30. It should be understood that no matter how the battery is illustrated herein, the battery of the present disclosure may adopt any conventional or suitable battery configuration, such as by forming into a button cell, a soft pack battery, a prismatic battery, a cylindrical battery, a flow battery, an alternating plate form or an egg roll form, etc.

[0102] Anode active material

[0103] Anode 18 may include an anode active material. In some embodiments, the anode includes one or more of lithium, sodium, potassium, magnesium, calcium, vanadium, aluminum, zinc, silicon, graphite, graphene, porous carbon, activated carbon, silicon compounds, metal oxides, and combinations thereof. The anode active material may be present as a coating, foil, mesh or grid, or another discrete anode component. Alternatively or additionally, the anode active material may be incorporated into the anode as a component element or component compound. In some embodiments, the anode includes a non-metallic oxide as the anode active material. In some embodiments, the anode may include graphite. In some embodiments, the anode may include silicon, graphite, graphene, activated carbon, or a metal or a combination thereof. In the case where the anode includes a metal, the metal may be an alkali metal or an alkaline earth metal. In some embodiments, the anode includes a metal oxide. In some embodiments, the anode includes a metal oxide such as Li4Ti5O 12 、TiO2、TiNb2O7、Nb 16 W5W 55 , Nb 18 W 16 O 93 、Nb2O5、Li3VO4、H2Ti6O 13 、LiMnBO3、LiV 0.5 Ti 0.5 S2, Li3V2O5, LixV2O5, Li3MoO4, Li5W2O7 or any combination thereof.

[0104] The anode active material can be produced in situ by carefully selecting the components of the electrochemical cell, such as the electrolyte and / or its additional components, and optionally by applying the anode current collector to the electrochemical cell. The choice of the anode active material is not particularly limited as long as the selected material can store and release ions. For example, the anode active material can be an alkali metal (such as lithium, sodium and / or potassium), an alkaline earth metal (such as magnesium and / or calcium), an amphoteric metal (such as aluminum and / or zinc), a metalloid (such as boron, germanium, arsenic, antimony, tin, tellurium, polonium and / or silicon), a metal complex, an inorganic carbon (such as graphite, graphene, graphene oxide, reduced graphene oxide, activated carbon, carbon nanotubes and / or carbon dots), sulfur, a sulfide (such as metal titanium disulfide MV 0.5 Ti 0.5 S2, wherein M is a metal, a metal sulfide (M2S), a metal polysulfide (e.g., M2S2, M2S4, M2S6, M2S8)), a sulfur-containing compound or material (such as a sulfate or an organic sulfur compound (e.g., poly(sulfide-random-(1,3-diisopropenylbenzene)), sulfided polyacrylonitrile)), an oxide (e.g., in the form of M x Ti5O 12 、TiO2、TiNb2O7、Nb2O5、M x VO4, H2Ti6O 13 、M x MnBO3, M x V2O5、M x MoO4、M x W2O7, M′ 1-x M″O2、M′ 1-w (M″ x M″′ y)O2 materials and / or metal titanates), organic materials or compounds (for example, trimerized indanone, trimerized indanone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives (for example, 10-acetylphenothiazine, 10-[2-(2-methoxyethoxy)ethyl]-10H-phenothiazine), quinone, quinone derivatives (for example, 2,2'-(2-vinylanthracene-9,10-diylidene) dicarbonitrile, 2-vinylanthraquinone, anthraquinone-2,6-disulfonate, anthraquinone-1,8-disulfonate, anthraquinone-1-sulfonate, anthraquinone-1,5-disulfonic acid, 2,2'-(2-vinylanthracene-9,10-diylidene)bis(1,3-disulfide)), diamine derivatives, phenazine, phenazine derivatives , quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, cyclohexane, cyclohexane derivatives, triazine, triazine derivatives, melamine, melamine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropene derivatives, amide derivatives, amino acids, amino acid derivatives, viologen, viologen derivatives (e.g., ethyl viologen), nitrogen oxide derivatives), organic free radicals (e.g., piperidine derivatives (e.g., 4-isothiocyanato-2,2,6,6-tetramethylpiperidinyl 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidinyl 1-oxyl, 4-(2-iodoacetylamino)-2,2,6,6-tetramethylpiperidinyl 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidinyl 1-oxyl, 4- Methacryloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-acetylamino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-(2-chloroacetylamino)-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-oxyglycidyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidinyl-1-oxyl, bis(2,2,6,6-tetramethyl-4-piperidinyl-1-oxy)sebacate, 4-methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl), pyrrolidine derivatives (e.g., 3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl, 16-DOXYL stearic acid), imidazoline derivatives (e.g., 2-phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl, 2-(4-nitrophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl), 1,1-diphenyl-2-picrylhydrazyl, galvanoxyl free radical) or any combination thereof.

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

[0106] Materials used as part of the cathode other than the cathode active material, such as conductive materials, polymer binders, plasticizers, carboxylic acids, can also be part of the anode. In the case where the anode includes a conductive material and one or more additional materials, a polymer binder, and a plasticizer, the conductive material can be applied to the current collector using any suitable application technique. For example, the conductive material can be cast into a film and then deposited onto the desired current collector.

[0107] Anode 18 may include an anode material as an anode active material, wherein the particles of the anode active material may be at least partially surrounded by a protective coating on the outer surface. The thickness of the protective coating may vary from about 1 nm to about 1 μm. Preferably, the thickness of the protective coating is about 2 nm to about 500 nm. More preferably, the thickness of the protective coating is about 5 nm to about 200 nm. In one embodiment, the anode surface protective coating comprises one or more of carbon and / or oxygen, wherein each element may exist in the form of a compound or a complex. The elements contained in the anode surface protective coating may be generated by a reaction gas. When the reaction gas is carbon monoxide and / or carbon dioxide, the elements contained in the anode surface coating preferably include one or more of carbon and / or oxygen. In some embodiments, the protective coating comprises a metal oxide such as LiNbO3, Li2CO3, and / or a metal halide such as LiCl, LiF. The role of the protective coating of the anode active material is to partially avoid direct contact with the solid electrolyte material to prevent any potential parasitic reactions and / or interdiffusion of the solid electrolyte material to the anode active material. When present, the protective surface coating is optionally electrically insulating. "Electrically insulating" means that the protective coating on the anode surface exhibits a resistance less than or equal to 10 - 3 S / cm. Preferably, the anode surface protective coating exhibits a conductivity of less than or equal to 10 -5 More preferably, the anode surface protective coating has a conductivity of less than or equal to 10 -7 The conductivity is S / cm.

[0108] Anode current collector 26 can include metal or metal alloy, such as copper, copper alloy, nickel, nickel alloy, duplex steel, stainless steel, silver, silver alloy or its any combination. In one embodiment, anode current collector is metal current collector, it includes metal or metal alloy containing one or more of molybdenum, titanium and zirconium. In another embodiment, anode current collector includes metal or metal alloy containing molybdenum. Molybdenum is particularly preferably included in anode current collector, because it has very high corrosion resistance. In some embodiments, anode current collector can be conductive material, such as porous carbon material, it is or includes carbon black, carbon nanotube, carbon nanofiber, carbon point, activated carbon, amorphous carbon, microporous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, graphene nanobelt, nitrogen-doped carbon, nitrogen-doped graphene, nitrogen-doped graphene oxide and its combination. In some embodiments, conductive material is in the form of particles, powder, paper, foam, fiber, sheet, disk, rod, foil or its any combination.

[0109] In some embodiments, the battery of the present disclosure may be a so-called "anode-free" battery. For example, Figure 4 An anode-free battery is schematically shown in . Battery 70 includes a cathode 72 according to the present disclosure, cathode 72 includes the above-mentioned combined cathode material 76, which may include one or more different cathode active materials applied to a cathode current collector 74. Battery 70 does not include an anode, but includes an anode current collector 78, wherein the cathode and the anode current collector are separated by an electrolyte separator 80. The anode-free battery is maintained in a battery casing or housing 82, which surrounds the battery components and can maintain the battery components in a desired gas composition or atmosphere. During charging, metal ions oxidized from the cathode are transported through the electrolyte and deposited on the anode current collector.

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

[0111] Electrolytes

[0112] As described above, electrolyte 30 may include electrolyte separator 32, which may be in contact with cathode 14, or separator 32 may be in contact with electrolyte 30. When electrochemical cell 12 includes an anode, electrolyte separator 32 may be located between cathode 14 and anode 18. One or both of the width and length of separator 32 may be greater than one or both of cathode current collector 24 and anode current collector 26 to avoid contact between cathode and anode, between cathode and anode current collector, between cathode current collector and anode, or between cathode current collector and anode current collector.

[0113] The electrolyte separator 32 may be disposed between the cathode 14 and the anode 18, and generally includes an electrolyte that provides for ion transport within the battery and acts as a channel for ion transport through its interaction with the anode material and the cathode material. The electrolyte separator may be in contact with the electrolyte. The separator may comprise an electrically insulating material. By "electrically insulating" it is meant that the conductivity of the separator is less than or equal to 10 -5 S / cm. Preferably, the conductivity of the separator is less than or equal to 10 -7 S / cm. More preferably, the conductivity of the separator is less than or equal to 10 -9 S / cm. In some embodiments, the melting point of the electrically insulating material of the separator is greater than 200°C. Preferably, the melting point of the electrically insulating material of the separator may be greater than 300°C. More preferably, the melting point of the electrically insulating material of the separator may be greater than 400°C. In some embodiments, the porosity of the electrically insulating material of the separator is greater than 50%. Preferably, the porosity of the electrically insulating material of the separator may be greater than 70%. More preferably, the porosity of the electrically insulating material of the separator may be greater than 90%. The separator may comprise a polymer material, such as a polymer film such as polyethylene, polypropylene, polytetrafluoroethylene or polyvinyl chloride. Typically, the polymer film (if present) comprises polypropylene and / or polyethylene. Alternatively, or additionally, the electrolyte separator may comprise non-woven fibers (such as nylon, polyester and glass, etc.), glass, ceramic or any combination thereof. In some embodiments, the separator comprises glass fiber. In some embodiments, the separator comprises a surfactant coating or treatment to enhance the wettability of the liquid electrolyte.

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

[0115] When the cathode active material of the battery includes a first cathode active material and a second cathode active material, the electrolyte may include an electrolytic solvent. In one embodiment, the electrolyte and / or the electrolytic solvent may be solid or semi-solid. In another embodiment, the electrolyte further comprises an additional solid or semi-solid electrolyte. In another embodiment, the battery includes a separator comprising a polymer material. When the electrolyte 30 includes a solid electrolyte material 36, the solid electrolyte material may include one or more polymers, glasses, phosphates, fluorophosphates, carbonates, amines, borates, fluoroborates, halides, halides, oxyhalides, oxides (e.g., MO2, M2O3, M2B2O5, M2O, MOH, M2O2, M2CO3, P2O5, MPO4, M2M'3O7, where M is a metal or a metalloid), perovskites, antiperovskites (e.g., M3OBr, M3OCl, M2OHBr, M2OHCl, where M is a metal or a metalloid), LISICON-type electrolytes (e.g., M 1+x M' x M” 2-x (PO4)3, M 2+2x M' 1-x M”O4、M (3+x) M' x V (1-x) O4, M (4-x) M' (1-x) P x O4, M 1+x+y M' x M” 2-x Si y P 3-y O 12 、M 1+x M' x M” y Ti 2-x-y P3O 12 、M 1+x+3y M' x M” 2-x (Si y PO4)3, M 14 M'M"4O 16 、M 4-x M' x V xO4, where M is a metal or metalloid), garnet (e.g., M7M'3M"2O 12 、M 7-x M’3M” 2-x Nb x O 12 、M7M' 3-x M” x Zr 2-x Nb x O 12 、M 6+x M’3M” 1+x Ta 1-x O 12 , where M is a metal or metalloid), sulfides (e.g., M6PS5Cl, M 9.54 M' 1.74 P 1.44 S 11.7 Cl 0.3 、M 10 M'P2S 12 、M7PS6、M7P3S 11 、M 3.25 P 0.95 S4, M 3+x M' x P 1-x S4, M2S, P2S5, M3PS4, MS2, M7M'PS8, M6PS5Br, M6PS5I, M3PO4, M3P7S 11 、M2M'S3、M4M'S4、M 4-2x M' x M"S4、MM'S2、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 , where 0<x<1, M is a metal or a metalloid), sulfide crystalline lithium superion conductor (thio-LISICON) type electrolyte (for example, M (4-x) M' (1-x) P x S4, where M is a metal or a metalloid), nitrogen oxides, nitrides, etc. (LISICON is the acronym for lithium superionic conductor). The solid or semi-solid electrolyte material may be an electrolytic solvent or an electrolyte, and may selectively include one or more electrolytic solvents and / or one or more salts dissolved in the electrolytic solvent.

[0116] In the case where the electrolyte 30 is present as a solid or semi-solid in the electrochemical cell unit, the electrolyte 30 may optionally be present in the form of a film, foil, tape, paper, sheet, layer, etc. The electrolyte of the present disclosure may optionally include a solid electrolyte material 36 that is solid, wherein the solid portion of the electrolyte material includes a first chlorine compound.

[0117] For the purposes of the present disclosure, selective and non-limiting examples of suitable first chlorine compounds 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 x Cl(0 < x < 1), M3ClO, M4Cl(OH)3, M5Cl3(OH)2, wherein M is a metal or metalloid.

[0118] Each of M, M', or M'' in the present disclosure may be selected from 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 may be an alkali metal, as including an alkali metal helps to increase the energy density. When present, it is preferred to use the same metal or metalloid as the electrolyte material in the cathode active material and / or the anode active material.

[0119] In the case where the electrolyte 30 is present as a solid in the electrochemical cell, the electrolyte 30 is optionally present as a composition of solid particles. The average particle size of a suitable electrolyte material 36 can vary from about 5 nm to about 30 μm, and can exhibit an average pore size of about 0.1 nm to about 500 nm. Typically, the average particle size or diameter of a suitable electrolyte material is less than about 30 μm. Preferably, the average particle size of the electrolyte material is greater than about 10 nm and less than about 20 μm. More preferably, the average particle size of the electrolyte material is greater than about 20 nm and less than about 10 μm. In the case where the electrolyte 30 is present as a composition of solid particles, the average pore size of the electrolyte material 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.

[0120] In the case where the electrolyte 30 includes a liquefied gas, the liquefied gas may include one or more of methane (e.g., methane, fluoromethane, difluoromethane), ethane (e.g., ethane, fluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane), propane (e.g., propane, 2-fluoropropane), butane (e.g., butane, fluorobutane), ethylene, acetylene, propylene, carbon monoxide, and carbon dioxide. The liquefied gas may be generated from the gas at a critical pressure at or below the condensation temperature of the gas, or at a critical temperature at or above the vapor pressure of the gas.

[0121] Where the electrolyte 30 comprises an organic liquid, the organic liquid may comprise one or more organic carbonates, ethers, esters, amides, halogenated liquids, nitriles, or ionic liquids.

[0122] When the electrolyte 30 includes an organic carbonate, the organic carbonate may be, for example, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, dipropyl carbonate, 4-vinyl-1,3-dioxolane-2-one, 4-chloro-1,3-dioxolane-2-one, diethyl 2,5-dioxadipic acid ester, bis(2,2,2-trifluoroethyl) carbonate, 4-fluoro-1,3-dioxolane-2-one, dimethyl 2,5-dioxadipic acid ester, or dibutyl carbonate, etc.

[0123] In the case where the electrolyte 30 includes an ether, the ether may be, for example, dimethoxyethane, dimethoxymethane, dimethyl ether, ethyl ether, ethylene glycol, ethylene glycol derivatives (diglyme, triglyme, tetraglyme), tetrahydrofuran, dioxolane, dioxane, or the like.

[0124] In the case where the electrolyte 30 includes an ester, the ester may be, for example, triethyl borate, trimethyl borate, tris(2,2,2-trifluoroethyl)borate, 2,4,6-trimethoxyboroxy ester, tributyl borate, trihexyl borate, tripropyl borate, or the like.

[0125] In the case where the electrolyte 30 includes an amide, the amide may be, for example, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylpropionamide, diethylpropionamide, 2,2,2-trifluorodimethylacetamide, dipropylacetamide, or the like.

[0126] In the case where the 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).

[0127] In the case where the 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-hexanetrinitrile, 1,2,2,3-propanetetracarbonitrile, malononitrile, fumaronitrile, valeronitrile, acrylonitrile, toluenenitrile, methoxybenzonitrile or 3-butoxypropionitrile, etc.

[0128] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid may be, for example, an imidazole derivative (such as, for example, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 2,3-dimethyl-1-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-decyl- 3-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(trifluoromethanesulfonyl)imide, 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-octylimidazole trifluoromethanesulfonate, 3-ethyl-1-vinyl Imidazole bis(trifluoromethanesulfonyl)imide, 1-methyl-3-n-octylimidazole tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-3-(4-sulfobutyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-methyl-1H-imidazole-3-hexafluorophosphate or 3,3'-(butane-1,4-diyl)bis(1-vinyl-3-imidazole)bis(trifluoromethanesulfonyl)imide, etc.

[0129] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, a pyrrolidine derivative (such as, for example, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 1-methyl-1-pentylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidine, bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-methylpyrrolidine tetrafluoroborate or 1-allyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, etc.).

[0130] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid may be, for example, a pyridine derivative (such as, for example, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-hexylpyridinium hexafluorophosphate, 1-ethyl-3-(hydroxymethyl)pyridinium ethyl sulfate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-ethyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-methylpyridinium bis(trifluoromethanesulfonyl)imide or 1,1'-bis[3-(trimethylammonium)propyl]-4,4'-bipyridine, etc.).

[0131] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid may be, for example, a piperidine derivative such as 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide or 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, or the like.

[0132] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, an ammonium derivative, such as methyl tri-n-octylammonium bis(trifluoromethanesulfonyl)imide, ethyl(3-methoxypropyl)dimethylammonium bis(trifluoromethanesulfonyl)imide, ethyl(2-methoxyethyl)dimethylammonium bis(trifluoromethanesulfonyl)imide, butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium trifluoromethanesulfonate, methyl tri-n-octylammonium bis(trifluoromethanesulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, tributylmethylammonium bis(trifluoromethanesulfonyl)imide, butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, or tetrabutylammonium hexafluorophosphate.

[0133] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid can be, for example, a phosphorus derivative, such as tributylmethylphosphorus bis(trifluoromethanesulfonyl)imide, tributyl(2-methoxyethyl)-phosphorus bis(trifluoromethanesulfonyl)imide, tetrabutylphosphorus tetrafluoroborate, tetrabutylphosphorus hexafluorophosphate, or tributylmethylphosphorus bis(trifluoromethanesulfonyl)imide.

[0134] In the case where the electrolyte 30 includes an ionic liquid, the ionic liquid may be, for example, a morpholine derivative, or a sulfonium derivative (such as, for example, triethylsulfonium bis(trifluoromethanesulfonyl)imide)).

[0135] In the case where the 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 one or more ionic metal complexes, such as, for example, bis(nonafluorobutanesulfonyl)imide, metal (fluorosulfonyl) (trifluoromethanesulfonyl)imide, metal trifluoromethanesulfonate, metal tetrafluoroborate, metal hexafluorophosphate, metal bis(fluorosulfonyl)imide, metal nonafluoro-1-butanesulfonate, metal bis(trifluoromethanesulfonyl)imide, metal tricyanomethane, metal nitrate, metal halide, metal bis(oxalate)borate, metal difluoro(oxalate)borate or metal perchlorate, etc.

[0136] The electrolyte 30 may optionally include one or more additives, wherein the additive may be a polymer material, a plasticizer, a phosphazene, a phosphate, a sulfonyl group, and a carboxylic acid. When present, the polymer material may include, in any combination, for example, one or more of polycaprolactone, polyacrylic acid, poly(methyl acrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinyl pyrrolidone, poly(4-vinyl pyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, styrene-butadiene-rubber, and sodium carboxymethyl cellulose. In one embodiment, the polymer material includes one of polyethylene oxide or polyvinylidene fluoride, etc.

[0137] In the case where the additive includes a plasticizer, the plasticizer may include, for example, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, γ-butyrolactone, cyclopentane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitates, adipates, sebacates, maleates, or any combination thereof.

[0138] In the case where the additive includes phosphazene, the phosphazene may include, for example, one or more of pentafluoro(phenoxy)cyclotriphosphazene, tripolychlorophosphazene, ethoxy(pentafluoro)cyclotriphosphazene, hexaphenoxycyclotriphosphazene, or hexafluorocyclotriphosphazene.

[0139] In the case where the additive includes a phosphate ester, the phosphate ester may include, for example, one or more of tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphate, tris(2-butoxyethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(1H,1H,5H-octafluoropentyl) phosphate, 2-ethylhexyl diphenyl phosphate, tripentyl phosphate, tri-o-cresyl phosphate, triallyl phosphate, tri-m-cresyl phosphate, triethyl phosphate, tri-p-cresyl phosphate, triphenyl phosphate, trimethyl phosphate, and tris(2,2,2-trifluoroethyl) phosphate.

[0140] In the case where the additive includes a sulfonyl group, the sulfonyl group may include, for example, one or more of isopropyl methyl sulfone, dimethyl sulfone, dimethyl sulfite, dipropyl sulfone, 1,3-propane sultone, 3-methylcyclopentane sulfone, 1,4-butane sultone, tetrahydrothiophene 1,1-dioxide, 1,3,2-dioxazolethiophene 2,2-dioxide, and 1,3,2-dioxazolethiophene 2-oxide.

[0141] In the case where the additive includes a carboxylic acid, the carboxylic acid can be, for example, a monocarboxylic acid or a polycarboxylic acid. When the carboxylic acid is a polycarboxylic acid, it can be oxalic acid. When present, the carboxylic acid can be present in the electrolyte in a weight percentage of between about 0.01 wt % and about 30 wt %, preferably between about 0.1 wt % and about 20 wt %, and more preferably between about 1 wt % and about 10 wt %.

[0142] In the case where the electrolyte 30 is or includes a gel, the gel is generally obtained by mixing a suitable liquid electrolyte material (as described above) with a suitable solid electrolyte material (as described above). Suitable means that the liquid and solid electrolyte materials are physically and chemically compatible and, when mixed together in a selected ratio, an electrolyte gel exhibiting the desired viscosity and electrolytic properties can be obtained.

[0143] In some embodiments, the battery may be referred to as a "single material" battery, in which the cathode active material disclosed herein may also be used as an electrolyte and / or separator. In such embodiments, the cathode active material that is not in contact with the conductive material or current collector is used as an electrolyte and / or separator.

[0144] Where the battery 10 includes a cathode 14 and an electrolyte 30, its composition can include a cathode:electrolyte ratio that can vary from 15:85 to 95:5 by weight. The cathode:electrolyte composition ratio can be about 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5. Typically, the cathode electrolyte ratio is at least 15 wt% cathode. Preferably, the cathode electrolyte ratio is at least 30 wt% cathode. More preferably, the cathode electrolyte ratio is at least 45 wt% cathode.

[0145] The solid-state battery may also include a reaction gas, which refers to a compound that is a gas at any given temperature or pressure, and the reaction gas will react chemically or electrochemically with the solid electrolyte material or the electrode (cathode or anode) active material. In one embodiment of the present disclosure, the reaction gas may include a compound having at least one oxygen atom (e.g., CO2, CO, O2, N2O, NO2, and SO2), at least one sulfur atom (e.g., S8, COS, CS2, SF6, H2S, SO2, CH3SH, (CH3)2S, and C2H5SH, and / or having at least one chlorine atom (e.g., Cl2, CCl4, CH3CCl3, CHClF2, and ClO2).

[0146] Due to its reaction with the solid electrolyte or electrode active material, the reaction gas can chemically or electrochemically produce a protective coating on the outer surface of one or more of the cathode active material, the anode active material and / or the conductive material. In some embodiments, after one or more molding cycles are performed under exposure to the reaction gas, or after the desired protective coating is generated on the surface of the battery cell assembly, the reaction gas is removed from the solid-state battery using a vacuum source. The molding cycle may include a step of applying a current or voltage to the battery from the anode to the cathode or from the cathode to the anode. The resulting protective coating is intended to partially prevent direct contact with the solid electrolyte material and reduce the charge transfer resistance between the electrode and the solid electrolyte material by maximizing the contact area for ion transfer without applying a large amount of stacking pressure. The reaction gas itself is neither a cathode active material nor an anode active material, and the reaction gas should not participate in the redox reaction of the electrochemical battery cell during battery operation.

[0147] It should be understood that although the description of various embodiments herein is in the context of a battery having a single battery cell, the same or similar principles may also be applied to a battery assembly (i.e., a battery pack, etc.) including more than one battery cell. Such multi-battery assemblies should be understood to be within the scope of the present disclosure.

[0148] Example 1: Fabrication of high energy cathode

[0149] Cathodes according to the present disclosure were fabricated and tested using the following procedure.

[0150] Lithium hydroxide (LiOH) monohydrate and lithium chloride (LiCl) hydrate were dissolved in a 1:4 oxalic acid (OA)-methanol (MeOH) mixture under vigorous stirring to prepare a 0.1M LiOH / 0.1M LiCl solution. 100 mg of carbon nanotubes (CNTs) were added to the solution under stirring, and the resulting mixture was sonicated for 10 minutes to intermix the carbon nanotubes. A solution of hydrogen peroxide (H2O2) and urea peroxide (CH6N2O3) was added to the reaction mixture under vigorous stirring at a temperature of 65°C.

[0151] The reaction mixture was then transferred to a Teflon-lined stainless-steel autoclave and heated to 130 °C for 12 hours. The resulting precipitate was separated from the mother liquor by filtration, washed with acetone, and dried in vacuo at 110 °C for 24 hours. The collected material was then rapidly transferred to an argon-filled glove box with minimal exposure to air. The composition of the prepared cathode active material is expected to be one or more of composites of LiCl-Li2O and LiCl-Li2O2, where the resulting clusters can be empirically described as Li3ClO and Li3ClO2, respectively.

[0152] Example 2: Fabrication of solid electrolyte

[0153] The first solid electrolyte was prepared by inverse vulcanization of elemental sulfur. Predried elemental sulfur was mixed with 1,3-diisopropenylbenzene (DIB) in a 50:50 mass ratio and stirred on a hot plate at 180 °C for about four hours inside an argon-filled glove box. During inverse vulcanization, once the color changed from yellow to red, the mixture was cooled to room temperature and left overnight. Then, the resulting material and predried LiCl and poly(ethylene oxide) were dissolved in chloroform. The composition of the first solid electrolyte is expected to be a composite polymer material of poly(S-r-DIB)-LiCl-PEO. Then, a high-porosity (90%) polybenzimidazole (PBI) nanofiber sheet (thickness less than 15 microns) was dropped into the resulting solution, dried for about one hour, and repeated at least three times to ensure that the surface of the separator was completely covered. The thickness of the resulting individual film was about 18 microns.

[0154] The second solid electrolyte precursor includes predried LiCl and LiOH. A few drops of methanol were added to the mixture of LiCl and LiOH to form a paste, and the resulting paste was placed in a tightly sealed Teflon reactor. It was heated at 250 °C for 48 hours before the reactor was opened. Subsequently, it was allowed to cool to room temperature while the water in the reactor was removed using a vacuum pump. 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. The melting point of the solid electrolyte was shown to be below 270 °C. Subsequently, the resulting solid electrolyte was placed in a stainless-steel barrel container, the outer surface of which was surrounded by heating elements and connected to a stainless-steel pipe, where the inside of the container was filled with a predried mixed gas containing CO2 and argon. The concept of the solid electrolyte reservoir is expected to reduce the manufacturing cost as the manufacturing space volume is minimized at a dew point below -60 °C.

[0155] Example 3: Fabrication of solid-state electrochemical battery cells

[0156] The cathode active material was mixed with Li2C6Cl4O2 (as additional cathode active material), carbon black (as conductive material), succinonitrile (as plasticizer) and polytetrafluoroethylene (as polymer binder). The resulting mixture was cast onto a 316L stainless steel bipolar current collector to create the cathode 90 of the battery cell 92. The prepared cathode was placed in a cylindrical battery cell with a first solid electrolyte coated PBI nanofiber separator 94, as shown in FIG. Figure 7 As shown. After assembly, the second solid electrolyte 96 in the external reservoir 98 is heated and liquefied at above 300°C and then introduced into the assembled battery cell 92 by a pump 100. The liquid electrolyte 96 penetrates into the pores of the separator and the electrode, and then transforms back into a solid phase after cooling to room temperature. Inert CO2 is added to the reservoir 98 and introduced into the battery cell 90 together with the second solid electrolyte 96, and is expected to produce a protective layer on the outer surface of the electrode material to partially avoid direct contact with the solid electrolyte material and reduce the charge transfer impedance between the electrode and the solid electrolyte material. After applying an electric current or voltage to the battery cell for one or more molding cycles, the remaining CO2 can be removed from the battery housing using, for example, a vacuum source (e.g., a vacuum pump) connected to a port through the battery housing.

[0157] Figure 7 92. An enlarged portion 102 of the structure of the battery cell 92 is shown. The example cross section 102 includes, from left to right, an anode current collector 104, an anode 106, an electrolytic separator 108, a cathode 110, and a cathode current collector 112. Similarly, an enlarged portion 114 of the electrolytic separator 108 shows a structure including a solid glass electrolyte 116 that surrounds a heat resistant polymer 118 but is separated from the polymer 118 by a solid polymer electrolyte 120.

[0158] Similarly, an enlarged portion 122 of cathode 110 shows particles of electrode material 124 surrounded by a protective layer 126 disposed within a solid electrolyte 128 .

[0159] Example 4: Determining the recharge capacity of a high energy battery

[0160] The high energy battery prepared in Example 3 was subjected to repeated discharge and recharge. Figure 8 As shown, the battery is at 0.1mA / cm 2 The high capacity was maintained over 15 cycles at a current density of 2.5 Å.

[0161] Example 5: Alternative Embodiments

[0162] This section describes other aspects and features of the disclosed cathode active materials, cathodes, and batteries, which are presented as a series of paragraphs without limitation, some or all of which may be represented by alphanumeric characters for clarity and efficiency. Each of these paragraphs may be combined with one or more other paragraphs and / or with the disclosures elsewhere in this application in any suitable manner. Some of the following paragraphs explicitly quote and further limit other paragraphs, thereby providing non-limiting examples of some suitable combinations.

[0163] A1. A solid-state battery, comprising: an electrolyte comprising an electrolyte material; wherein at least a portion of the electrolyte material is solid, and the solid portion of the electrolyte material comprises a first chlorine compound; and a cathode in contact with the electrolyte; wherein the cathode comprises a cathode active material comprising a second chlorine compound.

[0164] A2. A solid-state battery according to paragraph A1, wherein the battery is configured so that the first chlorine compound and the second chlorine compound are the same.

[0165] A3. A solid-state battery according to paragraph A1, wherein the battery is configured so 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.

[0166] A4. A solid-state battery according to paragraph A1, wherein the solid portion of the electrolyte material comprises sulfur.

[0167] A5. A solid-state battery according to paragraph A4, wherein the solid portion of the electrolyte material is made by reverse sulfidation of sulfur.

[0168] A6. A solid-state battery according to paragraph A1, wherein the melting point of the first chlorine compound is lower than 700°C.

[0169] A7. A solid-state battery according to paragraph A1, wherein the second chlorine compound comprises a metal complex of chlorine.

[0170] A8. A solid-state battery according to paragraph A1, wherein the cathode active material includes one or more metals selected from lithium, sodium, potassium, beryllium, magnesium, calcium, vanadium, iron, nickel, copper, zinc or aluminum.

[0171] A9. A solid-state battery according to paragraph A8, wherein the solid-state battery is configured so that charging the solid-state battery will oxidize the metal of the cathode active material into metal ions, and the metal ions are subsequently transported through the electrolyte.

[0172] A10. A solid-state battery according to paragraph A1, wherein the cathode active material comprises an organic compound and / or an organic group.

[0173] A11. A solid-state battery according to paragraph A1, wherein the cathode also includes a conductive material in contact with the cathode active material.

[0174] A12. A solid-state battery according to paragraph A11, wherein the conductive material and / or the cathode active material includes a protective coating.

[0175] A13. A solid-state battery according to paragraph A11, wherein the conductive material includes a porous carbon material selected from carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, graphite, graphene, graphene oxide and graphene nanoribbons.

[0176] A14. A 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.

[0177] A15. A solid-state battery according to paragraph A1, wherein the cathode further comprises one or more of a polymer binder, a plasticizer or a carboxylic acid.

[0178] A16. The solid-state battery according to paragraph A1 further includes an anode comprising an anode active material.

[0179] A17. The solid-state battery according to paragraph A1 also includes a reaction gas in contact with the electrolyte or dissolved in the electrolyte.

[0180] A18. A solid-state battery according to paragraph A17, wherein the reaction gas includes oxygen, chlorine and / or sulfur.

[0181] A19. A solid-state battery according to paragraph A17, wherein the reaction gas includes 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.

[0182] A20. The solid-state battery according to paragraph A1, further comprising a bipolar current collector, wherein the bipolar current collector comprises an alloy of one or more of molybdenum, titanium and zirconium.

[0183] A21. The solid-state battery according to paragraph A1 further includes a separator, wherein the separator includes an electrically insulating material.

[0184] A22. A solid-state battery according to paragraph A21, wherein the melting point of the electrically insulating material of the separator is higher than 200°C.

[0185] A23. A solid-state battery according to paragraph A21, wherein the porosity of the electrically insulating material of the separator is greater than 50%.

[0186] A24. A solid-state battery according to paragraph A1, wherein the solid electrolyte material has a mass percentage of chlorine greater than 3.

[0187] A25. A solid-state battery according to paragraph A1, wherein the second chlorine compound has a mass percentage of chlorine greater than 5.

[0188] A26. A solid-state battery comprising: an electrolyte containing an electrolyte material; wherein at least a portion of the electrolyte material is solid, and the solid portion of the electrolyte material is made by reverse sulfidation of sulfur; and a cathode in contact with the electrolyte; wherein the cathode includes a cathode active material.

[0189] Advantages, Features and Benefits

[0190] The solid-state batteries of the present disclosure, equipped with cathode active materials and solid-state electrolyte materials, allow for the manufacture of high energy density battery cells that are economical, have high discharge capacity and high discharge potential.

[0191] The selected battery of the present disclosure has a current density greater than or equal to 0.1 mA / cm 2 Under the conditions of Li / Li + An average operating discharge potential of at least 2.0V.

[0192] The selected battery of the present disclosure has a current density greater than or equal to 0.1 mA / cm 2 Under the conditions of, based on the amounts of the first and second cathode active materials, exhibit a discharge specific capacity of at least 200 mAh / g.

[0193] In certain embodiments, the battery of the present disclosure operates at a current density greater than or equal to 0.1 mA / cm 2 Under the conditions of, based on the amount of cathode active material, a discharge specific capacity of greater than 200 mAh / g, greater than 300 mAh / g and greater than 400 mAh / g can be exhibited.

[0194] Selected batteries of the present disclosure may exhibit relative Li / Li + An average operating discharge potential greater than 1.0 V. In some embodiments, the battery of the present disclosure may exhibit a relative Li / Li + The average operating discharge potential is greater than 2.0 V, greater than 3.0 V, or even greater than 4.0 V. Typically, at a discharge potential greater than or equal to 0.1 mA / cm 2 At a current density of 2.5 Å, this battery can produce a relative high current density of Li / Li + An average operating discharge potential of at least 3.0V.

[0195] Selected cells of the present disclosure, combined with their high discharge capacity and high discharge potential, are able to provide high cell-level energy density greater than 500 Wh / kg, while having a cell-level cost of less than $50 / kWh.

[0196] Selected batteries of the present disclosure, including those having a first cathode active material and a second cathode active material, can be substantially rechargeable. In one aspect of the present disclosure, a battery can be considered substantially rechargeable if the battery exhibits a cycle number greater than 100. Alternatively or additionally, selected batteries of the present disclosure, including those having a first cathode active material and a second cathode active material, can operate effectively at room temperature, which in one embodiment can be defined as 15°C-30°C.

[0197] The cathode active materials of the present disclosure exhibit a relative Li / Li + Above the standard redox potential of 3.0V.

[0198] Unless otherwise stated, the term "combination" or "combinations" refers to all types of combinations starting from two of the relevant components to a plurality or all of such components.

[0199] The description of method steps, whether shown in the drawings or described in the specification, should not be considered to indicate a specific order of method steps unless the order is specifically provided. The order of these steps may be different from the order depicted and described, and / or two or more steps may be performed simultaneously or with partial concurrence, unless otherwise stated.

[0200] Features and variants specified in individual embodiments and examples can be freely combined with features and variants of other examples and embodiments and serve in particular to characterize the invention in the claims, without necessarily implying further details of the respective embodiment or the respective example.

[0201] The above disclosure may include multiple different examples with independent utility. Although each of these has been disclosed in one or more illustrative forms, the specific embodiments thereof as disclosed and shown herein should not be considered restrictive, because many variations are possible. With respect to the section titles used in this disclosure, these titles are only used for organizational purposes. The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of the various elements, features, functions and / or performances disclosed herein. The following claims specifically point out certain combinations and sub-combinations that are considered novel and non-obvious. Other combinations and sub-combinations of features, functions, elements and / or performances may be claimed in applications claiming priority to this application or a related application. Such claims, whether broader, narrower, equal or different in scope than the original claims, are also considered to be included in the subject matter of the present disclosure.

Claims

1. A solid-state battery, comprising: an electrolyte comprising an electrolyte material; wherein at least a portion of the electrolyte material is solid, and the solid portion of the electrolyte material comprises a first chlorine compound; as well as a cathode in contact with the electrolyte; wherein the cathode comprises a cathode active material comprising a second chlorine compound.

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

5. A solid-state battery according to claim 4, wherein the solid portion of the electrolyte material is made by inverse sulfidation of sulfur. The solid-state battery according to claim 1 , wherein the melting point of the first chlorine compound is lower than 700° C. .

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

8. A solid-state battery according to claim 7, wherein the solid-state battery is configured such that charging the solid-state battery will oxidize the metal of the cathode active material into metal ions, and the metal ions are subsequently transported through the electrolyte.

9. The solid-state battery of claim 1, wherein the cathode active material comprises an organic compound and / or an organic moiety.

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

11. The solid-state battery of claim 10, wherein at least one of the conductive material or the cathode active material comprises a protective coating.

12. The solid-state battery of claim 1, further comprising an anode comprising an anode active material. 13 . The solid-state battery according to claim 1 , further comprising a reaction gas in contact with the electrolyte or dissolved in the electrolyte.

14. The solid-state battery according to claim 1, further comprising a bipolar current collector, wherein: The bipolar current collector includes an alloy of one or more of molybdenum, titanium, and zirconium.

15. The solid-state battery of claim 1, further comprising a separator, wherein the separator comprises an electrically insulating material.

16. The solid-state battery according to claim 15, wherein the melting point of the electrically insulating material of the separator is higher than 200°C.

17. The solid-state battery of claim 15, wherein the porosity of the electrically insulating material of the separator is higher than 50%.

18. The solid-state battery of claim 1, wherein the solid electrolyte material has a mass percentage of chlorine greater than 3.

19. The solid-state battery of claim 1, wherein the second chlorine compound has a mass percent of chlorine greater than 5.

20. A solid-state battery comprising: an electrolyte comprising an electrolyte material; wherein at least a portion of the electrolyte material is solid, and the solid portion of the electrolyte material is made by inverse sulfidation of sulfur; and a cathode in contact with the electrolyte; wherein the cathode comprises a cathode active material.

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