Solid-state battery and manufacturing method therefor

Abstract

The present disclosure provides: an additive material added to a sulfide-containing solid electrolyte material for use in a solid-state battery; a solid-state battery in which the additive material is used in the solid electrolyte material; and a method for manufacturing the solid-state battery. Due to the additive material provided in the present invention, the solid-state battery using the additive material can operate under pressure relatively lower than that of a solid-state battery with no additive material.

Description

Solid-state battery and method for manufacturing the same

[0001] Cross-reference to related applications

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 554,087, filed February 15, 2024, and U.S. Non-Provisional Application No. 18 / 972,560, filed December 6, 2024, the entire contents of which are expressly incorporated herein by reference in their entirety.

[0003] Technology field

[0004] The present disclosure relates to a solid-state battery and a method for manufacturing a solid-state battery.

[0005] secondary battery

[0006] Secondary batteries are increasingly becoming a desirable power source for a wide range of electronic devices, including automobiles, computers, mobile phones, tools, scooters, bicycles, electric vehicles, power storage systems, drones, and other devices. Among these, lithium-based batteries are particularly attractive due to their ability to provide a desirable balance of voltage and energy density. Beyond their performance advantages, lithium-ion secondary batteries contribute to climate change by enabling the electrification of transportation and promoting the integration of renewable energy sources. These batteries help reduce greenhouse gas emissions by powering electric vehicles and storing energy from intermittent renewable sources like solar and wind. Furthermore, the long cycle life and high energy density of lithium-ion batteries support the development of smart grids and distributed energy systems, potentially improving overall energy efficiency and reducing dependence on fossil fuels. Traditionally, lithium-ion secondary batteries contain a liquid electrolyte, typically a lithium salt dissolved in an organic solvent. However, there is growing interest in developing all-solid-state lithium-ion secondary batteries as an alternative to conventional liquid electrolyte-based systems. Solid-state batteries offer potential advantages in safety, stability, and energy density. Despite these potential advantages, the development of practical all-solid-state lithium secondary batteries faces several significant challenges.

[0007] Challenges of all-solid-state secondary batteries

[0008] One of the challenges in solid-state battery design is achieving and maintaining sufficient lithium ion diffusion within the solid electrolyte material. Furthermore, certain battery components, such as electrodes, can experience volume changes (e.g., expansion and contraction) during discharge and charging. These volume changes can induce mechanical stress or lead to loss of contact between various components within the battery structure. Loss of contact between battery components can not only degrade charge-discharge characteristics but also reduce overall battery capacity. Researchers and engineers in the energy storage field are actively working to address these challenges. They are focusing on developing new materials and battery designs that can achieve desirable lithium ion diffusion while accommodating the mechanical stresses associated with battery cycling. Improving the stability of interfaces within solid-state batteries remains an area of ​​research. Overcoming the current limitations of solid-state battery systems has the potential to significantly advance energy storage capabilities for a wide range of applications.

[0009] Prohibition of recognition of prior art

[0010] The discussion in this section is intended to provide background information related to the present disclosure and is not an admission of prior art.

[0011] Additives for solid electrolytes

[0012] The present disclosure relates to an additive material added to a sulfide-containing solid electrolyte material for use in a solid-state battery. The additive material provided herein allows a solid-state battery using such an additive material to operate at a relatively lower pressure than a solid-state battery without such an additive material.

[0013] solid state batteries

[0014] One aspect of the present disclosure provides a solid-state battery comprising: a positive electrode; a negative electrode; and a solid electrolyte layer positioned between the positive electrode and the negative electrode and configured to enable transport of lithium ions between the positive electrode and the negative electrode; wherein the solid electrolyte layer comprises particles comprising a sulfide-containing material; and an additive material represented by ABC (chemical formula 1), wherein A is a thiol group (SH) or a leaving group, B is a substituted or unsubstituted C3-C20 alkane group, and C is a phosphate or a salt thereof, A is configured to interact with sulfur of the sulfide-containing material of the particles, and at least a portion of the additive material is interposed between two immediately adjacent particles of the particles.

[0015] Solid-state batteries - different aspects

[0016] Another aspect of the present disclosure is a solid-state battery comprising: a cathode; a cathode; and a solid electrolyte layer positioned between the cathode and the anode and configured to enable transport of lithium ions between the cathode and the anode; wherein the solid electrolyte layer comprises particles comprising a sulfide-containing material; And an additive material represented by ABC (chemical formula 1); wherein A is a thiol group (SH) or a leaving group, A is configured to interact with sulfur of a sulfide-containing material of the particle, and at least a portion of the additive material is interposed between two immediately adjacent particles among the particles, and when A is a leaving group, it is selected from the group consisting of chloride, bromide, iodide, tosylate (p-toluenesulfonate) or mesylate (methanesulfonate) group, acetate or trifluoroacetate group, phosphate or phosphonate group, carboxylate group, alkoxide group, amine group, cyano (CN) group, azide (N3) group, sulfonate group, triethoxysilyl, trimethoxysilyl, and combinations thereof, and B is propane, n-butane (CH3CH2CH2CH3), isobutane (CH3CH(CH3)2), n-Pentane (CH3(CH2)3CH3), isopentane (2-methylbutane, CH3CH2CH(CH3)2), neopentane (2,2-dimethylpropane, (CH3)4C), n-hexane (CH3(CH2)4CH3), 2-methylpentane (CH3CH2CH2CH(CH3)CH3), 3-methylpentane (CH3CH2CH(CH3)CH2CH3), 2,2-dimethylbutane (CH3C(CH3)2CH2CH3), 2,3-dimethylbutane (CH3CH(CH3)CH(CH3)CH3), n-heptane (CH3(CH2)5CH3), 2-methylhexane (CH3CH2CH2CH2CH(CH3)CH3), 3-methylhexane (CH3CH2CH2CH(CH3)CH2CH3), 2,2-dimethylpentane (CH3C(CH3)2CH2CH2CH3), 2,3-dimethylpentane (CH3CH(CH3)CH2CH(CH3)CH3), 2,4-dimethylpentane (CH3CH(CH3)CH2CH2CH(CH3)CH3), 3,3-dimethylpentane (CH3CH2CH(CH3)2CH2CH3),3-Ethylpentane (CH3CH2CH2CH(CH2CH3)CH3), 2,2,3-Trimethylbutane ((CH3)2CHCH2CH(CH3)2), n-octane (CH3(CH2)6CH3), 2-Methylheptane (CH3CH2CH2CH2CH2CH(CH3)CH3), 3-Methylheptane (CH3CH2CH2CH2CH(CH3)CH2CH3), 4-Methylheptane (CH3CH2CH2CH(CH3)CH2CH2CH3), 2,2-Dimethylhexane (CH3C(CH3)2(CH2)4CH3), 2,3-Dimethylhexane (CH3CH(CH3)CH2CH2CH(CH3)CH3), 2,4-Dimethylhexane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH3), 3,3-Dimethylhexane (CH3CH2CH(CH3)2CH2CH2CH3), 3,4-dimethylhexane (CH3CH2CH(CH3)CH2CH(CH3)CH3), 2,2,4-trimethylpentane (isooctane, CH3CH(CH3)2CH2CH(CH3)2), 2-ethylhexane (CH3CH2CH(CH2CH3)CH2CH3), n-nonane (CH3(CH2)7CH3), 2-methyloctane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-methyloctane (CH3CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-dimethylheptane (CH3C(CH3)2(CH2)5CH3), 2,3-dimethylheptane (CH3CH(CH3)CH2CH2CH2CH2CH(CH3)CH3), 2,4-Dimethylheptane (CH3CH(CH3)CH2CH2CH(CH3)CH2CH3), 2,2,4-Trimethylhexane (CH3C(CH3)2CH2CH(CH3)2CH2CH3), 3,3-Dimethylheptane (CH3CH2CH(CH3)2CH2CH2CH2CH3), 3-Ethylheptane (CH3CH2CH2CH(CH2CH3)CH2CH3), n-Decane (CH3(CH2)8CH3), 2-Methylnonane (CH3CH2CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-Methylnonane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-Dimethyloctane (CH3C(CH3)2(CH2)6CH3), 2,3-Dimethyloctane (CH3CH(CH3)CH2CH2CH2CH2CH2CH(CH3)CH3), 2,4-Dimethyloctane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH2CH3), 2,5-dimethyloctane (CH3CH2CH(CH3)CH2CH2CH2CH2CH3), 3,3-dimethyloctane (CH3CH2CH(CH3)2CH2CH2CH2CH(CH3)CH2CH3), 2-ethyloctane (CH3CH2CH(CH2CH3)CH2CH2CH3), n-undecane (C, 11 H 24 ) and its branched isomers, n-dodecane (C 12 H 26 ) and its branched isomer, n-tridecane (C 13 H 28 ) and its branched isomer, n-tetradecane (C 14 H 30 ) and its branched isomer, n-pentadecane (C 15 H 32 ) and its branched isomers, n-hexadecane (C 16 H 34 ) and its branched isomer, n-heptadecane (C 17 H 36 ) and its branched isomer, n-octadecane (C 18 H 38 ) and its branched isomer, n-nonadecane (C 19 H 40 ) and its branched isomers, n-eicosane (C 20 H 42) and branched isomers thereof, and combinations thereof, and when B is a substituted C3-C20 alkane group, B is selected from the group consisting of fluoro (-F), chloro (-Cl), bromo (-Br), iodo (-I), hydroxyl (-OH), ether (-OR), aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxide (-OO-), amino (-NH2), secondary amine (-NHR), tertiary amine (-NR2), nitro (-NO2), cyanide (-CN), amide (-CONH2), substituted amide (-CONHR, -CONR2), thiol (-SH), sulfide (-SR), sulfonyl (-SO2R), sulfate (-SO4R), phosphate (-PO4R2), Phosphine (-PR2); alkyl (-R), alkylene (-R=R), cycloalkyl (-R), aryl (-Ar), benzyl (-C6H5CH2), alkenyl (-C=C-), alkynyl (-C≡C-), aromatic ring, acyl (-COR); sulfonyl (-SO2R); carbamoyl (-CONH2); isonitrile (-NC); azide (-N3), perfluoroalkyl (-CF3) and other fluoroalkyl chains, acetal (-RCH(OR)2), ketal (-RC(OR)2R), organometallic groups, and combinations thereof, wherein C is phosphate or is selected from the group consisting of sodium (Na), potassium (K), lithium (Li), rubidium sulfonate (Rb), cesium (Cs), calcium (Ca), magnesium (Mg), strontium sulfonate (Sr), barium (Ba), iron (II) (Fe II), iron (III) (Fe III), copper (I) (Cu I), copper (II) (Cu II), zinc (Zn), manganese (Mn), ammonium (NH4), methylammonium (CH3NH3), dimethylammonium ((CH3)2NH2), trimethylammonium ((CH3)3N + ), pyridinium (C5H5NH + ) ,Lead(II)(Pb), mercury(II)(Hg), cadmium(Cd), lanthanum(La), cerium(Ce), uranium(U), sodium-calcium(Na-Ca), potassium-magnesium(K-Mg), tetramethylammonium(N(CH3)4) + ), imidazolium (C3H4NH2 + ), phosphonium (P + (CH3)4), guanidinium (C(NH2)3 + ) phosphate, and combinations thereof, a phosphate salt selected from the group consisting of:

[0017] Surface attachment

[0018] In some embodiments, at least a portion of the additive material contacts a surface of one of the two adjacent particles. In some embodiments, at least a portion of the additive material contacts a surface of one of the two adjacent particles by at least one of a covalent bond or a non-covalent attachment. In some embodiments, the contact between at least a portion of the additive material and the adjacent particles provides a path for diffusion of lithium ions in the solid electrolyte layer. In some embodiments, the solid-state battery is configured to operate at a pressure less than 10 MPa, which is substantially lower than the pressure required in the absence of the additive material in the solid electrolyte layer. In some embodiments, the solid-state battery is configured to operate at a pressure less than 5 MPa. In some embodiments, the solid-state battery has a specific capacity greater than 100 mAh / g.

[0019] Sulfide-containing materials

[0020] In some embodiments, the sulfide-containing material comprises lithium phosphorus sulfur chloride (LPSCl). In some embodiments, the sulfide-containing material has a volume-based average particle size of from 0.1 μm to 50 μm as determined by laser diffraction particle size distribution measurement. In some embodiments, the sulfide-containing material has a first hardness of from 0.1 GPa to 1 GPa as determined by nanoindentation testing, and the additive material has a second hardness of from 0.001 GPa to 0.01 GPa as determined by nanoindentation testing. In some embodiments, the sulfide-containing material has the first hardness, the additive material has the second hardness, and the second hardness is at most 1% of the first hardness. In some embodiments, the additive material is in powder form.

[0021] additive materials

[0022] In some embodiments, the additive material is not in particle form. In some embodiments, the leaving group is triethoxysilyl or trimethoxysilyl. In some embodiments, the additive material is selected from the group consisting of:

[0023] (Chemical formula 2)

[0024] ;

[0025] (Chemical formula 3)

[0026] ;

[0027] (Chemical Formula 4)

[0028] ;

[0029] (Chemical formula 5)

[0030] ;

[0031] (Chemical formula 6)

[0032] ;

[0033] (Chemical formula 7)

[0034] ;

[0035] (Chemical formula 8)

[0036] ;

[0037] (Chemical formula 9)

[0038] ;

[0039] (Chemical formula 10)

[0040] ;

[0041] (Chemical formula 11)

[0042] ;

[0043] (Chemical formula 12)

[0044] ;

[0045] (Chemical formula 13)

[0046] ;

[0047] (Chemical Formula 14)

[0048] ;

[0049] (Chemical Formula 15)

[0050] ;

[0051] (Chemical formula 16)

[0052] ;

[0053] (Chemical formula 17)

[0054] ;

[0055] (Chemical formula 18)

[0056] ;

[0057] (Chemical Formula 19)

[0058] ;

[0059] (Chemical formula 20)

[0060] ;

[0061] (Chemical formula 21)

[0062] ;

[0063] (Chemical formula 22)

[0064] ;

[0065] (Chemical formula 23)

[0066] ;

[0067] (Chemical formula 24)

[0068] ;

[0069] (Chemical formula 25)

[0070] ; and

[0071] A combination of these.

[0072] solid electrolyte

[0073] In some embodiments, the solid electrolyte comprises a sulfide-containing material and an additive material in a weight ratio of 1:1 to 25:1. In some embodiments, the solid electrolyte has a porosity of 5% to 15%. In some embodiments, the solid electrolyte has a density greater than 10% increased compared to a solid electrolyte without the additive material.

[0074] Method for manufacturing a solid-state battery

[0075] Another aspect of the present disclosure provides a method for manufacturing a solid-state battery. The method comprises providing a solid electrolyte, wherein the step comprises ball milling the particles together with an additive material provided herein. In some embodiments, the ball milling allows A to interact with the sulfide-containing material of the particles, such that at least a portion of the additive material adheres to the surface of the particles.

[0076] attachment

[0077] In some embodiments, at least a portion of the additive material is attached to the surface of the particle by non-covalent attachment. In some embodiments, the non-covalent attachment is chemical adsorption, van der Waals interactions, or ionic interactions. In some embodiments, at least a portion of the additive material is attached to the surface of the particle by covalent bonding. In some embodiments, the covalent bond is a sulfide bond or a disulfide bond.

[0078] Solid-state batteries - additional aspects

[0079] Another aspect of the present disclosure provides a solid-state battery comprising: a positive electrode; a negative electrode; a solid electrolyte layer positioned between the positive electrode and the negative electrode and configured to enable transport of lithium ions between the positive electrode and the negative electrode; wherein the solid electrolyte layer comprises particles comprising a sulfide-containing material; and an additive material selected from the group consisting of:

[0080]

[0081] (Chemical formula 2)

[0082] ;

[0083] (Chemical formula 3)

[0084] ;

[0085] (Chemical Formula 4)

[0086] ;

[0087] (Chemical formula 5)

[0088] ;

[0089] (Chemical formula 6)

[0090] ;

[0091] (Chemical formula 7)

[0092] ;

[0093] (Chemical formula 8)

[0094] ;

[0095] (Chemical formula 9)

[0096] ;

[0097] (Chemical formula 10)

[0098] ;

[0099] (Chemical formula 11)

[0100] ;

[0101] (Chemical formula 12)

[0102] ;

[0103] (Chemical formula 13)

[0104] ;

[0105] (Chemical Formula 14)

[0106] ;

[0107] (Chemical Formula 15)

[0108] ;

[0109] (Chemical formula 16)

[0110] ;

[0111] (Chemical formula 17)

[0112] ;

[0113] (Chemical formula 18)

[0114] ;

[0115] (Chemical Formula 19)

[0116] ;

[0117] (Chemical formula 20)

[0118] ;

[0119] (Chemical formula 21)

[0120] ;

[0121] (Chemical formula 22)

[0122] ;

[0123] (Chemical formula 23)

[0124] ;

[0125] (Chemical formula 24)

[0126] ;

[0127] (Chemical formula 25)

[0128] ; and

[0129] A combination of these.

[0130] Interaction

[0131] In some embodiments, the additive material is configured to interact with sulfur of the sulfide-containing material of the particle, wherein at least a portion of the additive material is interposed between two immediately adjacent particles and contacts a surface of one of the two adjacent particles by covalent bonding and / or non-covalent attachment.

[0132] Solid-state batteries - different aspects

[0133] Another aspect of the present disclosure provides a solid-state battery comprising: a cathode; a cathode; and a solid electrolyte layer positioned between the cathode and the anode and configured to enable transport of lithium ions between the cathode and the anode; wherein the solid electrolyte layer comprises particles comprising a sulfide-containing material; and an additive material represented by ABC (chemical formula 1), wherein A is a thiol group (SH), B is a substituted or unsubstituted C3-C10 alkane group, and C is a phosphate or a salt thereof, wherein A is configured to interact with sulfur of the sulfide-containing material of the particles, and at least a portion of the additive material is interposed between two immediately adjacent particles of the particles.

[0134] substituent

[0135] In some embodiments, B is fluoro (-F), chloro (-Cl), bromo (-Br), iodo (-I), hydroxyl (-OH), ether (-OR), aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxide (-OO-), amino (-NH2), secondary amine (-NHR), tertiary amine (-NR2), nitro (-NO2), cyanide (-CN), amide (-CONH2), substituted amide (-CONHR, -CONR2), thiol (-SH), sulfide (-SR), sulfonyl (-SO2R), sulfate (-SO4R), phosphate (-PO4R2), phosphine (-PR2); A substituted C3-C10 alkane group comprising a substituent selected from the group consisting of alkyl (-R), alkylene (-R=R), cycloalkyl (-R), aryl (-Ar), benzyl (-C6H5CH2), alkenyl (-C=C-), alkynyl (-C≡C-), aromatic ring, acyl (-COR); sulfonyl (-SO2R); carbamoyl (-CONH2); isonitrile (-NC); azide (-N3), perfluoroalkyl (-CF3) and other fluoroalkyl chains, acetal (-RCH(OR)2), ketal (-RC(OR)2R), organometallic groups, and combinations thereof.

[0136] salt

[0137] In some embodiments, C is sodium (Na), potassium (K), lithium (Li), rubidium sulfonate (Rb), cesium (Cs), calcium (Ca), magnesium (Mg), strontium sulfonate (Sr), barium (Ba), iron(II) (Fe II), iron(III) (Fe III), copper(I) (Cu I), copper(II) (Cu II), zinc (Zn), manganese (Mn), ammonium (NH4), methylammonium (CH3NH3), dimethylammonium ((CH3)2NH2), trimethylammonium ((CH3)3N + ), pyridinium (C5H5NH +), lead(II)(Pb), mercury(II)(Hg), cadmium(Cd), lanthanum(La), cerium(Ce), uranium(U), sodium-calcium(Na-Ca), potassium-magnesium(K-Mg), tetramethylammonium(N(CH3)4 + ), imidazolium (C3H4NH2 + ), phosphonium (P + (CH3)4), guanidinium (C(NH2)3 + ) phosphate, and a phosphate salt selected from the group consisting of phosphates, and combinations thereof.

[0138] electric cars

[0139] Another aspect of the present disclosure is an electric vehicle comprising a solid-state battery provided herein according to another aspect of the present disclosure.

[0140] Example embodiment

[0141] These and other features of the present disclosure will be understood from the following detailed description ("Detailed Description of the Invention") and will become more fully apparent from the illustrative embodiments of the present disclosure. Furthermore, it will be readily apparent that the objects and advantages of the present disclosure can be realized by the means and combinations thereof set forth in the appended claims.

[0142] No outline restrictions

[0143] It is understood that the present disclosure is not limited to the examples outlined in this summary ("Summary of the Invention"). Various other embodiments are described and illustrated herein.

[0144] Figure 1 is an example of a solid-state battery according to one embodiment.

[0145] Non-limiting examples

[0146] The examples described herein are intended to illustrate specific non-limiting embodiments in one form only, and such examples should not be construed as limiting the scope of the appended claims in any way.

[0147] Examples and Embodiments

[0148] The subject matter of the present disclosure will now be described and discussed in more detail, with reference to the accompanying drawings, in which some, but not all, embodiments of the present disclosure are illustrated, with reference to certain specific embodiments and examples. Like numerals refer to like elements or parts throughout, unless otherwise stated. The subject matter of the present disclosure may be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided so that the present disclosure may satisfy applicable legal requirements. Indeed, many modifications and other embodiments of the subject matter of the present disclosure will occur to those skilled in the art to which the subject matter of the present disclosure pertains. Therefore, it is to be understood that the subject matter of the present disclosure is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims.

[0149] definition

[0150] singular

[0151] As used herein, the singular form of a word includes the plural, unless the context clearly dictates otherwise. The plural form encompasses the singular, and vice versa. Therefore, references to the singular form generally include the plural form of each term. For example, although the present disclosure is described using singular terms such as "layer," "substrate," "cell," etc., two or more of these components (including combinations) may be used.

[0152] "approximately"

[0153] The term "approximately" refers to and encompasses the indicated value and the range above and below that value.

[0154] "Comprises", "Consisting Essentially Of" and "Consisting Of"

[0155] The words "comprise(s)" and "comprising" are to be construed inclusively, not exclusively. Similarly, the terms "include(s)", "including(s)", and "or" are to be construed inclusively unless the context clearly prohibits an inclusive interpretation. A disclosure of an embodiment defined using the term "comprising(s)" is also a disclosure of an embodiment "consisting essentially of" the disclosed component and "consisting of" the disclosed component. The phrase "consisting of" excludes any element, step, or ingredient not specified.

[0156] "and / or"

[0157] The term "and / or" used in the context of "X and / or Y" shall be interpreted as "X", "Y", or "X and Y".

[0158] "On" and "Over"

[0159] As used herein, the terms "on," "applied onto," "formed onto," "deposited onto," "provided onto," and the like mean applied, formed, superimposed, deposited, or provided in contact with a subjacent surface or an upper surface. Conversely, the terms "on," "applied onto," "formed onto," "deposited onto," "overlaid," "provided onto," and the like mean applied, formed, overlaid, deposited, or provided on or over said surface, but not necessarily in contact with said surface. For example, a cambium layer "applied onto" a substrate layer may be in contact with the substrate without intervening materials, but the same phrase does not exclude the presence of one or more other layers of the same or different composition located between the cambium layer and the substrate layer.

[0160] Markush Group

[0161] The term "combination thereof" in any Markush expression used herein means a combination or mixture of one or more elements selected from the group of elements disclosed in the Markush expression, and indicates the presence of one or more elements selected from the group. The term "combination thereof" includes all possible combinations of the elements to which the term refers.

[0162] "between"

[0163] The term "between" as used herein includes the endpoints.

[0164] Numerical range

[0165] Additionally, all numerical ranges herein should be understood to include all integers, whole numbers, or fractions within that range. Additionally, any numerical range recited herein is intended to include all subranges subsumed therein, and these numerical ranges should be construed to support claims relating to any number or subset of numbers within that range. For example, a disclosure of 1 to 10 should be construed to support ranges of 1 to 8, 3 to 7, 1 to 9, 3.6 to 4.6, 3.5 to 9.9, etc. When a range is given, any endpoint of that range and / or any number within that range may be combined with the range of the present disclosure.

[0166] "including", "such as" and "for example"

[0167] As used herein, the terms “including,” “such as,” “for example,” and similar terms mean “including / such as / for example, but not limited to.”

[0168] Combination of embodiments

[0169] The term "example" as used herein, especially when followed by a list of terms, is intended to be illustrative only and should not be construed as exclusive or comprehensive. Any embodiment disclosed herein may be combined with any other embodiment disclosed herein, unless expressly stated otherwise.

[0170] particle size

[0171] The particle size used herein is the average particle diameter (D) measured using a microscope (e.g., optical microscope, electron microscope, scanning electron microscope (SEM), transmission electron microscope (TEM), atomic force microscope (AFM), confocal microscope, X-ray microscope, cryo-electron microscope, Raman microscope or fluorescence microscope). 50 ) refers to a particle. The size may be the diameter of a spherical particle or the length along the maximum dimension of an oval or other irregularly shaped particle. As used herein, the particle "D 50 " refers to the diameter at which 50% of the particles have a smaller diameter.

[0172] Operating pressure

[0173] Operating pressure

[0174] The operating pressure of solid-state batteries can vary depending on the specific design and materials used. Solid-state batteries are characterized by the use of solid electrolytes instead of the liquid electrolytes found in traditional lithium-ion batteries. As a result, they can potentially operate at different pressures compared to liquid-electrolyte batteries.

[0175] Factors that determine operating pressure

[0176] Generally, solid-state batteries are designed to operate at atmospheric pressure or slightly higher. The exact operating pressure may depend on factors such as the specific materials used for the solid electrolyte and electrodes, the cell design, and the intended use of the battery. For example, the solid electrolyte in these batteries can be made from a variety of materials, including ceramics, polymers, or sulfide compounds. These materials have properties that affect the operating pressure of the battery. For example, some ceramic electrolytes may require higher pressures to maintain good contact between components and ensure efficient ion transport. In contrast, certain polymer electrolytes, due to their flexibility, may allow operation at lower pressures.

[0177] Higher operating pressure

[0178] Some solid-state battery designs aim to operate at ambient pressure, similar to conventional lithium-ion batteries. However, some solid-state battery concepts can benefit from operating at higher pressures. Compared to liquid electrolytes, solid electrolytes often contain voids within the material, leading to poor contact between solid electrolyte materials (e.g., particle-like structures) and between lithium ions and the solid electrolyte material, resulting in poor electrical conductivity and poor lithium ion diffusion within the solid electrolyte layer. Increasing pressure can potentially improve contact between the solid electrolyte and electrode materials, potentially improving overall battery performance.

[0179] The challenge of high operating pressure

[0180] Solid-state batteries offer several advantages, including potential improvements in safety and energy density, but their high operating pressures can be a challenge.

[0181] mechanical stress

[0182] High pressures within a battery cell can cause mechanical stress on materials, including the solid electrolyte and electrodes. Over time, this stress can lead to component deformation, cracking, or failure, compromising the structural integrity of the battery.

[0183] Sealing task

[0184] Maintaining high-pressure environments may require effective sealing of battery cells. Achieving and maintaining reliable sealing under high pressure can be challenging, and any leaks can lead to the ingress of contaminants or air, compromising battery performance and safety.

[0185] Manufacturing complexity

[0186] Designing and manufacturing batteries capable of operating at high pressure can be more complex and costly. Meticulous engineering and manufacturing processes are required to ensure reliable sealing, prevent leakage, and prevent mechanical failure.

[0187] Material Compatibility

[0188] Materials used in solid-state batteries, including solid electrolytes and electrodes, may be compatible with high-pressure conditions. Some materials may degrade or undergo undesirable chemical reactions under high pressure, affecting the overall performance and cycle life of the battery.

[0189] Energy density tradeoff

[0190] Higher pressures can improve certain aspects of battery performance, but may also lead to trade-offs in energy density.

[0191] Temperature effect

[0192] High pressure can affect the thermal behavior of a battery. Managing heat dissipation is desirable to prevent overheating and ensure safe operation of solid-state batteries at high pressures.

[0193] New additive materials

[0194] Additives attached to solid electrolytes

[0195] The present disclosure addresses a key challenge in solid-state battery technology by introducing novel additive materials designed to enhance the performance of sulfide-containing solid electrolytes. Aspects of the present disclosure relate to additives added to sulfide-containing solid electrolyte materials for use in solid-state batteries, solid-state batteries using such additive materials in the solid electrolyte material, and methods for manufacturing such solid-state batteries. These additive materials are specifically formulated to interact with the sulfide-containing solid electrolyte material at the molecular level, thereby creating a unique adhesion mechanism in which at least a portion of the additive material binds or adheres to the surface of the sulfide-containing solid electrolyte material.

[0196] lithium ion diffusion

[0197] This surface adhesion serves several important functions. It promotes the overall conductivity or diffusion of lithium ions in the solid electrolyte layer. By creating a network of conductive pathways between adjacent electrolyte particles through contact between at least a portion of the additive material and the adjacent solid electrolyte material, the additive promotes more efficient lithium ion transport through the battery structure.

[0198] Contact between components

[0199] Additionally, the attached additive material acts as a flexible or moldable interface between the rigid electrolyte particles. The additive material may be in the form of individual molecules rather than particles. Each of these additive material molecules may be flexible, allowing them to bend or move without breaking, and retain the ability to return to their original shape after deformation. Alternatively, each of these additive material molecules may be moldable, allowing them to be shaped, molded, or deformed without breaking or losing their integrity. This flexibility or moldability helps maintain critical contact between components by accommodating volume changes that may occur during battery cycling.

[0200] stability

[0201] Furthermore, the additive materials provided herein can improve performance at relatively low pressures compared to solid-state batteries without such additive materials by enhancing particle-to-particle contact and overall electrolyte cohesion. The improved particle-to-particle contact holds the solid electrolyte material together, ensuring a continuous path for lithium ions to efficiently move between electrodes, enhancing the stability of the solid electrolyte, and preventing the solid electrolyte from deteriorating over time or cracking under stress.

[0202] Benefits of reduced operating pressure

[0203] The ability to operate solid-state batteries at reduced pressures represents a significant advancement in this field. Conventional solid-state batteries often require high pressures to maintain proper contact between components, which can result in mechanical stress, potential safety issues, and manufacturing complexity. The additive materials provided in the present disclosure enable low-pressure operation, which can offer several benefits, including but not limited to improved safety and lifespan due to reduced mechanical stress on battery components, simplified battery design and manufacturing processes, the potential for lighter and more compact battery structures, and an expansion of the potential applications of solid-state battery technology.

[0204] Manufacturing process

[0205] Additionally, the described method for incorporating these additive materials into solid-state batteries is designed to be compatible with existing manufacturing processes, making it readily adaptable for mass production by manufacturers.

[0206] additive materials

[0207] The additive material provided herein can be represented by the following chemical formula 1:

[0208] ABC (chemical formula 1)

[0209] Here, A is a thiol group (SH) or a leaving group, B is a substituted or unsubstituted C3-C20 alkane group, and C is a phosphate or its salt. The alkane group is composed entirely of singly bonded carbon and hydrogen atoms and has the general formula C n H 2n+2 have

[0210] covalent bond

[0211] In some embodiments, A in the additive material ABC (Formula 1) provided herein may be a thiol group (SH). In some embodiments, the thiol group may react with sulfur in the sulfide-containing solid electrolyte material to form a covalent bond, such as a sulfide bond or a disulfide bond. This covalent bond allows at least a portion of the additive material to attach to the surface of the solid electrolyte material particles. In some embodiments, when the sulfide-containing material includes a metal ion, a metal-sulfur covalent bond may be formed to create a strong anchoring point for the additive material.

[0212] Multiple covalent bonds

[0213] Additionally, the formation of multiple covalent bonds between a single additive molecule and multiple sulfur atoms on the electrolyte surface can create a cross-linked network, thereby enhancing the structural stability of the interface. Multiple electrolyte particles are linked by cross-linking between the additive molecule and multiple sulfur atoms to form a three-dimensional network, thereby increasing the strength, toughness, and / or elasticity of the electrolyte material, resulting in a more stable electrolyte material with enhanced durability and mechanical strength, and greater resistance to deformation or volume change.

[0214] Redox reaction

[0215] In some cases, covalent bonding may involve redox reactions, where thiol groups are oxidized to form disulfide bonds, potentially contributing to the electrochemical properties of solid-state batteries.

[0216] Strength and properties of covalent bonds

[0217] The strength and nature of these covalent bonds can be influenced by factors such as local pH, applied voltage, and the presence of other ions within the solid electrolyte system, potentially allowing for tuning of interfacial properties to optimize battery performance.

[0218] Non-covalent attachment

[0219] In some embodiments, the additive material having a thiol group can be adsorbed onto the particle surface of the sulfide-containing material within the solid electrolyte layer, such that at least a portion of the additive material is attached to the particle surface of the sulfide-containing material by non-covalent attachment. The non-covalent attachment can be chemical adsorption, van der Waals interaction, ionic interaction, hydrogen bonding, π-π stacking, dipole-dipole interaction, or electrostatic interaction.

[0220] chemical adsorption

[0221] Chemisorption refers to the formation of a chemical bond between the adsorbate and the surface, which may be stronger than typical physical adsorption but weaker than covalent bonds.

[0222] van der Waals forces

[0223] Van der Waals forces are weak attractive forces between molecules or atoms that result from temporary fluctuations in the distribution of electrons.

[0224] Tuning of non-shared attachment

[0225] The strength and nature of these bonds can be tuned by modifying the chemical structure of the additive material. For example, varying the number and location of hydrogen bond donors / acceptors can alter hydrogen bonding interactions. Incorporating different aromatic ring systems or heteroatoms can influence π-π stacking and dipole interactions. Adjusting side chain length, branching, and polarity can influence van der Waals forces and overall adsorption behavior. Adding charged functional groups or zwitterionic moieties can enhance electrostatic interactions and potentially improve ionic conductivity at the particle-additive interface.

[0226] Detachment

[0227] In some embodiments, A in the additive material ABC (formula 1) provided herein may be a leaving group. The term "leaving group" may be understood as defined by IUPAC and may be, for example, an atom or group of atoms that separates from a main moiety or a residue moiety of a substrate during a reaction or an elementary step of a reaction. For example, a leaving group may be a fragment that is separated along with a pair of electrons in heterolytic bond cleavage.

[0228] Examples of detachment

[0229] Additional examples of leaving groups include halides such as chloride, bromide, or iodide; tosylate (p-toluenesulfonate) or mesylate (methanesulfonate) groups; acetate or trifluoroacetate groups; phosphate or phosphonate groups; carboxylate groups such as formate or benzoate; alkoxide groups such as methoxide or ethoxide; amine groups such as dimethylamino or diethylamino; cyano (CN) groups; azide (N3) groups; and sulfonate groups such as triflate (trifluoromethanesulfonate).

[0230] Additional examples of detachment

[0231] In certain embodiments, the leaving group may be an anionic or neutral species that is released from a neutral or cationic substrate. Any suitable leaving group compatible with the solid electrolyte material may be used. In some embodiments, the leaving group may comprise a "triethoxysilyl" moiety (e.g., derived from HSi(OC2H5)3) or a "trimethoxysilyl" moiety (e.g., derived from HSi(OCH3)3).

[0232] The choice of the departure period

[0233] According to aspects of the present disclosure, the selection of the leaving group can be tailored to optimize reactivity with the sulfide-containing solid electrolyte material or to enhance specific properties of the resulting solid-state battery. Furthermore, the leaving group may be selected based on factors such as stability, ease of synthesis, or compatibility with battery manufacturing processes.

[0234] covalent bond

[0235] In some embodiments, the leaving group can react with sulfur in the sulfide-containing solid electrolyte material to form a covalent bond, such as a sulfide bond or a disulfide bond. This covalent bond allows at least a portion of the additive material to attach to the surface of the solid electrolyte material particles. The covalent bond formed between the leaving group and sulfur in the sulfide-containing solid electrolyte material can involve a variety of chemical interactions, including sulfide bonds, disulfide bonds, metal-sulfur bonds, or multiple covalent bonds that form a cross-linked network.

[0236] Coordination of shared attachment

[0237] The strength and nature of the covalent attachment can be tuned by modifying the chemical structure of the leaving group, such as by using different electron-withdrawing or electron-donating substituents, sterically bulky groups, or multifunctional leaving groups.

[0238] Shared attachment process

[0239] The covalent attachment process can be initiated or enhanced by thermal activation, photochemical activation, mechanical force during ball milling or pressing, or chemical catalysts.

[0240] Degree and distribution of shared attachment

[0241] The extent and distribution of covalent attachment across the solid electrolyte particles can be controlled by adjusting the ratio of additives to the solid electrolyte material, by exploiting preferential attachment to specific crystal facets or surface features, or by exploiting reversible attachment under specific conditions for dynamic reorganization.

[0242] Non-covalent attachment

[0243] In some embodiments, the additive material having a leaving group can interact with particles of the sulfide-containing material in the solid electrolyte layer. In some embodiments, the additive material is adsorbed to the surface of the particle, such that at least a portion of the additive material is attached to the surface of the particle of the sulfide-containing solid electrolyte material by non-covalent attachment. The non-covalent attachment can be chemical adsorption, van der Waals interaction, ionic interaction, hydrogen bonding, π-π stacking, dipole-dipole interaction, or electrostatic interaction.

[0244] Unsubstituted alkane group

[0245] In some embodiments, B in the additive material ABC (Formula 1) provided herein can be an unsubstituted C3-C20 alkane group. For example, B can be an unsubstituted C3-C5 alkane group, an unsubstituted C6-C16 alkane group, an unsubstituted C16-C20 alkane group, or an unsubstituted alkane group having any other number of carbons from 3 to 20.

[0246] substituted alkane group

[0247] In some embodiments, B of the additive material ABC (Formula 1) provided herein is halogen [fluoro (-F), chloro (-Cl), bromo (-Br), iodo (-I)]; Oxygen-containing substituents [hydroxyl (-OH), ether (-OR), carbonyl group (aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxide (-OO-)]; nitrogen-containing substituents [amino (-NH2), N-substituted amine (secondary amine (-NHR), tertiary amine (-NR2), nitro (-NO2), cyanide (-CN), amide (-CONH2) or substituted amide (-CONHR, -CONR2)]; sulfur-containing substituents [thiol (-SH), sulfide (-SR), sulfonyl (-SO2R), sulfate (-SO4R)]; phosphorus-containing substituents [phosphate (-PO4R2), phosphine (-PR2)]; hydrocarbon-based substituents [alkyl (-R), alkylene (-R=R), cycloalkyl (-R), aryl (-Ar), benzyl (-C6H5CH2)]; alkenyl (-C=C-); alkynyl (-C≡C-); aromatic ring; acyl (-COR); sulfonyl (-SO2R); carbamoyl (-CONH2); isonitrile (-NC); azide (-N3); polyfunctional groups [perfluoroalkyl (-CF3) and other fluoroalkyl chains, acetal (-RCH(OR)2), ketal (-RC(OR)2R)]; metal-based substituents [organometallic groups (e.g., methyl lithium (-CH3Li), Grignard reagent (-RMgX))]; and combinations thereof. For example, B may be a substituted C3-C5 alkane group, a substituted C6-C16 alkane group, a substituted C16-C20 alkane group, or a combination thereof, comprising a substituent that may be chlorine, bromine, an ester, a ketone, or any combination thereof. An alkane group, or a substituted alkane group having any other number of carbons from 3 to 20.

[0248] alkane group

[0249] In some embodiments, B in the additive material ABC (formula 1) provided herein can be an unsubstituted or substituted C3-C20 alkane group. For example, B can be unsubstituted or substituted C3, C4, C5, C6, C7, C8, C9, C10, C3-C4, C3-C5, C3-C6, C3-C7, C3-C8, C3-C9, C3-C10, C4-C5, C4-C6, C4-C7, C4-C8, C4-C9, C4-C10, C5-C6, C5-C7, C5-C8, C5-C9, C5-C10, C6-C7, C6-C8, C6-C9, C6-C10, C7-C8, C7-C9, C7-10, C8-C9, C8-10, C9-C10, etc.

[0250] Examples of alkane groups

[0251] Non-limiting examples of B of the additive material ABC (formula 1) provided herein include substituted or unsubstituted propane, n-butane (CH3CH2CH2CH3), isobutane (CH3CH(CH3)2), n-pentane (CH3(CH2)3CH3), isopentane (2-methylbutane, CH3CH2CH(CH3)2), neopentane (2,2-dimethylpropane, (CH3)4C), n-hexane (CH3(CH2)4CH3), 2-methylpentane (CH3CH2CH2CH(CH3)CH3), 3-methylpentane (CH3CH2CH(CH3)CH2CH3), 2,2-dimethylbutane (CH3C(CH3)2CH2CH3), 2,3-dimethylbutane (CH3CH(CH3)CH(CH3)CH3), n-heptane (CH3(CH2)5CH3), 2-Methylhexane (CH3CH2CH2CH2CH(CH3)CH3), 3-Methylhexane (CH3CH2CH2CH(CH3)CH2CH3), 2,2-dimethylpentane (CH3C(CH3)2CH2CH2CH3), 2,3-dimethylpentane (CH3CH(CH3)CH2CH(CH3)CH3), 2,4-dimethylpentane (CH3CH(CH3)CH2CH2CH(CH3)CH3), 3,3-dimethylpentane (CH3CH2CH(CH3)2CH2CH3), 3-ethylpentane (CH3CH2CH2CH(CH2CH3)CH3), 2,2,3-trimethylbutane ((CH3)2CHCH2CH(CH3)2), n-octane (CH3(CH2)6CH3), 2-methylheptane (CH3CH2CH2CH2CH2CH(CH3)CH3), 3-Methylheptane (CH3CH2CH2CH2CH(CH3)CH2CH3), 4-Methylheptane (CH3CH2CH2CH(CH3)CH2CH2CH3), 2,2-dimethylhexane (CH3C(CH3)2(CH2)4CH3), 2,3-dimethylhexane (CH3CH(CH3)CH2CH2CH(CH3)CH3), 2,4-dimethylhexane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH3), 3,3-dimethylhexane (CH3CH2CH(CH3)2CH2CH2CH3), 3,4-dimethylhexane (CH3CH2CH(CH3)CH2CH(CH3)CH3), 2,2,4-trimethylpentane (isooctane, CH3CH(CH3)2CH2CH(CH3)2), 2-ethylhexane (CH3CH2CH(CH2CH3)CH2CH3),n-nonane (CH3(CH2)7CH3), 2-methyloctane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-methyloctane (CH3CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-dimethylheptane (CH3C(CH3)2(CH2)5CH3), 2,3-dimethylheptane (CH3CH(CH3)CH2CH2CH2CH2CH(CH3)CH3), 2,4-dimethylheptane (CH3CH(CH3)CH2CH2CH(CH3)CH2CH3), 2,2,4-trimethylhexane (CH3C(CH3)2CH2CH(CH3)2CH2CH2CH3), 3,3-dimethylheptane (CH3CH2CH(CH3)2CH2CH2CH2CH3), 3-Ethylheptane (CH3CH2CH2CH(CH2CH3)CH2CH3), n-decane (CH3(CH2)8CH3), 2-methylnonane (CH3CH2CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-methylnonane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-dimethyloctane (CH3C(CH3)2(CH2)6CH3), 2,3-dimethyloctane (CH3CH(CH3)CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 2,4-dimethyloctane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH2CH3), 2,5-dimethyloctane (CH3CH2CH(CH3)CH2CH2CH2CH2CH3), 3,3-Dimethyloctane (CH3CH2CH(CH3)2CH2CH2CH(CH3)CH2CH3), 2-ethyloctane (CH3CH2CH(CH2CH3)CH2CH2CH3), n-undecane (C, 11 H 24 ) and its branched isomers, n-dodecane (C 12 H 26 ) and its branched isomer, n-tridecane (C 13 H 28 ) and its branched isomer, n-tetradecane (C 14 H 30 ) and its branched isomer, n-pentadecane (C 15 H 32 ) and its branched isomers, n-hexadecane (C 16 H 34 ) and its branched isomer, n-heptadecane (C 17H 36 ) and its branched isomer, n-octadecane (C 18 H 38 ) and its branched isomer, n-nonadecane (C 19 H 40 ) and its branched isomers, n-eicosane (C 20 H 42 ) and branched isomers thereof, but are not limited thereto.

[0252] salt

[0253] In some embodiments, C can be a phosphate salt. For example, C can be an alkali metal salt [sodium (Na), potassium (K), lithium (Li), rubidium sulfonate (Rb), and / or cesium (Cs) phosphate], an alkaline earth metal salt [calcium (Ca), magnesium (Mg), strontium sulfonate (Sr), and / or barium (Ba) phosphate], a transition metal salt [iron (II) (Fe II), iron (III) (Fe III), copper (I) (Cu I), copper (II) (Cu II), zinc (Zn), and / or manganese (Mn) phosphate], an ammonium and an organic amine salt [ammonium (NH4), methylammonium (CH3NH3), dimethylammonium ((CH3)2NH2), trimethylammonium ((CH3)3N + ) and / or pyridinium (C5H5NH + ) phosphate], heavy metal salts [lead (II) (Pb), mercury (II) (Hg) and / or cadmium (Cd) phosphate], lanthanide and actinide salts [lanthanum (La), cerium (Ce) and / or uranium (U) phosphate], mixed cation salts [sodium-calcium (Na-Ca) and / or potassium-magnesium (K-Mg) phosphate], exotic and polyatomic cation salts [tetramethylammonium (N(CH3)4 + ), imidazolium (C3H4NH2 + ), phosphonium (P + (CH3)4) and / or guanidinium (C(NH2)3 + ) may be phosphate.

[0254] Examples of additive materials

[0255] Non-limiting examples of additive materials provided herein include, but are not limited to, Chemical Formula 2-25:

[0256] (Chemical formula 2)

[0257] ;

[0258] (Chemical formula 3)

[0259] ;

[0260] (Chemical Formula 4)

[0261] ;

[0262] (Chemical formula 5)

[0263] ;

[0264] (Chemical formula 6)

[0265] ;

[0266] (Chemical formula 7)

[0267] ;

[0268] (Chemical formula 8)

[0269] ;

[0270] (Chemical formula 9)

[0271] ;

[0272] (Chemical formula 10)

[0273] ;

[0274] (Chemical formula 11)

[0275] ;

[0276] (Chemical formula 12)

[0277] ;

[0278] (Chemical formula 13)

[0279] ;

[0280] (Chemical Formula 14)

[0281] ;

[0282] (Chemical Formula 15)

[0283] ;

[0284] (Chemical formula 16)

[0285] ;

[0286] (Chemical formula 17)

[0287] ;

[0288] (Chemical formula 18)

[0289] ;

[0290] (Chemical Formula 19)

[0291] ;

[0292] (Chemical formula 20)

[0293] ;

[0294] (Chemical formula 21)

[0295] ;

[0296] (Chemical formula 22)

[0297] ;

[0298] (Chemical formula 23)

[0299] ;

[0300] (Chemical formula 24)

[0301] ;

[0302] (Chemical formula 25)

[0303] .

[0304] Form of additive material

[0305] The additive material may be in any form suitable for addition to and / or mixing with a sulfide-containing solid electrolyte material for use in a solid-state battery. The physical form of the additive material can significantly affect its interaction with the sulfide-containing solid electrolyte and its overall effectiveness in improving battery performance.

[0306] Powder form

[0307] In some embodiments, the additive material may be in powder form. Powder form may provide advantages such as increased surface area for interaction and improved dispersibility within the solid electrolyte matrix.

[0308] Other forms

[0309] However, depending on the specific manufacturing process and desired properties of the final solid-state battery, other forms of additive materials may also be suitable. For example, the additive material may be provided as a liquid, gel, or even a gas that can be deposited onto the solid electrolyte particles. In some cases, the additive material may be incorporated into the solid electrolyte through a solution-based process, dissolving it in a suitable solvent before mixing it with the sulfide-containing material.

[0310] Choice of form

[0311] The choice of form may depend on factors such as the chemical stability of the additive, its compatibility with other battery components, and the ease of achieving uniform distribution throughout the solid electrolyte layer.

[0312] solid electrolyte layer

[0313] General solid electrolyte layer

[0314] The solid electrolyte layer provided herein is suitable for and facilitates lithium ion diffusion between the positive and negative electrodes. The solid electrolyte layer is electrically connected to the positive and negative electrodes and provides an electrically conductive path for charge carrier movement between the positive and negative electrodes. In some embodiments, the solid electrolyte layer may be formed on the positive or negative electrode and may be in direct contact with the positive or negative electrode. In other embodiments, another functional layer may be interposed between the solid electrolyte layer and the positive and / or negative electrode.

[0315] General materials for solid electrolyte layers

[0316] In general, the material of the solid electrolyte layer is not particularly limited, as long as it allows for close contact with adjacent layers, has suitable electrical conductivity, and does not cause significant chemical changes in the solid battery within the voltage range of the solid battery. For example, the solid electrolyte layer may include, but is not limited to, various inorganic solid electrolytes, polymer solid electrolytes, and / or polymer gel electrolytes.

[0317] General sulfide-containing solid electrolyte materials

[0318] In the solid-state battery provided herein, the solid electrolyte is a sulfide-containing material, which may also be referred to as a "sulfide-based material." The "sulfide-containing electrolyte" used herein refers to an electrolyte containing ions (e.g., Li + ) refers to an electrolyte comprising an inorganic material containing S suitable for conducting sulfur (S) and electrically insulating the positive and negative electrodes of an electrochemical cell. The sulfide-based / containing solid electrolyte material includes sulfur (S) and has the ionic conductivity of a metal belonging to Group I or Group II of the periodic table, and may include a Li-PS-based glass or a Li-PS-based glass ceramic. For example, the sulfide-based / containing solid electrolyte material used herein may include lithium sulfide, silicon sulfide, germanium sulfide, and boron sulfide. Non-limiting examples of the inorganic solid electrolyte include xLi2S.yP2S5(x+y=1), Li3.833 Sn 0.833 As 0.166 S4, Li4SnS4, Li 3.25 Ge 0.25 P 0.75 S4, Li2S-P2S0, B2S3-Li2S, XLi2S-(100-x)P2S5(x=70-80), Li2S-SiS2-Li3N, Li2S-P2S5-LiI, Li2S-SiS2-LiI, Li2S-B2S3-LiI, Li3N, LISICON, LIPON(Li 3+y PO 4-x N x ), thio-LISICON(Li 3.25 Ge 0.25 P 0.75 S4), Li2O-Al2O3-TiO2-P2O5(LATP), Li2S-P2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5, Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2, Li2S-GeS2-ZnS, etc., or a combination thereof.

[0319] Specific sulfide-containing solid electrolyte materials

[0320] In some embodiments of the solid-state battery provided herein, the sulfide-containing solid electrolyte material may include an inorganic solid electrolyte material. In some embodiments, the sulfide-containing solid electrolyte material includes an inorganic solid electrolyte material. In some embodiments, the sulfide-containing solid electrolyte material is Li3P7S. 11 , Li 10 GeP2S 12 , Na3PS4, Li 6-y PS 5-y Cl 1+y (y<1) and / or Li6PS5X (X is Cl, Br or I).

[0321] lithium phosphate sulfur chloride

[0322] In some embodiments, the sulfide-containing solid electrolyte material comprises Li6PS5Cl (lithium phosphorus sulfur chloride, "LPSCl"). LPSCl is known for its high ionic conductivity, an important property for solid electrolyte materials. High ionic conductivity facilitates the efficient movement of lithium ions within the material, facilitating the charge-discharge process of solid-state batteries. LPSCl also exhibits excellent chemical and thermal stability, which is crucial for the long-term performance and safety of solid-state batteries. Stability is particularly important for high-temperature and high-voltage applications. Furthermore, LPSCl exhibits a wide electrochemical stability window and can withstand a wide range of voltages without undesirable reactions. This is essential for supporting a variety of anode and cathode materials.

[0323] Solid electrolyte material particle size

[0324] In the solid-state battery provided herein, the solid electrolyte material is provided in the form of particles. In some embodiments, the sulfide-containing material has a volume-based average particle size, as measured by laser diffraction particle size distribution measurement, of, for example, 0.1 μm to 50 μm, 0.1 μm to 40 μm, 0.1 μm to 30 μm, 0.1 μm to 20 μm, 0.1 μm to 10 μm, 0.1 μm to 5 μm, 0.1 μm to 1 μm, 1 μm to 50 μm, 1 μm to 40 μm, 1 μm to 30 μm, 1 μm to 20 μm, 1 μm to 10 μm, 1 μm to 5 μm, 5 μm to 50 μm, 5 μm to 40 μm, 5 μm to 30 μm, 5 μm to 20 μm, 5 μm to 10 μm, 10 μm to 50μm, 10μm to 40μm, 10μm to 30μm, 10μm to 20μm, 20μm to 50μm, 20μm to 40μm, 20μm to 40μm, 20μm to 30μm, 30μm to 50μm, 30μm to 40μm, 40μm to 50μm, etc. In embodiments, the sulfide-containing solid electrolyte material can have an average particle size in the range of 0.1 μm to 50 μm, such as any of 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 μm. In an embodiment, the particle size of the positive electrode active material can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 0.1 μm to 50 μm.

[0325] Lithium phosphorus sulfur chloride particles forming covalent bonds

[0326] In some embodiments where LPSCl is used as a solid electrolyte material, LPSCl is provided in particle form. In some of these embodiments where the additive material provided herein comprises a thiol group, the thiol group can interact with sulfur of the LPSCl particle to form a sulfide bond or a disulfide bond, thereby allowing at least a portion of the additive material to attach to the surface of the LPSCl particle.

[0327] Interaction between additive materials and solid electrolyte particles

[0328] As provided herein, the interaction between the thiol group or leaving group of the additive material provided herein and the solid electrolyte particles allows the terminal end of the thiol group or leaving group of at least a portion of the additive material to attach to the surface of the solid electrolyte material particle. This attachment allows at least a portion of the additive material attached to the surface of the solid electrolyte particle to reside in and fill the space formed between adjacent solid electrolyte particles. The hydrophobic tail at the other end of at least a portion of the additive material attached to the surface of the solid electrolyte particle also contacts the adjacent solid electrolyte particle. Using the additive material provided herein, the materials within the solid electrolyte layer generally contact each other better, and the solid electrolyte layer has a higher density.

[0329] Benefits of the interaction between additive materials and solid electrolyte particles

[0330] Moreover, the additive material is softer and more fluid than the solid electrolyte particles, so it can expand and contract more easily. During the charge and discharge of the solid battery, the size of the solid electrolyte particles expands or contracts, while the additive material attached to the surface of the solid electrolyte particles changes its own size (e.g., the length of the additive material molecule, or the particle diameter in the case of particles) accordingly and remains in the spaces between the solid electrolyte particles, continuously filling these spaces. This helps prevent the loss of contact between the solid electrolyte particles when the additive material is not used, and helps maintain contact between the solid electrolyte particles and also with the additive material. Therefore, this better contact improves the lithium ion conductivity of the solid electrolyte layer, and maintains the lithium ion conductivity of the solid electrolyte layer during the charge and discharge of the solid battery.

[0331] hardness

[0332] The additive material provided herein may be softer than the solid electrolyte particles. In some embodiments, the sulfide-containing solid electrolyte material may have a hardness of from 0.1 to 1 GPa as determined by nanoindentation testing, and the additive material may have a hardness of from 0.001 to 0.01 GPa as determined by nanoindentation testing. In some embodiments, the hardness of the additive material may be at most 10% of the hardness of the sulfide-containing material, for example, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.01%, or within a range formed by selecting any two values ​​enumerated above or selecting any two values ​​in the range of 0.01% to 10%.

[0333] Weight ratio

[0334] In some embodiments, the solid electrolyte comprises a sulfide-containing material and an additive material, for example, in a ratio of 1:1 to 25:1, 1:1 to 24:1, 1:1 to 23:1, 1:1 to 22:1, 1:1 to 21:1, 1:1 to 20:1, 1:1 to 19:1, 1:1 to 18:1, 1:1 to 17:1, 1:1 to 16:1, 1:1 to 15:1, 1:1 to 14:1, 1:1 to 13:1, 1:1 to 12:1, 1:1 to 11:1, 1:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 1:1 to 6:1, 1:1 to 5:1, 1:1 to 4:1, 1:1 to 3:1, 1:1 to 4:1, or 1:1; or 1:1 to 25:1, 1:1 to 24:1, 1:1 to 23:1, 1:1 to 22:1, 1:1 to 21:1, 1:1 to 20:1, 1:1 to 19:1, 1:1 to 18:1, 1:1 to 17:1, 1:1 to 16:1, 1:1 to 15:1, 1:1 to 14:1, 1:1 to 13:1, 1:1 to 12:1, 1:1 to 11:1, 1:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 1:1 to 6:1, 1:1 to 5:1, 1:1 to 4:1, 1:1 to 3:1, 1:1 to 4:1, or 1:1; or any other ratio in the range of 1:1 to 25:1 or 1:1 to 25:1. In embodiments, the weight ratio of the sulfide-containing material to the additive material can be in the range of 1:1 to 25:1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1 or 25:1.In an embodiment, the weight ratio of the sulfide-containing material and the additive material can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 1:1 to 25:1.

[0335] Air pores

[0336] While the additive material fills the spaces between the particles of the solid electrolyte material, the solid electrolyte layer still maintains a porosity suitable for lithium ions to move through the solid electrolyte layer. In some embodiments, the solid electrolyte layer provided herein has a porosity greater than 5%, for example, from 5% to 15%, from 5% to 14%, from 5% to 13%, from 5% to 12%, from 5% to 11%, from 5% to 10%, from 5% to 9%, from 5% to 8%, from 5% to 7%, from 5% to 6%, or any other % in the range greater than 5%, for example, from 5% to 15% or any other % in the range of 5% to 15%. In embodiments, the porosity of the solid electrolyte layer can be greater than 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%. In embodiments, the porosity of the solid electrolyte layer can be within a range formed by selecting any two values ​​listed above or by selecting any value between 5% and 99%.

[0337] density

[0338] An additive material added to the solid electrolyte material and filling the space between the solid electrolyte material particles increases the density of the solid electrolyte layer. In some embodiments, the solid electrolyte layer has a density increase of greater than 10% compared to when the solid electrolyte layer does not have the additive material. For example, the density of the solid electrolyte layer can be increased by, or by, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any other percentage greater than 10%. In embodiments, the density of the solid electrolyte layer can be increased by any number within a range formed by selecting any two numbers listed above or selecting any two numbers greater than 10%.

[0339] Lower operating pressure

[0340] The additive material within the solid electrolyte layer provided herein allows the interaction between the additive material and the solid electrolyte material particles to cause at least a portion of the additive material to adhere to the surface of the solid electrolyte material particles, thereby improving and / or providing closer contact between the materials within the solid electrolyte layer, for example, between at least a portion of the additive material and adjacent solid electrolyte material particles, as well as between the solid electrolyte material particles themselves. This improved contact is maintained during charging and discharging of the solid battery due to this interaction and adhesion. This improved contact promotes the conductivity of lithium ions in the solid electrolyte layer, thereby enabling the solid battery provided herein to operate at a pressure of less than 10 MPa, which is substantially lower than the pressure required in the absence of the additive material in the solid electrolyte layer. In some embodiments, the solid battery can operate at a pressure of, for example, 9 MPa, 8 MPa, 7 MPa, 6 MPa, 5 MPa, 4 MPa, 3 MPa, 2 MPa, or 1 MPa. In embodiments, the solid-state battery can operate under a pressure within a range formed by selecting any two values ​​listed above or selecting any two values ​​in a range less than 10 MPa.

[0341] Cost

[0342] The lower operating pressure can prevent, reduce, and / or eliminate problems typically associated with high operating pressures applied to solid-state batteries, as described herein. For example, the stability and specific capacity of the solid-state battery can be improved. In some embodiments, the solid-state battery has a specific capacity greater than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420. 430, 440, 450, 460, 470, 480, 490, or 500 mAh / g. In embodiments, the specific capacity of the solid-state battery can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​in a range greater than 100 mAh / g.

[0343] Manufacturing of solid-state batteries

[0344] Method for manufacturing a solid-state battery

[0345] Another aspect of the present disclosure provides a method for manufacturing a solid-state battery. The method comprises providing a solid electrolyte, which comprises ball milling a mixture of particles of a sulfide-containing solid electrolyte material and an additive material provided herein. While ball milling is used as an example herein, other known methods for mixing or combining the solid electrolyte material and the additive material may also be employed. Examples of such known methods include solution-based techniques such as meteoric mixing, high-shear mixing, ultrasonic mixing, mechanical alloying, or spray drying followed by co-precipitation, sol-gel processing, or heat treatment.

[0346] Weight ratio

[0347] In some embodiments, the mixture comprises a sulfide-containing solid electrolyte material and an additive material, for example, in a ratio of 1:1 to 25:1, 1:1 to 24:1, 1:1 to 23:1, 1:1 to 22:1, 1:1 to 21:1, 1:1 to 20:1, 1:1 to 19:1, 1:1 to 18:1, 1:1 to 17:1, 1:1 to 16:1, 1:1 to 15:1, 1:1 to 14:1, 1:1 to 13:1, 1:1 to 12:1, 1:1 to 11:1, 1:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 1:1 to 6:1, 1:1 to 5:1, 1:1 to 4:1, 1:1 to 3:1, 1:1 to 4:1, or 1:1; or 1:1 to 25:1, 1:1 to 24:1, 1:1 to 23:1, 1:1 to 22:1, 1:1 to 21:1, 1:1 to 20:1, 1:1 to 19:1, 1:1 to 18:1, 1:1 to 17:1, 1:1 to 16:1, 1:1 to 15:1, 1:1 to 14:1, 1:1 to 13:1, 1:1 to 12:1, 1:1 to 11:1, 1:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 1:1 to 6:1, 1:1 to 5:1, 1:1 to 4:1, 1:1 to 3:1, 1:1 to 4:1, or 1:1; or any other ratio in the range of 1:1 to 25:1 or 1:1 to 25:1. In embodiments, the weight ratio of the sulfide-containing material to the additive material can be in the range of 1:1 to 25:1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1 or 25:1.In an embodiment, the weight ratio of the sulfide-containing material and the additive material can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 1:1 to 25:1.

[0348] Ball milling general

[0349] Ball milling is a useful technique for mixing and preparing materials for solid-state batteries. Ball milling is a widely used mechanical technique for grinding powders into fine particles and blending materials for a variety of applications, including the preparation of solid-state battery components. For solid-state batteries, ball milling is often employed to mix and blend electrode materials, solid electrolytes, and other components. Examples of ball milling devices include planetary ball mills, attritor mills, and vibrating ball mills. These devices typically consist of a rotating or vibrating chamber containing grinding balls made of materials such as steel, ceramic, or zirconia.

[0350] Homogeneous mixing

[0351] Ball milling is effective in obtaining a homogeneous mixture of different powders. This is crucial for ensuring a uniform distribution of components within the electrode material and solid electrolyte, which affects the overall performance of the battery.

[0352] Reduction of particle size

[0353] Ball milling can reduce the particle size of the relevant material, increasing surface area and improving reactivity. Smaller particle sizes improve electrochemical reaction kinetics, contributing to better battery performance.

[0354] Enhanced electrode-electrolyte interface

[0355] Ball milling can facilitate the formation of a well-defined interface between the electrode and the solid electrolyte, which is crucial for promoting efficient ion transport and minimizing interfacial resistance within solid-state batteries.

[0356] Acceleration of solid-state reactions

[0357] Ball milling can promote the formation of desired phases and structures in materials by inducing solid-state reactions between different components. This is particularly relevant for the synthesis of composite electrode materials or the preparation of composite electrolyte materials provided herein.

[0358] Optimization of challenge

[0359] Ball milling can be used to optimize the conductivity of electrode materials by ensuring good distribution of conductive additives, such as carbon or metal nanoparticles, within the composite, or additive materials within the solid electrolyte.

[0360] Control of morphology

[0361] The milling process can also affect the material's morphology, including particle shape and size distribution. Controlling these aspects is crucial for achieving desired electrochemical properties and overall performance of solid-state batteries.

[0362] Energy Considerations

[0363] Ball milling is an energy-intensive process, and the duration and speed of milling must be carefully controlled to avoid excessive heating, which can lead to unwanted reactions or material damage.

[0364] speed

[0365] In some embodiments, ball milling is performed at, for example, 250 RPM to 750 RPM, 250 RPM to 700 RPM, 250 RPM to 650 RPM, 250 RPM to 600 RPM, 250 RPM to 550 RPM, 250 RPM to 500 RPM, 250 RPM to 450 RPM, 250 RPM to 400 RPM, 250 RPM to 350 RPM, 250 RPM to 300 RPM, 300 RPM to 750 RPM, 300 RPM to 700 RPM, 300 RPM to 650 RPM, 300 RPM to 600 RPM, 300 RPM to 550 RPM, 300 RPM to 450 RPM, 300 RPM to 400 RPM, 300 RPM to 350 RPM, 350 RPM to 750 RPM, 350 RPM to 700 RPM, 350 RPM to 650 RPM, 350 RPM to 600 RPM, 350 RPM to 550 RPM, 350 RPM to 450 RPM, 350 RPM to 400 RPM, 400 RPM to 750 RPM, 400 RPM to 700 RPM, 400 RPM to 650 RPM, 400 RPM to 600 RPM, 400 RPM to 550 RPM, 400 RPM to 500 RPM, 400 RPM to 450 RPM, 450 RPM to 750 RPM, 450 RPM to 700 RPM, 450 RPM to 650 RPM, 450 RPM to 600 RPM, 450 RPM to 550 RPM, 450 RPM to 500 RPM, 500 RPM to 750 RPM, 500 RPM to 700 RPM, 500 RPM to 650 RPM, 500 RPM to 600 RPM, 500 RPM to 550 RPM, 550 RPM to 750 RPM, 550 RPM to 700 RPM, 550 RPM to 650 RPM, 550 RPM to 600 RPM, 600 RPM to 750 RPM, 600 RPM to 700 RPM, 600 RPM to 650 RPM, 650 RPM to 750 RPM, 650 RPM to 700 RPM, or 700 RPM to 750 RPM, 250 RPM, 300 RPM,It is performed at a speed of 350 RPM, 400 RPM, 450 RPM, 500 RPM, 550 RPM, 600 RPM, 650 RPM, 700 RPM, 750 RPM, etc. In an embodiment, the speed at which ball milling is performed can be within a range formed by selecting any two numbers listed above or selecting any two numbers in the range of 250 RPM to 750 RPM.

[0366] period

[0367] In some embodiments, ball milling is performed for, for example, 1 minute to 20 hours, 1 minute to 19 hours, 1 minute to 18 hours, 1 minute to 17 hours, 1 minute to 16 hours, 1 minute to 15 hours, 1 minute to 14 hours, 1 minute to 13 hours, 1 minute to 12 hours, 1 minute to 11 hours, 1 minute to 10 hours, 1 minute to 9 hours, 1 minute to 8 hours, 1 minute to 7 hours, 1 minute to 6 hours, 1 minute to 5 hours, 1 minute to 4 hours, 1 minute to 3 hours, 1 minute to 2 hours, 1 minute to 1 hour, 1 hour to 20 hours, 1 hour to 19 hours, 1 hour to 18 hours, 1 hour to 17 hours, 1 hour to 16 hours, 1 hour to 15 hours, 1 hour to 14 hours, It is performed for 1 hour to 13 hours, 1 hour to 12 hours, 1 hour to 11 hours, 1 hour to 10 hours, 1 hour to 9 hours, 1 hour to 8 hours, 1 hour to 7 hours, 1 hour to 6 hours, 1 hour to 5 hours, 1 hour to 4 hours, 1 hour to 3 hours, 1 hour to 2 hours, 0.1 hour, 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, etc. In embodiments, ball milling can be performed for a period of time within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 1 minute to 20 hours.

[0368] Effects of ball milling

[0369] In some embodiments, ball milling causes the thiol group or leaving group to interact with the sulfur of the sulfide-containing solid electrolyte material, thereby causing at least a portion of the additive material to attach to the surface of the particle. In some embodiments, at least a portion of the additive material attaches to the surface of the particle by non-covalent attachment. In some embodiments, the non-covalent attachment is chemical adsorption, van der Waals interaction, or ionic interaction. In some embodiments, at least a portion of the additive material attaches to the surface of the particle by covalent bonding. In some embodiments, the covalent bond is a sulfide bond or a disulfide bond.

[0370] Conductivity or diffusivity of lithium ions

[0371] When at least a portion of the additive material is surface-attached to the sulfide-containing solid electrolyte particles, the contact between at least a portion of the additive material and the adjacent solid electrolyte material creates a network of conductive paths between the adjacent electrolyte particles. This network of conductive paths promotes more efficient lithium ion transport through the battery structure. Furthermore, the enhanced particle-to-particle contact holds the solid electrolyte material together, ensuring a continuous path for lithium ions to efficiently migrate between the electrodes.

[0372] Lower operating pressure

[0373] When the additive material and the sulfide-containing solid electrolyte material are ball milled to form a solid electrolyte layer, the interaction between the additive material and the solid electrolyte material particles allows at least a portion of the additive material to adhere to the surface of the solid electrolyte material particles, resulting in better and / or closer contact between materials within the solid electrolyte layer, for example, between at least a portion of the additive material and adjacent solid electrolyte material, as well as between the solid electrolyte material particles. This interaction and adhesion allows this improved contact to be maintained during charging and discharging of the solid battery. This improved contact promotes the conductivity of lithium ions in the solid electrolyte layer, allowing the solid battery provided herein to operate at a pressure of less than 10 MPa, which is substantially lower than the pressure required when the solid electrolyte layer is free of the additive material. In some embodiments, the solid battery can operate at a pressure of, for example, 9 MPa, 8 MPa, 7 MPa, 6 MPa, 5 MPa, 4 MPa, 3 MPa, 2 MPa, or 1 MPa. In embodiments, the solid-state battery can operate under a pressure within a range formed by selecting any two values ​​listed above or selecting any two values ​​in a range less than 10 MPa.

[0374] Cost

[0375] Lower operating pressures can prevent, reduce, or eliminate problems typically associated with high operating pressures applied to solid-state batteries, as described herein. For example, the stability and specific capacity of solid-state batteries can be improved. In some embodiments, the solid-state battery has a specific capacity greater than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420. 430, 440, 450, 460, 470, 480, 490, or 500 mAh / g. In embodiments, the specific capacity of the solid-state battery can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​in a range greater than 100 mAh / g.

[0376] Reaction and testing environment

[0377] Since sulfide-containing materials are sensitive to air and moisture and can decompose to produce toxic gases such as H2-S, the manufacturing and testing steps of the solid-state batteries provided herein may be performed in a sealed device filled with an inert gas such as argon (e.g., MBraun MB 200B, H2O < 0.5 ppm, O2 < 0.5 ppm).

[0378] Other aspects

[0379] The following provides other aspects of the present disclosure. Additional features, embodiments, and examples discussed below may be applied to various aspects of the present invention discussed above. However, if there is a conflict between the information in the preceding discussion and the information in the following discussion, the information in the preceding section shall apply.

[0380] solid-state lithium-ion batteries

[0381] Solid-state batteries can charge and discharge electrical loads multiple times. Solid-state batteries include anode and cathode electrodes, and an electrolyte that allows lithium ions to move between the electrodes. Unlike conventional liquid electrolyte batteries, solid-state batteries do not contain a liquid. Electricity flows between the electrodes when a circuit is formed between the electrodes. During charging of a lithium-ion rechargeable battery, lithium ions are released from the cathode electrode and incorporated into the active material of the cathode electrode. During discharging of a lithium-ion rechargeable battery, lithium ions are released from the cathode electrode and incorporated into the active material of the cathode electrode. As the lithium ions travel back and forth between the electrodes, they transfer energy.

[0382] Solid-state battery configuration

[0383] The present disclosure provides a solid-state battery (100) comprising a positive electrode (102), a negative electrode (104), and a solid electrolyte layer (106) interposed between the positive electrode (102) and the negative electrode (104). Although listed as examples, the solid-state battery (100) does not require all of these components. For example, in some configurations, such as an anodeless system, the negative electrode (104) may be omitted.

[0384] Any additional layer

[0385] The solid state battery (100) may optionally include additional layers or layers, such as, for example, a separator layer, a protective layer, a suppression layer, a solid electrolyte interfacial layer, or a combination thereof.

[0386] protective layer

[0387] For example, a protective layer may be incorporated between the electrodes (102 and 104) and the solid electrolyte layer (106). The protective layer may also serve to improve the overall cycle life and safety of the battery, particularly by mitigating dendrite formation on the positive electrode side. In some cases, the protective layer may help improve the interfacial stability between the electrode and electrolyte, potentially reducing undesirable side reactions. Additionally, the protective layer may improve the mechanical properties of the electrode-electrolyte interface, which may be beneficial in maintaining good contact during cycling.

[0388] protective layer material

[0389] This protective layer may include materials such as lithium phosphate, lithium titanate, or lithium lanthanum zirconium oxide (LLZO), which may help prevent undesirable side reactions at the electrode-electrolyte interface. Other options for the protective layer material include, but are not limited to, lithium niobium oxide (LiNbO3), lithium tantalum oxide (LiTaO3), lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium silicate, and lithium boron oxide.

[0390] membrane layer

[0391] Some configurations of the solid-state battery (100) may also include a separator layer. These separator layers can provide additional mechanical support to the battery structure while still allowing efficient ion transport. The separator layer may also be designed to have a gradient structure with properties optimized for contact with both the positive and negative electrode materials. This gradient structure may involve, for example, varying the porosity, composition, or surface properties across the thickness of the separator. In some embodiments, the separator surface may be functionalized with ion-conducting groups or coatings to enhance lithium ion transport at the electrode-separator interface. The separator layer may further be designed as a multilayer by incorporating different materials optimized for specific functions, such as a mechanically strong core layer sandwiched between ion-conducting outer layers. The separator layer may further be designed to be self-healing, such as by reforming bonds after mechanical stress to prevent short circuits due to dendrite growth.

[0392] Membrane layer material

[0393] While traditional liquid electrolyte batteries often use porous polymer separator layers, solid-state batteries can employ thin ceramic or glass-ceramic layers as separators. Materials such as LLZO, LATP (lithium aluminum titanium phosphate), or LAGP (lithium aluminum germanium phosphate) can be used for this purpose. Other separator layer materials that may be suitable for solid-state batteries include lithium phosphate oxynitride (LiPON), lithium lanthanum titanate (LLTO), lithium garnet-type materials such as Li6BaLa2Ta2O12, sulfide-type materials such as Li10GeP2S12, and polymer-ceramic composites that combine materials such as polyethylene oxide (PEO) with ceramic fillers.

[0394] solid-state battery cells

[0395] FIG. 1 is a diagram illustrating a cell (101) of a solid-state battery (100) according to one embodiment. The cell (101) includes a positive electrode (102), a negative electrode (104), and a solid electrolyte layer (106) intermediate the positive electrode (102) and the negative electrode (104). The cell (101) may optionally include additional layers, such as, for example, a separator layer, a protective layer, a suppression layer, a solid electrolyte interfacial layer, or a combination thereof.

[0396] Cell configuration

[0397] As illustrated in FIG. 1, the solid-state battery (100) may include a single cell (101). In other examples, the solid-state battery (100) may include a plurality of cells, such as at least two cells, at least three cells, or at least four cells. Connecting the cells in series increases the voltage of the solid-state battery (100), and connecting the cells in parallel increases the ampere-hour capacity of the solid-state battery (100).

[0398] Cell dimensions

[0399] A cell (101) may have a width (w1), a length (l1), and a thickness (t1).

[0400] Cell thickness

[0401] The thickness (t1) of the cell (101) is 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400,410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1100, 1200, 1300, Any number in the range of 100 μm to 5000 μm, such as 1400, 1500, 1600, 1700, 1800, 1900, 2000, 3000, 4000 or 5000 μm, or about that number. In some embodiments, the thickness (t1) of the cell (101) can be in a range formed by selecting any two numbers listed above or selecting any two numbers within the range of 100 μm to 5000 μm, for example, within a range between 100 μm and 5,000 μm or between 100 μm and 1,000 μm.

[0402] Aspect ratio of width

[0403] The width (w1) of the cell (101) may be substantially larger than the thickness (t1) of the cell (101). In some embodiments, the aspect ratio of the width (w1) to the thickness (t1) is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, at least 260, at least 270, at least 280, at least 290, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550, at least 600, at least 650, at least 700, at least It can be 750, at least 800, at least 850, at least 900, at least 950, at least 1000, at least 2000, at least 3000, at least 4000, at least 5000, at least 6000, at least 7000, at least 8000, at least 9000 or at least 10000.

[0404] Aspect ratio of length

[0405] The length (l1) of the cell (101) may be substantially greater than the thickness (t1) of the cell (101). In some embodiments, the aspect ratio of length (l1) to thickness (t1) is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, at least 260, at least 270, at least 280, at least 290, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550, at least 600, at least 650, at least 700, at least It can be 750, at least 800, at least 850, at least 900, at least 950, at least 1000, at least 2000, at least 3000, at least 4000, at least 5000, at least 6000, at least 7000, at least 8000, at least 9000 or at least 10000.

[0406] anode electrode

[0407] The positive electrode (102) is associated with one polarity (e.g., the positive electrode) of the solid battery (100). The positive electrode (102) is configured as a positive electrode during discharge of the solid battery (100). The positive electrode (102) is suitable for lithium ion diffusion between the current collector (108) and the solid electrolyte layer (106). The positive electrode (102) is in electrical communication with the current collector (108).

[0408] Positioning of the anode electrode

[0409] In one embodiment, the positive electrode (102) is formed on and in direct contact with the current collector (108). In another embodiment, another functional layer may be interposed between the positive electrode (102) and the current collector (108).

[0410] Materials for anode electrodes

[0411] The positive electrode (102) may be capable of reversible absorption and release of lithium ions. For example, the positive electrode (102) may include only a positive electrode active material. In another example, the positive electrode (102) may optionally include one or more of conductive carbon, a solid electrolyte material, and a binder. Optionally, the positive electrode (102) may further include additives, such as, for example, an oxidation stabilizer, a reduction stabilizer, a flame retardant, a heat stabilizer, an antifogging agent, a thickener, a plasticizer, an ion conductivity improver, a binder (described in more detail below), a dispersant, a wetting agent, an adhesion promoter, a crosslinking agent, a colorant, or the like, or a combination thereof.

[0412] Examples of additives

[0413] Examples of these additives may include butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT) as oxidation stabilizers, ascorbic acid or sodium sulfite as reduction stabilizers, aluminum hydroxide or magnesium hydroxide as flame retardants, phenolic compounds or phosphites as heat stabilizers, polyethylene glycol or silica nanoparticles as antifogging agents, carboxymethyl cellulose (CMC) or xanthan gum as thickeners, dibutyl phthalate or triethyl citrate as plasticizers, ceramic fillers or ionic liquids as ionic conductivity enhancers, polyvinylpyrrolidone or sodium dodecyl sulfate as dispersants, polysorbates or poloxamers as wetting agents, silanes or titanates as adhesion promoters, peroxides or aziridines as crosslinking agents, and carbon black or metal oxides as colorants.

[0414] positive electrode active material

[0415] The cathode active material is lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), Li[Ni a Co b Mn c M 1 d]O2(here M 1 is any one element selected from the group consisting of Al, Ga, In or a combination thereof, and 0.3≤a<1.0, 0≤b≤0.5, 0≤c≤0.5, 0≤d≤0.1 and a+b+c+d=1), Li(Li e M 2 f-e-f M 3 f' )O 2-g A g (Here, 0≤e≤0.2, 0.6≤f≤1, 0≤f'≤0.2, 0≤g≤0.2, and M 2 contains at least one element selected from the group consisting of Mn, and Ni, Co, Fe, Cr, V, Cu, Zn and Ti, and M 3 is at least one element selected from the group consisting of Al, Mg and B, and A is at least one element selected from the group consisting of P, F, S and N), or a compound substituted with one or more transition metals; Li 1+h Mn 2-h Lithium manganese oxide, such as LiMnO3, LiMn2O3, LiMnO2, etc., represented by the chemical formula O4 (where 0≤h≤0.33); lithium copper oxide (Li2CuO2); vanadium oxide, such as LiV3O8, V2O5, or Cu2V2O7; LiNi 1-i M 4 i O2 (M here 4 =Ni-site type lithium nickel oxide represented by the chemical formula (Co, Mn, Al, Cu, Fe, Mg, B or Ga, and 0.01≤y≤0.3); LiMn 2-j M 5 j O2 (M here 5 =Co, Ni, Fe, Cr, Zn or Ta, and 0.01≤y≤0.1) or Li2Mn3M 6 O8 (M here 6=Fe, Co, Ni, Cu or Zn); LiMn2O4 where Li is partially substituted with an alkaline earth metal ion; disulfide compounds; LiFe3O4, Fe2(MoO4)3; etc.; or combinations thereof.

[0416] Phosphate-based materials

[0417] In addition to the positive electrode active materials described above, the positive electrode may include other types of materials. For example, lithium iron phosphate (LiFePO4) can be used as the positive electrode active material because of its excellent thermal stability and long cycle life. Lithium manganese iron phosphate (LiMn x Fe 1-x Other phosphate-based materials may also be suitable, such as lithium vanadium phosphate (LiVOPO4), lithium titanium phosphate (LiTi2(PO4)3), lithium nickel phosphate (LiNiPO4), fluorophosphates such as LiVPO4F or LiFeSO4F, or lithium cobalt phosphate (LiCoPO4).

[0418] layered oxide materials

[0419] The cathode active material is also Li(Ni 1-x-y Co x Mn y )O2(NCM) or Li(Ni 1-x-y Co x Al y )O2(NCA), where the ratios of Ni, Co, Mn, and Al can be adjusted to optimize performance characteristics. For example, to achieve higher energy density, NCM811(LiNi 0.8 Co 0.1 Mn 0.1 NCM materials with high nickel content, such as O2, can be used. In some cases, the cathode active material can be LiNi, which can provide high-voltage operation. 0.5 Mn 1.5It may contain a spinel structure such as O4. Alternatively, LiFeSO4 for the possibility of high energy density and good thermal stability. F or LiVPO4 F Materials with preferred structures such as may also be employed.

[0420] Composite or blended cathode materials

[0421] Composite or blended cathode materials combining two or more active materials can also be used. For example, a blend of layered oxides and spinel materials can be employed to balance energy density and power performance. As another example, lithium iron phosphate can be blended with one or more of the aforementioned cathode active materials. In some embodiments, the cathode active material may include a surface-modified version of the aforementioned compounds, wherein the surface modification is aimed at improving stability, conductivity, or other performance indicators.

[0422] Emerging Classes of Materials

[0423] Cathode active materials may also include novel materials such as disordered rock salt structures (e.g., Li3NbO4-based materials), lithium-rich antiperovskites (e.g., Li3OCl), cation-disordered oxides (e.g., Li-Mn-VO3-based materials), or high-entropy oxides, which may provide a desirable combination of high capacity and structural stability. In some cases, the cathode active materials may be further tailored to their electrochemical properties by incorporating dopants or substitutional elements.

[0424] Particle nature of positive electrode active material

[0425] The positive electrode active material may be in particle form. Anode active materials are 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 310nm, 320nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm, 400nm, 410nm, 420nm, 430nm, 440nm, 450nm, 460nm, 470nm, 480nm, 490nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, 55μm, 60μm, 65μm, 70μm, 75μm, 80μm, 85μm, 90μm, 95μm, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm, 200μm, 210μm, 220μm, 230μm, 240μm, 250μm, 260μm, 270μm, 280μm, 290μm, 300μm, 310μm, 320μm, 330μm, 340μm, 350μm, 360μm, 370μm, 380μm, 390μm, 400μm, 410μm, 420μm, 430μm, 440μm, 450μm, 460μm, The particle size may range from 1 nm to 1000 μm, such as any of 470 μm, 480 μm, 490 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm or 1,000 μm.In an embodiment, the particle size of the positive electrode active material may be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 1 nm to 1000 μm, for example, within a range between 10 nm and 1,000 μm. The gap between the positive electrode active material particles within the positive electrode (102) may be filled with a solid electrolyte material.

[0426] Amount of positive active material in the positive electrode

[0427] The amount of the positive electrode active material of the solid-state battery (100) affects the charge-discharge capacity of the solid-state battery (100). To manufacture a high-capacity positive electrode (102), a high level of positive electrode active material may be included in the positive electrode (102). For example, the positive electrode (102) includes 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99 wt%, about that wt%, or more that wt% of the positive electrode active material, based on the total weight of the positive electrode (102). In an embodiment, the positive electrode active material of the positive electrode (102) may be in a range formed by selecting any two values ​​listed above or by selecting any two values ​​within a range of greater than 0 to 100 wt%, for example, within a range between 40 wt% and 98 wt%.

[0428] Conductive material of the anode electrode

[0429] The conductive material of the positive electrode (102) is not particularly limited as long as it has conductivity without causing a chemical change in the solid-state battery (100). For example, the conductive material may include graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Kejen black, channel black, furnace black, lamp black, or thermal black; conductive fibers such as carbon fibers or metal fibers; carbon nanotubes (CNTs) including both single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs); metal powders such as fluorocarbon, aluminum, or nickel powders; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; conductive polymers such as polyphenylene derivatives; It may include graphene, metal nanowires (e.g., silver nanowires), indium tin oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), conductive ceramics such as titanium nitride or titanium carbide, or combinations thereof.

[0430] Amount of conductive material in the anode electrode

[0431] The anode electrode (102) comprises a conductive material in an amount of 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%, or about that wt%, based on the total weight of the anode electrode (102). In an embodiment, the conductive material of the anode electrode (102) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence, for example, within a range between 1 wt% and 30 wt%.

[0432] Materials for binders

[0433] Binders include, for example, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluoroelastomer, polyacrylic acid, polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), poly(ethylene-co-vinyl acetate) (PEVA), poly(vinyl acetate) (PVA), chitosan, guar gum (GG), xanthan gum, carrageenan, pectin, water-soluble polymers, lignin, and polymers thereof containing hydrogen. It may include various types of binder polymers, such as polymers in which atoms are substituted with Li, Na or Ca, various copolymers thereof, or combinations thereof.

[0434] Other binder materials

[0435] In addition to the binder materials described above, other types of binder materials can be used in the anode electrode to improve its performance and stability. For example, water-soluble binders such as sodium alginate, gelatin, or polyacrylamide can be employed to improve the environmental friendliness of the electrode manufacturing process. These binders can also provide advantages in electrode flexibility and adhesion strength. In some cases, conductive binders such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) or polyaniline (PANI) can be used to simultaneously improve the mechanical integrity and electrical conductivity of the electrode.

[0436] New binder system

[0437] Novel binder systems, such as self-healing polymers or supramolecular assemblies, can be incorporated to improve the long-term stability and cycle life of the battery. Additionally, composite binders combining multiple polymers or incorporating inorganic nanoparticles can be used to tailor the mechanical, thermal, and electrochemical properties of the electrode. In some embodiments, bio-derived or biodegradable binders, such as cellulose derivatives or chitosan, can be employed to reduce the environmental impact of battery production and disposal.

[0438] Amount of binder in the positive electrode

[0439] The anode electrode (102) can include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt %, or about that wt %, of the binder, based on the total weight of the anode electrode (102). In an embodiment, the binder in the anode electrode (102) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence, for example, within a range between 1 wt % and 30 wt %.

[0440] solid electrolyte material

[0441] The solid electrolyte material of the anode electrode (102) may be composed identically to the material for the solid electrolyte layer (106) discussed below. The solid electrolyte material of the anode electrode (102) may be identical to or different from the material for the solid electrolyte layer (106).

[0442] Amount of solid electrolyte material in the positive electrode

[0443] The anode electrode (102) can include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 wt% of the solid electrolyte material based on the total weight of the anode electrode (102). In an embodiment, the amount of the solid electrolyte material of the anode electrode (102) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence, for example, within a range between 1 wt% and 30 wt%.

[0444] Thickness of the anode electrode

[0445] The thickness (t2) of the positive electrode (102) is 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, Any number in the range of greater than 0 to 1000 μm, such as 970, 980, 990, 1,000 μm, or about that number. In an embodiment, the thickness (t2) of the positive electrode (102) may be in a range formed by selecting any two numbers listed above or selecting any two numbers in the range of greater than 0 to 1000 μm, for example, in a range between 10 μm and 1,000 μm.

[0446] Porosity of the anode electrode

[0447] The porosity of the anode electrode (102) can be any number or about any number in the range of 0 to 20 vol%, such as 0, 1, 2 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 vol%, based on the total volume of the anode electrode (102), or any other vol% or about vol% within the range of 0 to 20 vol%. In an embodiment, the porosity of the anode electrode (102) can be within a range formed by selecting any two numbers listed above or selecting any two numbers within the range of 0 to 20 vol%, for example, within a range between 0 vol% and 18 vol%.

[0448] Lithium ion diffusion in the positive electrode

[0449] The anode electrode (102) is 1 x 10 -14 cm 2 / s, 1 x 10 -13 cm 2 / s, 1 x 10 -12 cm 2 / s, 1 x 10 -11 cm 2 / s, 1 x 10 -10 cm 2 / s, 1 x 10 -9 cm 2 / s, 1 x 10 -8 cm 2 / s or 1 x 10 -7 m 2 / s, greater than 0 to 1 x 10 -7 cm 2 / s may include a lithium ion diffusivity of any number in the range or about that number. In an embodiment, the lithium ion diffusivity of the positive electrode (102) is selected from any two numbers listed above or is greater than 0 to 1 x 10 -7 cm 2 A range formed by selecting two random numbers within the range of / s, for example, 1 x 10 -14 cm 2 / s and 1 x 10-7 cm 2 It can be within the range of / s.

[0450] Current collector of positive electrode

[0451] The collector (108) collects the electric energy generated from the positive electrode (102) and supports the positive electrode (102).

[0452] Materials for current collectors of positive electrodes

[0453] The material of the current collector (108) is not particularly limited as long as it enables adhesion of the positive electrode (102), has suitable electrical conductivity, and does not cause significant chemical changes in the solid-state battery (100) within the voltage range of the solid-state battery (100). For example, the current collector (108) may be made of or include various materials such as, but not limited to, metals, conductive carbons, or conductive ceramics. The metal of the current collector (108) may include, but is not limited to, one or more selected from the group consisting of aluminum, aluminum alloys, copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, iron, iron alloys (e.g., steel, stainless steel), silver, silver alloys, gold, platinum, palladium, chromium, molybdenum, tungsten, tantalum, niobium, zirconium, vanadium, manganese, cobalt, indium, tin, lead, bismuth, or combinations thereof.

[0454] The geometry of the entire house

[0455] The collector (108) may also be configured in a variety of other geometries to optimize its performance and integration with the anode electrode (102), and may be sized to fit specific form factors, such as pouch, cylindrical, and / or prismatic form factors.

[0456] Shape of the current collector of the positive electrode

[0457] By forming fine surface irregularities on the surface of the current collector (108), the adhesion between the positive electrode (102) and the current collector (108) can be improved. The current collector (108) can have various shapes, such as, for example, a film, a sheet, a foil, a net, a porous body, a foam, a non-woven web, or a combination thereof.

[0458] Examples of the shape and size of the entire house

[0459] For example, the current collector (108) may be structured as a mesh or grid, which can provide enhanced mechanical support while maintaining a high surface area for electrode adhesion. In some embodiments, the current collector (108) may be designed in a pleated or wavy pattern, which potentially increases the contact area with the positive electrode material and improves overall conductivity. The current collector (108) may also be fabricated as a perforated sheet, which allows for better electrolyte penetration and ion transport. In certain cases, the current collector (108) may be formed as a three-dimensional structure, such as an interconnected fiber network or a honeycomb configuration, which can facilitate efficient current collection while improving the structural integrity of the electrode assembly.

[0460] Thickness of the current collector of the positive electrode

[0461] The thickness (t3) of the entire body (108) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400,410, 420, Any number greater than 0 and in the range of 500 μm or about that number, such as 430, 440, 450, 460, 470, 480, 490 or 500 μm. In an embodiment, the thickness (t3) of the current collector (108) can be in a range formed by selecting any two numbers listed above or selecting any two numbers greater than 0 and in the range of 500 μm, for example, in a range between 5 μm and 500 μm.

[0462] Method for manufacturing anode electrode

[0463] The anode electrode (102) can be obtained by various methods.

[0464] Dry powder coating process

[0465] For example, a dry powder coating process may be employed, in which a negative electrode active material, a conductive additive, and a binder are mixed in a dry state and then directly applied to the current collector (108) using electrostatic deposition or mechanical compression. This method can reduce the environmental impact by reducing the use of solvents.

[0466] 3D printing

[0467] In some cases, the anode electrode (102) may be fabricated using additive manufacturing techniques, such as 3D printing. This approach allows for precise control of the electrode structure and porosity, potentially improving the electrode's performance and energy density. Depending on the specific material and desired electrode properties, various 3D printing methods, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW), may be utilized.

[0468] Electrospinning

[0469] Another method for manufacturing the positive electrode (102) may involve electrospinning. In this process, a solution containing a negative electrode active material, a conductive additive, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be directly collected on a current collector (108) to form a highly porous electrode structure with increased surface area.

[0470] Tape Casting

[0471] In some embodiments, the positive electrode (102) can be prepared using a tape casting method. This technique involves spreading a slurry of electrode material onto a moving carrier film using a doctor blade, followed by drying and calendering. The resulting electrode tape can then be laminated to a current collector (108).

[0472] spray coating

[0473] Alternatively, the positive electrode (102) can be fabricated using a spray coating technique. In this method, a fine mist of electrode slurry is sprayed onto a current collector (108) using compressed air or ultrasonic atomization. This approach can produce a thin, uniform electrode layer and may be particularly useful for large-scale production.

[0474] Freeze-casting

[0475] In certain cases, the positive electrode (102) may be prepared using a freeze casting process. This process involves freezing a slurry of electrode material and then sublimating the ice to create a porous structure. The resulting porous electrode may then be sintered and attached to a current collector (108).

[0476] sol-gel process

[0477] For some applications, the positive electrode (102) may be prepared using a sol-gel process. This process involves forming a colloidal suspension (sol) and then converting it into a gel-like network containing the positive electrode active material and other components. This gel may be applied to a current collector (108) and subsequently heat-treated to form the final electrode structure.

[0478] slurry-based process

[0479] For example, a slurry can be formed by mixing and stirring a positive electrode active material with a solvent, and optionally a binder, a conductive agent, and a dispersant. Then, the slurry can be applied (e.g., coated) to a current collector (108), and then pressed and dried to obtain a positive electrode (102).

[0480] Method for applying slurry for anode electrode

[0481] Application of the slurry for the anode electrode (102) may include using a technique selected from the group consisting of slot die coating, gravure coating, spin coating, spray coating, roll coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, toppan printing, intaglio printing, offset printing, and the like, and combinations thereof.

[0482] Double layer slot die coating

[0483] In some embodiments, the positive electrode (102) can be fabricated using a double-layer slot die coating (DLD) technique. This method involves simultaneously applying two separate layers of electrode material to the current collector (108) in a single pass. The DLD process creates a gradient structure within the electrode, potentially optimizing both the electrochemical performance and mechanical properties of the positive electrode. Additionally, this technique can integrate functional interlayers or protective coatings as part of the electrode fabrication process, potentially improving overall battery performance and cycle life.

[0484] Solvent for slurry for positive electrode

[0485] The solvent for forming the positive electrode (102) may include water and / or an organic solvent, such as, for example, N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), acetone, dimethyl acetamide, dimethyl sulfoxide (DMSO), isopropyl alcohol, or the like, or a combination thereof. The solvent may be used in an amount sufficient to dissolve and disperse electrode components, such as the positive electrode active material, binder, and conductive agent, taking into account the slurry coating thickness, production yield, or a combination thereof. Additional solvents that may be used include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0486] Solvent-free method

[0487] In some embodiments of the present disclosure, the positive electrode (102) can be prepared using solvent-free methods such as dry powder processing or melt extrusion, which can reduce the use of liquid solvents and provide environmental and cost advantages.

[0488] Dispersant for slurry for positive electrode

[0489] The dispersant forming the anode electrode (102) may include an aqueous dispersant and / or an organic dispersant such as, for example, N-methyl-2-pyrrolidone. Other possible dispersants may include polyvinylpyrrolidone (PVP), carboxymethyl cellulose (CMC), sodium dodecyl sulfate (SDS), Triton X-100, polyethylene glycol (PEG), polyacrylic acid (PAA), and various surfactants such as polysorbates or poloxamers.

[0490] Drying technology for slurry for anode electrodes

[0491] The slurry for the anode electrode (102) can be dried by evaporating the solvent by irradiating it with heat, electron beams (E-beams), gamma rays, ultraviolet rays (G, H, I-rays), or a combination thereof. For example, the slurry can be vacuum-dried at room temperature. During the drying step, the solvent is removed through evaporation, but other components remain without evaporation to form the anode electrode (102).

[0492] Additional drying technology

[0493] In addition to the drying techniques described above, the positive electrode (102) may be dried using other methods such as infrared (IR) drying, microwave drying, or freeze drying.

[0494] Combination of drying technologies

[0495] In some embodiments, a combination of drying techniques may be employed, such as using convection heating followed by vacuum drying, to optimize the drying process and ensure complete solvent removal while maintaining the integrity of the electrode structure.

[0496] Cathode electrode general

[0497] The negative electrode (104) is associated with one polarity (e.g., the negative electrode) of the solid-state battery (100) that is different from the polarity of the positive electrode (102). The negative electrode (104) is configured as the negative electrode during discharge of the solid-state battery (100). The negative electrode (104) is suitable for lithium ion diffusion between the current collector (110) and the solid electrolyte layer (106).

[0498] Positioning of the cathode electrode

[0499] The negative electrode (104) is in electrical communication with the current collector (110). In an embodiment, the negative electrode (104) is formed on the current collector (110) and is in direct contact with the current collector (110). In another embodiment, another functional layer may be interposed between the negative electrode (104) and the current collector (110).

[0500] Non-cathode electrode system

[0501] As described above, in some embodiments, the solid-state battery (100) may utilize a non-anode electrode system. In such a configuration, the anode electrode (104) may be omitted, and lithium metal may be deposited directly on the current collector (110) during charging. This approach could potentially increase the energy density of the battery and eliminate the need for a separate anode material, while also potentially reducing the overall thickness of the battery structure.

[0502] Materials for cathode electrodes

[0503] The negative electrode (104) may be capable of reversible absorption and release of lithium ions. For example, the negative electrode (104) may include only the negative electrode active material. In other embodiments, the negative electrode (104) may include conductive particles, a binder, or a combination thereof.

[0504] Additives for cathode electrodes

[0505] Optionally, the cathode electrode (104) may further include additives, such as, for example, oxidation stabilizers (e.g., butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tert-butylhydroquinone), reduction stabilizers (e.g., ascorbic acid, sodium sulfite, erythorbic acid, sodium metabisulfite), flame retardants (e.g., aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine cyanurate), heat or light stabilizers (e.g., phenolic compounds, phosphites, hindered amine light stabilizers, UV absorbers such as benzophenone or benzotriazole), antifogging agents (e.g., polyethylene glycol, silica nanoparticles, glycerol, sorbitol), thickeners (e.g., carboxymethyl cellulose, xanthan gum), or the like, or combinations thereof.

[0506] Other additives for cathode electrodes

[0507] Additionally, conductive additives such as carbon black, graphene, or carbon nanotubes can be incorporated to enhance electrical conductivity, and binder modifiers such as styrene-butadiene rubber or polyacrylic acid can be used to improve adhesion and mechanical stability. Functional additives such as fluoroethylene carbonate or vinylene carbonate can also be included to promote the formation of a stable solid electrolyte interfacial layer on the cathode surface.

[0508] Materials for negative electrode active materials

[0509] The negative electrode active material may be made of or include various materials, such as, but not limited to, alkali metals, alkaline earth metals, Group 3B metals, transition metals, metalloids, alloys thereof, conductive carbon, and the like. In embodiments, the negative electrode active material may include, but is not limited to, silicon, a silicon alloy, lithium, a lithium alloy, conductive carbon, or a combination thereof. In embodiments, the lithium alloy is made of or includes a lithium alloy that includes silicon, chlorine, or a combination thereof. A lithium metal thin film may also be used as the negative electrode active material.

[0510] Other materials for negative electrode active materials

[0511] The negative active material is a carbon-based material such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, etc.; a metal compound that can be alloyed with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, Al alloy, etc.; SiO x (0 <x<2), SnO2, 바나듐 산화물 또는 리튬 바나듐 산화물과 같은 리튬 이온을 도핑 및 탈도핑할 수 있는 금속 산화물; 및 Si-C 복합체 또는 Sn-C 복합체와 같은 금속 화합물과 탄소계 재료를 포함하는 복합체를 포함할 수 있다.

[0512] carbon-based materials

[0513] The carbonaceous material may include low-crystalline carbon, high-crystalline carbon, or a combination thereof. Representative examples of low-crystalline carbon include soft carbon or hard carbon, and representative examples of high-crystalline carbon include high-temperature calcined carbon such as amorphous, platelet-like, flaky, spherical, or fibrous natural or artificial graphite, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesocarbon microbeads, mesophase pitch, coke derived from petroleum or coal tar pitch, or a combination thereof.

[0514] metal carbon composite materials

[0515] Alternatively, according to an aspect of the present disclosure, the cathode electrode (104) may include a cathode material having a metal carbon composite, such as a silver-carbon composite or composite in which silver particles are complexed between amorphous and / or crystalline carbon particles. Silver is used as an example herein, but other metals may be used, including, for example, tin and / or zinc. Silicon may also be used instead of silver.

[0516] Additional materials for negative electrode active materials

[0517] In addition to the materials mentioned above, the negative active material is lithium titanate (Li4Ti5O), which can provide excellent cycling stability and high rate performance. 12 ) or titanium compounds such as titanium dioxide (TiO2). Another potential material is molybdenum oxide (MoO2), which can provide high theoretical capacity. x ), iron oxide (FeO x ) or nickel oxide (NiO x ) may include transition metal oxides such as silicon-graphite composites or tin-carbon composites. In some cases, composite materials combining different active materials, such as silicon-graphite composites or tin-carbon composites, can be used to alleviate individual limitations while taking advantage of the advantages of multiple materials.

[0518] Dentrite formation

[0519] When the negative electrode (104) is made of or includes lithium or a lithium alloy, dendrites may form on the negative electrode (104). Dendrites are metallic lithium structures that form when excess lithium ions accumulate on the surface of the negative electrode (104). The formed dendrites may damage the solid electrolyte layer (106), reduce the battery capacity of the solid-state battery (100), and / or cause undesirable performance of the solid-state battery (100). Dendrite formation is a significant challenge in lithium-based batteries because these structures can grow through the electrolyte, potentially causing short circuits and safety hazards. The growth rate and morphology of dendrites can be influenced by factors such as current density, temperature, and the nature of the electrolyte-electrode interface.

[0520] Benefits of Solid Electrolytes in Mitigating Dentrite Formation

[0521] Solid electrolytes offer several advantages over liquid electrolytes in mitigating dendrite formation. The mechanical strength of solid electrolytes can help suppress dendrite growth by providing a physical barrier to lithium metal penetration. Additionally, the uniform ion distribution of solid electrolytes can promote more even lithium deposition, reducing the likelihood of localized dendrite nucleation. Some solid electrolytes can also form a stable interface with the lithium metal anode, further suppressing dendrite formation. However, while solid electrolytes can significantly reduce the risk of dendrite growth, they cannot completely eliminate it. Research is ongoing to develop advanced solid electrolyte materials with enhanced dendrite suppression capabilities.

[0522] Shape of negative active material

[0523] The negative active material may be in the form of particles or in a continuous unitary form (e.g., a thin film or sheet).

[0524] particle size

[0525] In an embodiment in which the negative active material is in the form of particles, the negative active material has a particle size of 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm, 400nm, 410nm, 420nm, 430nm, 440nm, 450nm, 460nm, 470nm, 480nm, 490nm, 500nm, 510nm, 520nm, 530nm, 540nm, 550nm, 560nm, 570nm, 580nm, 590nm, 600nm, 610nm, 620nm, 630nm, 640nm, 660nm, 640nm, 650nm, 660nm, 670nm, 680nm, 690nm, 700nm, 710nm, 720nm, 730nm, 740nm, 750nm, 760nm, 770nm, 780nm, 790nm, 800nm, 810nm, 820nm, 830nm, 840nm, 850nm, 860nm, 870nm, 880nm, 890nm, 900nm, 910nm, 920nm, 930nm, 940nm, 950nm, 960nm, 970nm, 980nm, 890nm, 980nm, 990nm, 1000nm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, 55μm, 60μm, 65μm, 70μm, 75μm, 80μm, 85μm, 90μm, 95μm, 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm,170μm, 180μm, 190μm, 200μm, 210μm, 220μm, 230μm, 240μm, 250μm, 260μm, 270μm, 280μm, 290μm, 300μm, 310μm, 320μm, 330μm, 340μm, 350μm, 360μm, 370μm, 380μm, 390μm, 400μm, 410μm, 420μm, 430μm, 440μm, 450μm, 460μm, 470μm, 480μm, 490μm, 500μm, 510μm, 520μm, 530μm, 540μm, 550μm, 560μm, 570μm, 580μm, 590μm, 600μm, 610μm, 620μm, 630μm, 640μm, 650μm, 660μm, 670μm, 680μm, 690μm, 700μm, 710μm, 720μm, 730μm, 740μm, 750μm, 760μm, 770μm, 780μm, 790μm, 800μm, 810μm, 820μm, 830μm, 840μm, 850μm, The negative active material may include a particle size of any number in the range of 10 nm to 1000 μm or 10 nm to 1000 μm, such as 860 μm, 870 μm, 880 μm, 890 μm, 900 μm, 910 μm, 920 μm, 930 μm, 940 μm, 950 μm, 960 μm, 970 μm, 980 μm, 990 μm or 1,000 μm, or about such μm. In an embodiment, the particle size of the negative active material may be within a range formed by selecting any two numbers listed above or selecting any two numbers in the range of 10 nm to 1,000 μm or 10 nm to 1,000 μm, for example, within a range between 10 nm and 1,000 μm.

[0526] Amount of negative active material in the negative electrode

[0527] The amount of negative active material within the solid-state battery (100) affects the charge-discharge capacity of the solid-state battery (100). To produce a high-capacity negative electrode (104), the negative electrode (104) may include a high level of negative active material. For example, the negative electrode (104) includes 70, 80, 90, 95, 98, 99, or 100 wt %, about that wt %, or more that wt % of the negative active material, based on the total weight of the negative electrode (104). In embodiments, the negative active material of the negative electrode (104) may be within a range formed by selecting any two values ​​enumerated in the immediately preceding sentence, for example, within a range between 70 wt % and 100 wt %.

[0528] Binder material for cathode electrode

[0529] The binder may include various types of binder polymers, such as, for example, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluoroelastomer, polyacrylic acid, polymers thereof in which hydrogen atoms are substituted with Li, Na, or Ca, various copolymers thereof, or combinations thereof.

[0530] Examples of binder materials for cathode electrodes

[0531] In addition to the binders mentioned above, other binders suitable for use in the positive electrode may include polyimides, polyamide-imides, polyurethanes, polyethylene oxide (PEO), poly(ethylene-covinyl acetate) (PEVA), poly(vinyl acetate) (PVA), alginates, chitosan, guar gum, xanthan gum, carrageenan, pectin, gelatin, lignin, and various water-soluble polymers or derivatives thereof. In some cases, conductive polymers such as polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene) (PEDOT) may also be used as binders to simultaneously improve adhesion and electrical conductivity within the negative electrode.

[0532] Amount of binder in the negative electrode

[0533] The cathode electrode (104) can comprise the binder in an amount of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt%, or about that wt%, or any other wt% in a range between 0 and 30 wt%, based on the total weight of the cathode electrode (104). In an embodiment, the binder of the cathode electrode (104) can be in a range formed by selecting any two values ​​enumerated above, or selecting any two values ​​in a range between 0 and 30 wt%, for example, in a range between 0 wt% and 30 wt%.

[0534] Thickness of the cathode electrode

[0535] The cathode electrode (104) can have a thickness of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 μm, or about that thickness. In an embodiment, the thickness (t4) of the cathode electrode (104) can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 10 μm to 100 μm, for example, within a range between 10 μm and 100 μm or between 10 μm and 20 μm.

[0536] Porosity of the cathode electrode

[0537] The porosity of the cathode electrode (104) may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 vol% based on the total volume of the cathode electrode (104), or any other vol% in the range of 0 to 18 vol%. In an embodiment, the porosity of the cathode electrode (104) may be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range between 0 vol% and 18 vol%.

[0538] Lithium ion diffusion in the negative electrode.

[0539] The cathode electrode (104) is 1 x 10 -14 cm 2 / s, 1 x 10 -13 cm 2 / s, 1 x 10 -12 cm 2 / s, 1 x 10 -11 cm 2 / s, 1 x 10 -10 cm 2 / s, 1 x 10 -9 cm 2 / s, 1 x 10 -8 cm 2 / s or 1 x 10 -7 cm 2 / s, or about that cm 2 / s may include a lithium ion diffusivity of. In an embodiment, the lithium ion diffusivity of the negative electrode (104) is selected from any two values ​​listed above or 1 x 10 -14 cm 2 / s to 1 x 10 -7 cm 2 / s or 1 x 10 -14 cm 2 / s to 1 x 10 -7 cm 2 It can be within a range formed by selecting any two numbers in the range of / s.

[0540] Current collector of the negative electrode

[0541] The current collector (110) collects the electric energy generated from the cathode electrode (104) and supports the cathode electrode (104).

[0542] Material for current collector of negative electrode

[0543] The material of the current collector (110) is not particularly limited, as long as it enables close contact of the negative electrode (104), has suitable electrical conductivity, and does not cause significant chemical changes in the solid-state battery (100) within the voltage range of the solid-state battery (100). For example, the current collector (110) is made of or includes, but is not limited to, a metal or conductive carbon.

[0544] Metal for current collector

[0545] The metal of the current collector (110) may include, but is not limited to, one or more selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, iron, iron alloy (e.g., steel, stainless steel), silver, silver alloy, or combinations thereof.

[0546] Shape of the current collector of the negative electrode

[0547] By forming fine surface irregularities on the surface of the current collector (110), the adhesion of the negative electrode (104) to the current collector (110) can be increased. The current collector (110) can have various shapes, such as, for example, a film, a sheet, a foil, a net, a porous body, a foam, a non-woven web, or a combination thereof. In addition to the above-described shapes, the current collector (110) can also be configured as a honeycomb structure, a perforated sheet, a woven or non-woven mesh, a sintered porous body, or a three-dimensional interconnected network. These various shapes can be tailored to optimize the surface area, mechanical strength, and current collection efficiency of the current collector (110).

[0548] Design of the current collector of the negative electrode

[0549] Additionally, the current collector (110) can be designed to accommodate solid-state batteries of different form factors, such as pouch cells, cylindrical cells, or prismatic cells, each of which may provide advantages in packaging efficiency, thermal management, and overall battery performance.

[0550] Thickness of the current collector of the negative electrode

[0551] The thickness (t5) of the collector (110) is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 or 500 μm, or about that μm. In an embodiment, the thickness (t5) of the current collector (110) may be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 1 μm to 500 μm or 1 μm to 500 μm, for example, within a range between 5 μm and 500 μm.

[0552] Method for manufacturing a cathode electrode

[0553] The cathode electrode (104) can be obtained by various methods, such as atomic deposition, extrusion, rolling, slurry methods, or combinations thereof. In addition to the methods described above, the cathode electrode (104) can be manufactured using various other techniques, including a dry electrode process. These alternative methods may offer advantages in terms of environmental impact, cost-effectiveness, and scalability.

[0554] dry powder coating

[0555] Dry powder coating can be employed as an alternative to the slurry method. In this process, the negative active material, conductive additive, and binder are mixed in a dry state and then applied directly to the current collector (110) using electrostatic deposition or mechanical compression. This method can potentially reduce environmental impact and processing time by reducing the use of solvents.

[0556] 3D printing

[0557] Additive manufacturing techniques, such as 3D printing, can be used to fabricate the cathode electrode (104). Depending on the specific material and desired electrode properties, various 3D printing methods, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW), can be utilized. These approaches allow for precise control of the electrode structure and porosity.

[0558] electrospinning

[0559] Electrospinning is another potential method for manufacturing a cathode electrode (104). In this process, a solution containing a cathode active material, a conductive additive, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be directly collected on a current collector (110) to form a porous electrode structure with increased surface area.

[0560] Tape casting

[0561] Tape casting can be employed to prepare the negative electrode (104). This technique involves spreading a slurry of electrode material onto a moving carrier film using a doctor blade, followed by drying and calendering. The resulting electrode tape can then be laminated onto a current collector (110).

[0562] spray coating

[0563] A spray coating technique can be used to fabricate the cathode electrode (104). A fine mist of electrode slurry is sprayed onto a current collector (110) using compressed air or ultrasonic atomization. This approach can produce a thin, uniform electrode layer and may be particularly useful for large-scale production.

[0564] freeze casting

[0565] Freeze casting is another potential method for manufacturing the cathode electrode (104). This process involves freezing a slurry of electrode material, then sublimating the ice to create a porous structure. The resulting porous electrode can then be sintered and attached to a current collector (110).

[0566] sol-gel process

[0567] In some cases, a sol-gel process may be used to prepare the negative electrode (104). This method involves forming a colloidal suspension (sol) and then converting it into a gel-like network containing the negative electrode active material and other components. This gel may be applied to a current collector (110) and subsequently heat-treated to form the final electrode structure.

[0568] meteorological deposition

[0569] For certain applications, physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques can be employed to form a thin film anode directly on the current collector (110). These methods can produce a very uniform and dense electrode layer, which can be particularly advantageous for certain types of solid-state batteries.

[0570] Alloying and ball milling

[0571] Composite anode materials can be prepared using mechanical alloying and high-energy ball milling, and then pressed onto an electrode or applied to a current collector (110) using one of the methods described above. This technique can be particularly useful for creating nanostructured or amorphous anode materials with enhanced electrochemical properties.

[0572] Slurry method

[0573] For example, a negative electrode active material can be mixed and stirred with a solvent and optionally a binder and dispersant to form a slurry. Then, the slurry can be applied (e.g., coated) to a current collector (110), and then pressed and dried to obtain a negative electrode (104).

[0574] Method for applying slurry for cathode electrode

[0575] Application of the slurry for the negative electrode (104) may include using a technique selected from the group consisting of slot die coating, gravure coating, spin coating, spray coating, roll coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, topographic printing, intaglio printing, offset printing, and the like, and combinations thereof. In addition to the techniques described above, other methods of applying the negative electrode slurry to the current collector may include doctor blade coating, dip coating, and meniscus coating.

[0576] Double slot die layer coating

[0577] Double-slot die layer coating can also be employed, allowing for the simultaneous application of two distinct layers of electrode material to the current collector in a single pass. This method potentially creates a gradient structure within the electrode, optimizing both electrochemical performance and mechanical properties.

[0578] Solvent for slurry for cathode electrode

[0579] The solvent for forming the negative electrode (104) may include water and / or an organic solvent, such as, for example, N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), acetone, dimethyl acetamide, dimethyl sulfoxide (DMSO), isopropyl alcohol, or a combination thereof. The solvent may be used in an amount sufficient to dissolve and disperse electrode components, such as the negative electrode active material and binder, taking into account the slurry coating thickness, production yield, etc., or a combination thereof. Additional organic solvents that may be used include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0580] Solvent-free method

[0581] In some embodiments, the cathode electrode (104) can be prepared using a solvent-free method, such as dry powder processing or melt extrusion, which can eliminate the need for liquid solvents and provide environmental and cost advantages.

[0582] Dispersant for slurry for cathode electrode

[0583] The dispersant forming the cathode electrode (104) may include an aqueous dispersant and / or an organic dispersant, such as, for example, N-methyl-2-pyrrolidone. Other examples of aqueous dispersants may include sodium dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP), and carboxymethyl cellulose (CMC), and additional organic dispersants may include various surfactants, such as Triton X-100, polyethylene glycol (PEG), and polysorbates or poloxamers.

[0584] Dispersant-free method

[0585] In some embodiments, the cathode electrode (104) can be prepared using a method that does not require a dispersant, such as dry powder processing or certain additive manufacturing techniques.

[0586] Drying technology for slurry for cathode electrode

[0587] The slurry for the cathode electrode (104) can be dried by irradiating heat, electron beams (E-beams), gamma rays, ultraviolet rays (G, H, I-rays), or a combination thereof to vaporize the solvent. For example, the slurry can also be vacuum-dried at room temperature. During the drying step, the solvent is removed through evaporation, but other components remain without evaporation to form the cathode electrode (104).

[0588] Other drying techniques

[0589] In addition to the drying techniques described above, several other methods can be employed to dry the cathode electrode slurry. These additional techniques can offer various advantages depending on the specific material, production requirements, and desired electrode properties.

[0590] Infrared (IR) drying

[0591] Infrared (IR) drying can be used to rapidly heat the electrode surface, promoting efficient solvent evaporation. This method is particularly effective for thin electrode coatings and allows for precise control of the drying process.

[0592] Microwave drying

[0593] Microwave drying is another option that provides volumetric heating of the electrode material, potentially leading to more uniform drying across the entire electrode thickness. In some cases, a combination of convection and microwave drying can be employed to optimize both drying speed and uniformity.

[0594] Freeze drying

[0595] Freeze-drying (also known as lyophilization) can be used for certain electrode formulations. This process involves freezing the slurry and then sublimating the solvent under vacuum conditions. Freeze-drying can help maintain the porous structure of the electrode, which can be beneficial for electrolyte penetration and ion transport.

[0596] Supercritical CO2 drying

[0597] Supercritical CO2 drying is an advanced technique that can be applied to specialized electrode materials. This method involves replacing the solvent with liquid CO2, then evacuating it to a supercritical state. This approach can help preserve the delicate nanostructures within the electrode and is particularly useful for aerogel-based electrodes.

[0598] Stage 2 drying

[0599] In some cases, a two-step drying process may be employed. For example, an initial drying step at low temperature may be performed to remove the bulk solvent, followed by a higher temperature step to remove any residual solvent and potentially initiate any desired chemical reactions within the electrode material.

[0600] Ultrasonic drying

[0601] Ultrasonic drying may also be considered for certain electrode formulations. This technique uses high-frequency sound waves to agitate solvent molecules, potentially accelerating the drying process and improving solvent removal from the porous structure within the electrode.

[0602] General solid electrolyte layer

[0603] The solid electrolyte layer (106) is suitable for lithium ion diffusion between the positive electrode (102) and the negative electrode (104). The solid electrolyte layer (106) provides an electrically conductive path for the movement of charge carriers between the positive electrode (102) and the negative electrode (104). The solid electrolyte layer (106) is in electrical communication with the positive electrode (102) and the negative electrode (104).

[0604] Positioning of solid electrolyte

[0605] In an embodiment, the solid electrolyte layer (106) is formed on the anode electrode (102) or the cathode electrode (104) and is in direct contact with the anode electrode (102) or the cathode electrode (104). In an embodiment, the solid electrolyte layer (106) is in direct contact with the anode electrode (102) and the cathode electrode (104). In another embodiment, another functional layer may be interposed between the solid electrolyte layer (106) and the anode electrode (102) and / or the cathode electrode (104).

[0606] Materials for solid electrolyte layers

[0607] The solid electrolyte layer (106) can transport lithium ions. The material of the solid electrolyte layer (106) is not particularly limited, as long as it allows for close contact with adjacent layers, has suitable electrical conductivity, and does not cause significant chemical changes in the solid battery (100) within the voltage range of the solid battery (100). For example, the solid electrolyte layer (106) may include, but is not limited to, various inorganic solid electrolytes, polymer solid electrolytes, and / or polymer gel electrolytes. Additionally or alternatively, the solid electrolyte layer (106) may include, but is not limited to, ceramic electrolytes, glass electrolytes, hybrid organic-inorganic electrolytes, and nanostructured electrolytes.

[0608] Inorganic solid electrolyte

[0609] Inorganic solid electrolytes may include, but are not limited to, crystalline solid electrolytes, amorphous solid electrolytes, glass ceramic solid electrolytes, and the like, or combinations thereof. The inorganic solid electrolytes may be sulfide-based, oxide-based, and the like, or combinations thereof. In addition to sulfide-based and oxide-based inorganic solid electrolytes, other types of inorganic solid electrolytes may include halide-based electrolytes, nitride-based electrolytes, and borate-based electrolytes. For example, lithium-rich antiperovskites (LiRAPs), such as Li3OCl and Li3OBr, lithium nitride (Li3N), and lithium borohydride (LiBH4), have been studied as potential solid electrolyte materials for lithium ion batteries.

[0610] Sulfide-based solid electrolyte

[0611] The sulfide-based solid electrolyte contains sulfur (S) and has the ionic conductivity of a metal belonging to group I or group II of the periodic table, and may include Li-PS-based glass or Li-PS-based glass ceramic.

[0612] Examples of sulfide-based solid electrolytes

[0613] For example, sulfide-based solid electrolytes may include lithium sulfide, silicon sulfide, germanium sulfide, and boron sulfide. Specific examples of inorganic solid electrolytes include Li 3.833 Sn 0.833 As 0.166 S4, Li4SnS4, Li 3.25 Ge 0.25 P 0.75 S4, Li2S-P2S0, B2S3-Li2S, XLi2S-(100-x)P2S 5( x=70-80), Li2S-SiS2-Li3N, Li2S-P2S5-LiI, Li2S-SiS2-LiI, Li2S-B2S3-LiI, Li3N, LISICON, LIPON(Li 3+y PO 4-x N x ), thio-LISICON(Li 3.25 Ge 0.25 P 0.75S4), Li2O-Al2O3-TiO2-P2O 5( LATP), Li2S-P2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5, Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2, Li2S-GeS2-ZnS, Li 10 GeP2S 12 (LGPS), Li7P3S 11 , Li6PS5Cl, Li6PS5Br, Li6PS5I, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , Li 11 Si2PS 12 etc., or a combination thereof.

[0614] Doped Variant

[0615] In some cases, doped variants of these materials are used to further improve ionic conductivity or stability, for example, Al-doped Li. 10 GeP2S 12 Alternatively, Sb-doped Li6PS5Cl may be employed.

[0616] Oxide-based solid electrolyte

[0617] Oxide-based solid electrolyte materials contain oxygen (O) and have the ionic conductivity of a metal belonging to group I or II of the periodic table.

[0618] Examples of oxide-based solid electrolyte materials

[0619] Oxide-based solid electrolyte materials include LLTO-based compounds, Li6La2CaTa2O 12 , Li6La2ANb2O 12 (A is Ca or Sr), Li2Nd3TeSbO 12 , Li3BO 2.5 N 0.5, Li9SiA1O8, LAGP compounds, LATP compounds, Li 1+x Ti 2-x Al x Si y (PO4) 3-y (0≤x≤1, 0≤y≤1), LiAl x Zr 2-x (PO4)3(0≤x≤1, 0≤y≤1), LiTi x Zr 2-x (PO4)3(0≤x≤1, 0≤y≤1), LISICON compounds, LIPON compounds, perovskite compounds, NASICON compounds, and LLZO compounds or LLZO-derived compounds (e.g., Al-doped Li7La3Zr2O 12 and Ta-doped Li7La3Zr2O 12 ) may include at least one selected from the group consisting of Li3OCl and Li3OBr. Lithium-rich antiperovskites, such as Li3OCl and Li3OBr, have also been studied as potential oxide-based solid electrolytes.

[0620] composite oxide electrolyte

[0621] In some cases, composite oxide electrolytes combining multiple oxide materials, such as LLZO-LATP composites, can be employed to take advantage of the advantages of different oxide systems.

[0622] polymer solid electrolyte

[0623] Polymer solid electrolytes are composites of electrolyte salts and polymer resins and have lithium ion conductivity. Polymer solid electrolytes may include polyether polymers, polycarbonate polymers, acrylate polymers, polysiloxane polymers, phosphazene polymers, polyethylene derivatives, alkylene oxide derivatives, phosphate polymers, polyaggregated lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, polymers containing ionically dissociable groups, biopolymers such as poly(ethylene imine) (PEI), poly(methyl methacrylate) (PMMA), poly(acrylonitrile) (PAN), poly(ethylene succinate) (PES), chitosan, and cellulose derivatives, or combinations thereof.

[0624] Polymer resin for solid polymer electrolyte

[0625] The solid polymer electrolyte may include a polymer resin such as a branched copolymer comprising a polyethylene oxide (PEO) backbone copolymerized with a comonomer comprising an amorphous polymer such as, for example, PMMA, polycarbonate, polydiloxane (PDMS), and / or phosphazene, a comb polymer, a cross-linked polymer resin, polyethylene glycol (PEG), polypropylene oxide (PPO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(ethylene oxide-co-propylene oxide) (PEO-PPO), poly(ethylene imine) (PEI), poly(vinyl pyrrolidone) (PVP), poly(vinyl alcohol) (PVA), various block copolymers or graft copolymers incorporating these materials, or combinations thereof.

[0626] polymer gel electrolyte

[0627] Polymer gel electrolytes can be formed by mixing an organic electrolyte containing an organic solvent and an electrolyte salt, an ionic liquid, a monomer, or an oligomer into a polymer resin or the like, or by combining these. Polymer resins for polymer gels can include polyether polymers, PVC polymers, PMMA polymers, polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene: PVDF-co-HFP), or the like, or combinations thereof.

[0628] Examples of polymer gel electrolytes

[0629] Examples of polymer gel electrolytes that may be suitable for solid-state batteries include poly(ethylene oxide) (PEO), poly(methyl methacrylate-co-ethyl acrylate) (PMMA-EA), poly(acrylonitrile-co-methyl methacrylate) (PAN-MMA), poly(vinyl acetate) (PVAc), poly(ethylene glycol diacrylate) (PEGDA), poly(vinyl pyrrolidone) (PVP), poly(ethylene glycol methyl ether acrylate) (PEGMEA), poly(ethylene glycol methyl ether methacrylate) (PEGMEMA), poly(ionic liquid) (PIL), poly(ethylene glycol-co-propylene glycol) (PEG-PPG), poly(vinyl alcohol-co-ethylene) (PVA-PE), poly(acrylamide) (PAM), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(ethylene It includes a gel electrolyte based on glycol-co-polyethylene oxide (PEG-PEO) and poly(methacrylic acid) (PMAA).

[0630] electrolyte salt

[0631] The electrolyte salt is an ionizable lithium salt and is Li + X - can be displayed as X - is F - , Cl - , Br - , NO3 - , N(CN)2 -, BF4 - , ClO4 - , AlO4 - , AlCl4 - , PF6 - , SbF6 - , AsF6 - , BF2C2O4 - , BC4O8 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , CF3SO3 - , C4F9SO3 - , CF3CF2SO3 - , (CF3SO2)2N - , (F2SO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH, CF3(CF2)7SO3 - , CF3CO2 - , CH3CO2 - , SCN - , (CF3CF2SO2)2N - It may include an anion selected from the group consisting of:

[0632] Examples of lithium salts

[0633] For example, lithium salts include LiTFSI, LiCl, LiBr, LiI, LiClO4, lithium tetrafluoroborate (LiBF4), LiB 10 Cl 10, lithium hexafluorophosphate (LiPF6), LiAsF6, LiSbF6, LiAlCl4, LiSCN, LiCF3CO2, LiCH3SO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC4F9SO3, LiC(CF3SO2)3, (CF3SO2)2NLi, lithium chloroborate, lithium lower aliphatic carboxylate, lithium imide 4-phenylborate, lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(fluorosulfonyl)imide (LiFSI) and combinations thereof. The electrolyte salt may comprise any combination of the salts described herein.

[0634] Amount of electrolyte salt

[0635] The solid electrolyte layer (106) may contain 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, or 400 parts, or about the parts, of the electrolyte salt based on the total weight of the solid electrolyte layer (106). In an embodiment, the electrolyte salt within the solid electrolyte layer (106) may be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​between 0 and 400 parts or 60 and 400 parts based on the total weight of the solid electrolyte layer (106).

[0636] Ionic conductivity of the solid electrolyte layer

[0637] The solid electrolyte layer (106) may have suitable reduction stability and / or ionic conductivity. Since the solid electrolyte layer (106) mainly functions to transport lithium ions between the electrodes, the solid electrolyte layer (106) may be, for example, 10 -7 S / cm, 10 -6 S / cm, 10 -5 S / cm or 10 -4 It may include a desirable ionic conductivity of about S / cm, about S / cm, or greater than about S / cm.

[0638] Thickness of the solid electrolyte layer

[0639] The thickness (t6) of the solid electrolyte layer (106) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990 or 1,000 μm, or about that μm. In an embodiment, the thickness (t6) of the solid electrolyte layer (106) can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in a range between 0 and 1,000 μm or between 0 and 1,000 μm, for example, within a range between 5 μm and 1,000 μm, between 30 μm and 100 μm or between 30 μm and 50 μm.

[0640] unfinished product

[0641] The cell (101) as illustrated in FIG. 1 may be provided as an unfinished product. In an embodiment, the cell (101) is stored, transported, and / or delivered to a reseller, customer, or the like, who will complete the manufacture of a battery assembly or battery product comprising the cell (101). In another embodiment, the cell (101) is a finished battery assembly or battery product.

[0642] Battery sealing

[0643] The manufacturing of the solid-state battery (100) can be completed by sealing the enclosure (112) of the solid-state battery to ensure its operation as a battery. The sealing process can involve various techniques to ensure the internal components are protected from external environmental factors and to maintain the integrity of the battery structure. For example, the enclosure (112) can be hermetically sealed using methods such as laser welding, ultrasonic welding, or adhesive bonding. In some cases, the sealing process can also include introducing a protective atmosphere or removing air to create a vacuum within the enclosure. This sealing step can help prevent moisture ingress, which could degrade the performance of the sulfide-based solid electrolyte. Additionally, the sealing process can incorporate safety features, such as a pressure relief mechanism, to manage any gas buildup that may occur during battery operation.

[0644] After sealing the battery

[0645] Once properly sealed, the solid-state battery (100) is ready for final quality control testing, which may include electrical testing, leak detection, and visual inspection. Upon passing these tests, the solid-state battery (100) can be packaged and sold as a finished product ready for integration into various electronic devices, electric vehicles, energy storage systems, and the like.

[0646] Battery configuration

[0647] The solid-state battery (100) is available in various configurations to suit different applications and device requirements. In some embodiments, the battery may be manufactured in a cylindrical shape, which may be advantageous for certain types of portable electronic devices or automotive applications. Alternatively, the solid-state battery (100) may be manufactured in a prismatic shape, which may allow for more efficient space utilization in devices with a rectangular form factor. In other cases, a pouch shape may be employed, which provides shape flexibility and potentially reduces overall battery weight. The pouch shape may be particularly suitable for solid-state batteries because it allows for easy application and control of uniform pressure within the battery.

[0648] Selection of configuration

[0649] The choice of configuration may vary depending on factors such as the intended use, space constraints, thermal management requirements, and manufacturing considerations. In some embodiments, hybrid or customized configurations combining different types of elements may be utilized as desired. The diversity of battery form factors allows for the integration of solid-state batteries into a wide range of products, from small wearable devices to large-scale energy storage systems.

[0650] voltage

[0651] Solid state battery (100) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370. 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 or 500 V, or about that V, is configured to output a voltage. In an embodiment, the output voltage of the solid-state battery (100) may be within a range formed by selecting any two numbers listed above or by selecting any two numbers in a range between 0 and 500 V or between 0 and 500 V, for example, within a range between 1 V DC and 500 V DC.

[0652] volume

[0653] The solid-state battery (100) can be configured to have a capacity of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, or 300 mAh / g, about that mAh / g, or more. In an embodiment, the output voltage of the solid-state battery (100) can have a capacity formed by selecting any two numbers listed above or by selecting any two numbers in the range between 0 and 300 mAh / g, for example, a capacity between 100 mAh / g and 300 mAh / g.

[0654] Volume expansion calculation

[0655] The solid state battery (100) can be configured to have a desirable volume expansion ratio. The volume expansion ratio is the first charge / discharge cycle compared to the initial thickness. 　 It can be calculated from the thickness change after the cycle. The volume expansion ratio can be the ratio of the thickness change to the initial thickness. The first charge-discharge cycle is performed by CC-CV charging in which the battery is charged at 0.1C and cut off at 0.02C at 4.25 to 4.4V, and CC discharging in which the battery is discharged at 0.1C and cut off at 3V. The volume expansion ratio is calculated by Equation 1 below, where A represents the thickness before charge-discharge and B represents the thickness after charge-discharge. The thickness can be measured using a Mouser micrometer or a scanning electron microscope (SEM).

[0656] Equation 1:

[0657] Volume expansion ratio = [(BA) / A]×100

[0658] C-rate

[0659] The C-rate used herein refers to the rate at which a battery discharges relative to its maximum capacity. For example, a 1C rate means that the discharge current discharges the entire battery within 1 hour. That is, for a battery with a capacity of 20 ampere-hours, the discharge current at 1C is 20 amperes.

[0660] Other examples of volume expansion

[0661] Other methods for measuring and calculating the volume expansion of solid-state batteries may include volume expansion measurements (e.g., gas pycnometry), in-situ dilatometry, X-ray tomography, strain gauge measurements, optical methods (e.g., digital image correlation or laser interferometry), pressure-based methods, and electrochemical strain microscopy.

[0662]

[0663] Example

[0664] Hereinafter, examples will be described more fully to facilitate understanding of the present disclosure. However, the following examples are for illustrative purposes only and the scope of the present disclosure is not limited thereto.

[0665]

[0666] Example 1: Solid electrolyte material

[0667] Example 1.1: LPSCl

[0668] LPSCl is obtained in powder form. The particle size is between 0.1 μm and 50 μm.

[0669] Example 1.2: LPSBr

[0670] LPSBr is obtained in powder form. The particle size is between 0.1 μm and 50 μm.

[0671] Example 1.3: LPSI

[0672] LPSI is obtained in powder form. The particle size is between 0.1 μm and 50 μm.

[0673]

[0674] Example 2: Additive materials

[0675] Example 2.1: Additive material represented by chemical formula 2

[0676] An additive material represented by the chemical formula 2 in powder form is obtained:

[0677] (Chemical formula 2)

[0678]

[0679] Example 2.2: Additive material represented by chemical formula 5

[0680] An additive material represented by the chemical formula 5 in powder form is obtained:

[0681] (Chemical formula 5)

[0682]

[0683] Example 2.3: Additive material represented by chemical formula 8

[0684] An additive material represented by the chemical formula 8 in powder form is obtained:

[0685] (Chemical formula 8)

[0686]

[0687] Example 2.4: Additive material represented by chemical formula 11

[0688] An additive material represented by the chemical formula 11 in powder form is obtained:

[0689] (Chemical formula 11)

[0690]

[0691] Example 2.5: Additive material represented by chemical formula 14

[0692] An additive material represented by the chemical formula 14 in powder form is obtained:

[0693] (Chemical Formula 14)

[0694]

[0695] Example 2.6: Additive material represented by chemical formula 17

[0696] An additive material represented by the chemical formula 17 in powder form is obtained:

[0697] (Chemical formula 17)

[0698]

[0699] Example 2.7: Additive material represented by chemical formula 20

[0700] An additive material represented by the chemical formula 20 in powder form is obtained:

[0701] (Chemical formula 20)

[0702]

[0703] Example 2.8: Additive material represented by chemical formula 23

[0704] An additive material represented by the chemical formula 23 in powder form is obtained:

[0705] (Chemical formula 23)

[0706]

[0707]

[0708] Example 3: Formation of a mixture for a solid electrolyte

[0709] Example 3.1.1

[0710] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.1 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0711] Example 3.1.2

[0712] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.2 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0713] Example 3.1.3

[0714] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.3 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0715] Example 3.1.4

[0716] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.4 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0717] Example 3.1.5

[0718] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.5 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0719] Example 3.1.6

[0720] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.6 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0721] Example 3.1.7

[0722] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.7 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0723] Example 3.1.8

[0724] A mixture is obtained by mixing the LPSCl of Example 1.1 and the additive material of Example 2.8 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0725] Example 3.2.1

[0726] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.1 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0727] Example 3.2.2

[0728] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.2 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0729] Example 3.2.3

[0730] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.3 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode layer.

[0731] Example 3.2.4

[0732] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.4 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0733] Example 3.2.5

[0734] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.5 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0735] Example 3.2.6

[0736] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.6 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0737] Example 3.2.7

[0738] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.7 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0739] Example 3.2.8

[0740] A mixture is obtained by mixing the LPSBr of Example 1.2 and the additive material of Example 2.8 in a weight ratio of 1:1. The mixture is ball milled to prepare a solid electrode material.

[0741] Example 3.3.1

[0742] The LPSI of Example 1.3 and the additive material of Example 2.1 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0743] Example 3.3.2

[0744] The LPSI of Example 1.3 and the additive material of Example 2.2 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0745] Example 3.3.3

[0746] The LPSI of Example 1.3 and the additive material of Example 2.3 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0747] Example 3.3.4

[0748] The LPSI of Example 1.3 and the additive material of Example 2.4 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0749] Example 3.3.5

[0750] The LPSI of Example 1.3 and the additive material of Example 2.5 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0751] Example 3.3.6

[0752] The LPSI of Example 1.3 and the additive material of Example 2.6 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0753] Example 3.3.7

[0754] The LPSI of Example 1.3 and the additive material of Example 2.7 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0755] Example 3.3.8

[0756] The LPSI of Example 1.3 and the additive material of Example 2.8 are mixed in a weight ratio of 1:1 to obtain a mixture. The mixture is ball milled to prepare a solid electrode material.

[0757] Example 4: Assembly of the battery

[0758] Example 4.1.1

[0759] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.1 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0760] Example 4.1.2

[0761] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.2 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0762] Example 4.1.3

[0763] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.3 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0764] Example 4.1.4

[0765] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.4 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0766] Example 4.1.5

[0767] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.5 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0768] Example 4.1.6

[0769] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.6 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0770] Example 4.1.7

[0771] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.7 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0772] Example 4.1.8

[0773] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.1.8 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0774] Example 4.2.1

[0775] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.1 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0776] Example 4.2.2

[0777] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.2 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0778] Example 4.2.3

[0779] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.3 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0780] Example 4.2.4

[0781] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.4 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0782] Example 4.2.5

[0783] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.5 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0784] Example 4.2.6

[0785] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.6 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0786] Example 4.2.7

[0787] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.7 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0788] Example 4.2.8

[0789] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.2.8 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0790] Example 4.3.1

[0791] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.1 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0792] Example 4.3.2

[0793] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.2 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0794] Example 4.3.3

[0795] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.3 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0796] Example 4.3.4

[0797] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.4 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0798] Example 4.3.5

[0799] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.5 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0800] Example 4.3.6

[0801] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.6 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0802] Example 4.3.7

[0803] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.7 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0804] Example 4.3.8

[0805] Obtain a positive electrode. Obtain a negative electrode. A solid electrolyte layer containing the solid electrolyte material of Example 3.3.8 is positioned between the positive electrode and the negative electrode to prepare a battery.

[0806] Example 5: Measurement of lithium ion diffusion

[0807] Example 5.1.1.1

[0808] The battery of Example 4.1.1 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0809] Example 5.1.1.2

[0810] The battery of Example 4.1.2 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0811] Example 5.1.1.3

[0812] The battery of Example 4.1.3 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0813] Example 5.1.1.4

[0814] The battery of Example 4.1.4 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0815] Example 5.1.1.5

[0816] The battery of Example 4.1.5 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0817] Example 5.1.1.6

[0818] The battery of Example 4.1.6 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0819] Example 5.1.1.7

[0820] The battery of Example 4.1.7 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0821] Example 5.1.1.8

[0822] The battery of Example 4.1.8 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0823] Example 5.1.2.1

[0824] The battery of Example 4.2.1 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0825] Example 5.1.2.2

[0826] The battery of Example 4.2.2 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0827] Example 5.1.2.3

[0828] The battery of Example 4.2.3 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0829] Example 5.1.2.4

[0830] The battery of Example 4.2.4 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0831] Example 5.1.2.5

[0832] The battery of Example 4.2.5 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0833] Example 5.1.2.6

[0834] The battery of Example 4.2.6 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0835] Example 5.1.2.7

[0836] The battery of Example 4.2.7 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0837] Example 5.1.2.8

[0838] The battery of Example 4.2.8 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0839] Example 5.1.3.1

[0840] The battery of Example 4.3.1 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0841] Example 5.1.3.2

[0842] The battery of Example 4.3.2 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0843] Example 5.1.3.3

[0844] The battery of Example 4.3.3 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0845] Example 5.1.3.4

[0846] The battery of Example 4.3.4 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0847] Example 5.1.3.5

[0848] The battery of Example 4.3.5 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0849] Example 5.1.3.6

[0850] The battery of Example 4.3.6 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0851] Example 5.1.3.7

[0852] The battery of Example 4.3.7 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0853] Example 5.1.3.8

[0854] The battery of Example 4.3.8 is operated under a pressure of 1 MPa. The lithium ion diffusion rate of the battery is measured.

[0855] Example 5.2.1.1

[0856] The battery of Example 4.1.1 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0857] Example 5.2.1.2

[0858] The battery of Example 4.1.2 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0859] Example 5.2.1.3

[0860] The battery of Example 4.1.3 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0861] Example 5.2.1.4

[0862] The battery of Example 4.1.4 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0863] Example 5.2.1.5

[0864] The battery of Example 4.1.5 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0865] Example 5.2.1.6

[0866] The battery of Example 4.1.6 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0867] Example 5.2.1.7

[0868] The battery of Example 4.1.7 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0869] Example 5.2.1.8

[0870] The battery of Example 4.1.8 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0871] Example 5.2.2.1

[0872] The battery of Example 4.2.1 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0873] Example 5.2.2.2

[0874] The battery of Example 4.2.2 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0875] Example 5.2.2.3

[0876] The battery of Example 4.2.3 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0877] Example 5.2.2.4

[0878] The battery of Example 4.2.4 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0879] Example 5.2.2.5

[0880] The battery of Example 4.2.5 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0881] Example 5.2.2.6

[0882] The battery of Example 4.2.6 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0883] Example 5.2.2.7

[0884] The battery of Example 4.2.7 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0885] Example 5.2.2.8

[0886] The battery of Example 4.2.8 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0887] Example 5.2.3.1

[0888] The battery of Example 4.3.1 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0889] Example 5.2.3.2

[0890] The battery of Example 4.3.2 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0891] Example 5.2.3.3

[0892] The battery of Example 4.3.3 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0893] Example 5.2.3.4

[0894] The battery of Example 4.3.4 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0895] Example 5.2.3.5

[0896] The battery of Example 4.3.5 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0897] Example 5.2.3.6

[0898] The battery of Example 4.3.6 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0899] Example 5.2.3.7

[0900] The battery of Example 4.3.7 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0901] Example 5.2.3.8

[0902] The battery of Example 4.3.8 is operated under a pressure of 2 MPa. The lithium ion diffusion rate of the battery is measured.

[0903] Example 5.3.1.1

[0904] The battery of Example 4.1.1 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0905] Example 5.3.1.2

[0906] The battery of Example 4.1.2 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0907] Example 5.3.1.3

[0908] The battery of Example 4.1.3 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0909] Example 5.3.1.4

[0910] The battery of Example 4.1.4 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0911] Example 5.3.1.5

[0912] The battery of Example 4.1.5 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0913] Example 5.3.1.6

[0914] The battery of Example 4.1.6 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0915] Example 5.3.1.7

[0916] The battery of Example 4.1.7 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0917] Example 5.3.1.8

[0918] The battery of Example 4.1.8 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0919] Example 5.3.2.1

[0920] The battery of Example 4.2.1 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0921] Example 5.3.2.2

[0922] The battery of Example 4.2.2 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0923] Example 5.3.2.3

[0924] The battery of Example 4.2.3 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0925] Example 5.3.2.4

[0926] The battery of Example 4.2.4 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0927] Example 5.3.2.5

[0928] The battery of Example 4.2.5 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0929] Example 5.3.2.6

[0930] The battery of Example 4.2.6 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0931] Example 5.3.2.7

[0932] The battery of Example 4.2.7 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0933] Example 5.3.2.8

[0934] The battery of Example 4.2.8 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0935] Example 5.3.3.1

[0936] The battery of Example 4.3.1 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0937] Example 5.3.3.2

[0938] The battery of Example 4.3.2 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0939] Example 5.3.3.3

[0940] The battery of Example 4.3.3 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0941] Example 5.3.3.4

[0942] The battery of Example 4.3.4 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0943] Example 5.3.3.5

[0944] The battery of Example 4.3.5 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0945] Example 5.3.3.6

[0946] The battery of Example 4.3.6 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0947] Example 5.3.3.7

[0948] The battery of Example 4.3.7 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0949] Example 5.3.3.8

[0950] The battery of Example 4.3.8 is operated under a pressure of 3 MPa. The lithium ion diffusion rate of the battery is measured.

[0951] Example 5.4.1.1

[0952] The battery of Example 4.1.1 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0953] Example 5.4.1.2

[0954] The battery of Example 4.1.2 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0955] Example 5.4.1.3

[0956] The battery of Example 4.1.3 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0957] Example 5.4.1.4

[0958] The battery of Example 4.4.1.4 is operated under a pressure of 4 MPa. The lithium ion diffusion of the battery is measured.

[0959] Example 5.4.1.5

[0960] The battery of Example 4.1.5 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0961] Example 5.4.1.6

[0962] The battery of Example 4.1.6 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0963] Example 5.4.1.7

[0964] The battery of Example 4.1.7 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0965] Example 5.4.1.8

[0966] The battery of Example 4.1.8 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0967] Example 5.4.2.1

[0968] The battery of Example 4.2.1 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0969] Example 5.4.2.2

[0970] The battery of Example 4.2.2 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0971] Example 5.4.2.3

[0972] The battery of Example 4.2.3 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0973] Example 5.4.2.4

[0974] The battery of Example 4.2.4 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0975] Example 5.4.2.5

[0976] The battery of Example 4.2.5 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0977] Example 5.4.2.6

[0978] The battery of Example 4.2.6 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0979] Example 5.4.2.7

[0980] The battery of Example 4.2.7 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0981] Example 5.4.2.8

[0982] The battery of Example 4.2.8 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0983] Example 5.4.3.1

[0984] The battery of Example 4.3.1 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0985] Example 5.4.3.2

[0986] The battery of Example 4.3.2 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0987] Example 5.4.3.3

[0988] The battery of Example 4.3.3 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0989] Example 5.4.3.4

[0990] The battery of Example 4.3.4 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0991] Example 5.4.3.5

[0992] The battery of Example 4.3.5 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0993] Example 5.4.3.6

[0994] The battery of Example 4.3.6 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0995] Example 5.4.3.7

[0996] The battery of Example 4.3.7 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0997] Example 5.4.3.8

[0998] The battery of Example 4.3.8 is operated under a pressure of 4 MPa. The lithium ion diffusion rate of the battery is measured.

[0999] Example 5.5.1.1

[1000] The battery of Example 4.1.1 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1001] Example 5.5.1.2

[1002] The battery of Example 4.1.2 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1003] Example 5.5.1.3

[1004] The battery of Example 4.1.3 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1005] Example 5.5.1.4

[1006] The battery of Example 4.1.4 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1007] Example 5.5.1.5

[1008] The battery of Example 4.1.5 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1009] Example 5.5.1.6

[1010] The battery of Example 4.1.6 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1011] Example 5.5.1.7

[1012] The battery of Example 4.1.7 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1013] Example 5.5.1.8

[1014] The battery of Example 4.1.8 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1015] Example 5.5.2.1

[1016] The battery of Example 4.2.1 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1017] Example 5.5.2.2

[1018] The battery of Example 4.2.2 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1019] Example 5.5.2.3

[1020] The battery of Example 4.2.3 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1021] Example 5.5.2.4

[1022] The battery of Example 4.2.4 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1023] Example 5.5.2.5

[1024] The battery of Example 4.2.5 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1025] Example 5.5.2.6

[1026] The battery of Example 4.2.6 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1027] Example 5.5.2.7

[1028] The battery of Example 4.2.7 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1029] Example 5.5.2.8

[1030] The battery of Example 4.2.8 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1031] Example 5.5.3.1

[1032] The battery of Example 4.3.1 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1033] Example 5.5.3.2

[1034] The battery of Example 4.3.2 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1035] Example 5.5.3.3

[1036] The battery of Example 4.3.3 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1037] Example 5.5.3.4

[1038] The battery of Example 4.3.4 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1039] Example 5.5.3.5

[1040] The battery of Example 4.3.5 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1041] Example 5.5.3.6

[1042] The battery of Example 4.3.6 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1043] Example 5.5.3.7

[1044] The battery of Example 4.3.7 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1045] Example 5.5.3.8

[1046] The battery of Example 4.3.8 is operated under a pressure of 5 MPa. The lithium ion diffusion rate of the battery is measured.

[1047] Example 6: Measurement of specific capacity

[1048] Example 6.1.1.1

[1049] The battery of Example 4.1.1 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1050] Example 6.1.1.2

[1051] The battery of Example 4.1.2 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1052] Example 6.1.1.3

[1053] The battery of Example 4.1.3 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1054] Example 6.1.1.4

[1055] The battery of Example 4.1.4 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1056] Example 6.1.1.5

[1057] The battery of Example 4.1.5 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1058] Example 6.1.1.6

[1059] The battery of Example 4.1.6 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1060] Example 6.1.1.7

[1061] The battery of Example 4.1.7 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1062] Example 6.1.1.8

[1063] The battery of Example 4.1.8 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1064] Example 6.1.2.1

[1065] The battery of Example 4.2.1 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1066] Example 6.1.2.2

[1067] The battery of Example 4.2.2 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1068] Example 6.1.2.3

[1069] The battery of Example 4.2.3 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1070] Example 6.1.2.4

[1071] The battery of Example 4.2.4 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1072] Example 6.1.2.5

[1073] The battery of Example 4.2.5 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1074] Example 6.1.2.6

[1075] The battery of Example 4.2.6 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1076] Example 6.1.2.7

[1077] The battery of Example 4.2.7 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1078] Example 6.1.2.8

[1079] The battery of Example 4.2.8 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1080] Example 6.1.3.1

[1081] The battery of Example 4.3.1 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1082] Example 6.1.3.2

[1083] The battery of Example 4.3.2 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1084] Example 6.1.3.3

[1085] The battery of Example 4.3.3 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1086] Example 6.1.3.4

[1087] The battery of Example 4.3.4 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1088] Example 6.1.3.5

[1089] The battery of Example 4.3.5 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1090] Example 6.1.3.6

[1091] The battery of Example 4.3.6 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1092] Example 6.1.3.7

[1093] The battery of Example 4.3.7 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1094] Example 6.1.3.8

[1095] The battery of Example 4.3.8 is operated under a pressure of 1 MPa. The specific capacity of the battery is measured.

[1096] Example 6.2.1.1

[1097] The battery of Example 4.1.1 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1098] Example 6.2.1.2

[1099] The battery of Example 4.1.2 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1100] Example 6.2.1.3

[1101] The battery of Example 4.1.3 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1102] Example 6.2.1.4

[1103] The battery of Example 4.1.4 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1104] Example 6.2.1.5

[1105] The battery of Example 4.1.5 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1106] Example 6.2.1.6

[1107] The battery of Example 4.1.6 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1108] Example 6.2.1.7

[1109] The battery of Example 4.1.7 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1110] Example 6.2.1.8

[1111] The battery of Example 4.1.8 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1112] Example 6.2.2.1

[1113] The battery of Example 4.2.1 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1114] Example 6.2.2.2

[1115] The battery of Example 4.2.2 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1116] Example 6.2.2.3

[1117] The battery of Example 4.2.3 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1118] Example 6.2.2.4

[1119] The battery of Example 4.2.4 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1120] Example 6.2.2.5

[1121] The battery of Example 4.2.5 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1122] Example 6.2.2.6

[1123] The battery of Example 4.2.6 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1124] Example 6.2.2.7

[1125] The battery of Example 4.2.7 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1126] Example 6.2.2.8

[1127] The battery of Example 4.2.8 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1128] Example 6.2.3.1

[1129] The battery of Example 4.3.1 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1130] Example 6.2.3.2

[1131] The battery of Example 4.3.2 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1132] Example 6.2.3.3

[1133] The battery of Example 4.3.3 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1134] Example 6.2.3.4

[1135] The battery of Example 4.3.4 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1136] Example 6.2.3.5

[1137] The battery of Example 4.3.5 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1138] Example 6.2.3.6

[1139] The battery of Example 4.3.6 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1140] Example 6.2.3.7

[1141] The battery of Example 4.3.7 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1142] Example 6.2.3.8

[1143] The battery of Example 4.3.8 is operated under a pressure of 2 MPa. The specific capacity of the battery is measured.

[1144] Example 6.3.1.1

[1145] The battery of Example 4.1.1 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1146] Example 6.3.1.2

[1147] The battery of Example 4.1.2 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1148] Example 6.3.1.3

[1149] The battery of Example 4.1.3 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1150] Example 6.3.1.4

[1151] The battery of Example 4.1.4 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1152] Example 6.3.1.5

[1153] The battery of Example 4.1.5 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1154] Example 6.3.1.6

[1155] The battery of Example 4.1.6 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1156] Example 6.3.1.7

[1157] The battery of Example 4.1.7 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1158] Example 6.3.1.8

[1159] The battery of Example 4.1.8 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1160] Example 6.3.2.1

[1161] The battery of Example 4.2.1 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1162] Example 6.3.2.2

[1163] The battery of Example 4.2.2 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1164] Example 6.3.2.3

[1165] The battery of Example 4.2.3 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1166] Example 6.3.2.4

[1167] The battery of Example 4.2.4 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1168] Example 6.3.2.5

[1169] The battery of Example 4.2.5 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1170] Example 6.3.2.6

[1171] The battery of Example 4.2.6 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1172] Example 6.3.2.7

[1173] The battery of Example 4.2.7 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1174] Example 6.3.2.8

[1175] The battery of Example 4.2.8 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1176] Example 6.3.3.1

[1177] The battery of Example 4.3.1 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1178] Example 6.3.3.2

[1179] The battery of Example 4.3.2 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1180] Example 6.3.3.3

[1181] The battery of Example 4.3.3 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1182] Example 6.3.3.4

[1183] The battery of Example 4.3.4 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1184] Example 6.3.3.5

[1185] The battery of Example 4.3.5 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1186] Example 6.3.3.6

[1187] The battery of Example 4.3.6 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1188] Example 6.3.3.7

[1189] The battery of Example 4.3.7 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1190] Example 6.3.3.8

[1191] The battery of Example 4.3.8 is operated under a pressure of 3 MPa. The specific capacity of the battery is measured.

[1192] Example 6.4.1.1

[1193] The battery of Example 4.1.1 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1194] Example 6.4.1.2

[1195] The battery of Example 4.1.2 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1196] Example 6.4.1.3

[1197] The battery of Example 4.1.3 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1198] Example 6.4.1.4

[1199] The battery of Example 4.4.1.4 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1200] Example 6.4.1.5

[1201] The battery of Example 4.1.5 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1202] Example 6.4.1.6

[1203] The battery of Example 4.1.6 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1204] Example 6.4.1.7

[1205] The battery of Example 4.1.7 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1206] Example 6.4.1.8

[1207] The battery of Example 4.1.8 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1208] Example 6.4.2.1

[1209] The battery of Example 4.2.1 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1210] Example 6.4.2.2

[1211] The battery of Example 4.2.2 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1212] Example 6.4.2.3

[1213] The battery of Example 4.2.3 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1214] Example 6.4.2.4

[1215] The battery of Example 4.2.4 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1216] Example 6.4.2.5

[1217] The battery of Example 4.2.5 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1218] Example 6.4.2.6

[1219] The battery of Example 4.2.6 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1220] Example 6.4.2.7

[1221] The battery of Example 4.2.7 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1222] Example 6.4.2.8

[1223] The battery of Example 4.2.8 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1224] Example 6.4.3.1

[1225] The battery of Example 4.3.1 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1226] Example 6.4.3.2

[1227] The battery of Example 4.3.2 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1228] Example 6.4.3.3

[1229] The battery of Example 4.3.3 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1230] Example 6.4.3.4

[1231] The battery of Example 4.3.4 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1232] Example 6.4.3.5

[1233] The battery of Example 4.3.5 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1234] Example 6.4.3.6

[1235] The battery of Example 4.3.6 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1236] Example 6.4.3.7

[1237] The battery of Example 4.3.7 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured.

[1238] Example 6.4.3.8

[1239] The battery of Example 4.3.8 is operated under a pressure of 4 MPa. The specific capacity of the battery is measured as follows.

[1240] Example 6.5.1.1

[1241] The battery of Example 4.1.1 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1242] Example 6.5.1.2

[1243] The battery of Example 4.1.2 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1244] Example 6.5.1.3

[1245] The battery of Example 4.1.3 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1246] Example 6.5.1.4

[1247] The battery of Example 4.1.4 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1248] Example 6.5.1.5

[1249] The battery of Example 4.1.5 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1250] Example 6.5.1.6

[1251] The battery of Example 4.1.6 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1252] Example 6.5.1.7

[1253] The battery of Example 4.1.7 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1254] Example 6.5.1.8

[1255] The battery of Example 4.1.8 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1256] Example 6.5.2.1

[1257] The battery of Example 4.2.1 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1258] Example 6.5.2.2

[1259] The battery of Example 4.2.2 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1260] Example 6.5.2.3

[1261] The battery of Example 4.2.3 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1262] Example 6.5.2.4

[1263] The battery of Example 4.2.4 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1264] Example 6.5.2.5

[1265] The battery of Example 4.2.5 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1266] Example 6.5.2.6

[1267] The battery of Example 4.2.6 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1268] Example 6.5.2.7

[1269] The battery of Example 4.2.7 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1270] Example 6.5.2.8

[1271] The battery of Example 4.2.8 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1272] Example 6.5.3.1

[1273] The battery of Example 4.3.1 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1274] Example 6.5.3.2

[1275] The battery of Example 4.3.2 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1276] Example 6.5.3.3

[1277] The battery of Example 4.3.3 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1278] Example 6.5.3.4

[1279] The battery of Example 4.3.4 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1280] Example 6.5.3.5

[1281] The battery of Example 4.3.5 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1282] Example 6.5.3.6

[1283] The battery of Example 4.3.6 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1284] Example 6.5.3.7

[1285] The battery of Example 4.3.7 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1286] Example 6.5.3.8

[1287] The battery of Example 4.3.8 is operated under a pressure of 5 MPa. The specific capacity of the battery is measured.

[1288] Combinations and characteristics included

[1289] Various features and characteristics are described herein to provide an understanding of the composition, structure, production, function, and / or operation of the present disclosure, including the disclosed compositions, coatings, and methods. It is to be understood that the various features and characteristics of the present disclosure described herein may be combined in any suitable manner, regardless of whether such features and characteristics are explicitly described in combination herein. The inventors and applicants expressly intend that such combinations of features and characteristics be included within the scope of the present disclosure described herein. Accordingly, the claims may be amended to recite any features and characteristics explicitly or essentially set forth in, or explicitly or essentially supported by, this specification, in any combination. Furthermore, applicants reserve the right to amend the claims to affirmatively disclaim features and characteristics that may exist in the prior art, even if those features and characteristics are not explicitly described herein. Accordingly, any such amendment does not add new matter to the specification or claims, but is subject to the detailed description requirements, the sufficiency of description requirements, and the novelty requirements.

[1290] Cited by reference

[1291] Any patent, publication, or other document identified in this specification is incorporated by reference in its entirety unless otherwise indicated, but only to the extent that the incorporated material does not conflict with prior descriptions, definitions, statements, examples, or other disclosure material expressly set forth herein. Accordingly, to the extent necessary, the explicit disclosure set forth herein supersedes any conflicting material incorporated by reference. Any material, or portion thereof, incorporated by reference herein but that conflicts with prior definitions, statements, or other disclosure material set forth herein is incorporated only to the extent that no conflict arises between the incorporated material and the prior disclosure material. Applicant reserves the right to amend this specification to explicitly cite any subject matter incorporated by reference, or portions thereof. Any amendment to this specification to add such incorporated subject matter shall comply with the detailed description requirements, the sufficiency of description requirements, and the novelty requirements.

[1292] Examples of various forms

[1293] While this disclosure provides a description of various specific embodiments for the purpose of illustrating various aspects and / or potential uses of the disclosure, it is understood that variations and modifications will occur to those skilled in the art. Accordingly, this disclosure is to be construed at least as broadly as the claims, and not more narrowly defined by the specific exemplary embodiments provided herein.

Claims

1. Bipolar; cathode; A solid battery comprising a solid electrolyte layer positioned between the positive electrode and the negative electrode and configured to enable transport of lithium ions between the positive electrode and the negative electrode; The above solid electrolyte layer Particles comprising a sulfide-containing material; and Contains an additive material represented by ABC (chemical formula 1); A is a thiol group (SH) or a leaving group, A is configured to interact with the sulfur of the sulfide-containing material of said particles, and at least a portion of said additive material is interposed between two immediately adjacent particles of said particles, When A is a leaving group, A is selected from the group consisting of chloride, bromide, iodide, tosylate (p-toluenesulfonate) or mesylate (methanesulfonate) group, acetate or trifluoroacetate group, phosphate or phosphonate group, carboxylate group, alkoxide group, amine group, cyano (CN) group, azide (N3) group, sulfonate group, triethoxysilyl moiety, trimethoxysilyl moiety, and combinations thereof, B is propane, n-butane (CH3CH2CH2CH3), isobutane (CH3CH(CH3)2), n-pentane (CH3(CH2)3CH3), isopentane (2-methylbutane, CH3CH2CH(CH3)2), neopentane (2,2-dimethylpropane, (CH3)4C), n-hexane (CH3(CH2)4CH3), 2-methylpentane (CH3CH2CH2CH(CH3)CH3), 3-methylpentane (CH3CH2CH(CH3)CH2CH3), 2,2-dimethylbutane (CH3C(CH3)2CH2CH3), 2,3-dimethylbutane (CH3CH(CH3)CH(CH3)CH3), n-heptane (CH3(CH2)5CH3), 2-methylhexane (CH3CH2CH2CH2CH(CH3)CH3), 3-Methylhexane (CH3CH2CH2CH(CH3)CH2CH3), 2,2-dimethylpentane (CH3C(CH3)2CH2CH2CH3), 2,3-dimethylpentane (CH3CH(CH3)CH2CH(CH3)CH3), 2,4-dimethylpentane (CH3CH(CH3)CH2CH2CH(CH3)CH3), 3,3-dimethylpentane (CH3CH2CH(CH3)2CH2CH3), 3-ethylpentane (CH3CH2CH2CH(CH2CH3)CH3), 2,2,3-trimethylbutane ((CH3)2CHCH2CH(CH3)2), n-octane (CH3(CH2)6CH3), 2-methylheptane (CH3CH2CH2CH2CH2CH(CH3)CH3), 3-methylheptane (CH3CH2CH2CH2CH(CH3)CH2CH3), 4-Methylheptane (CH3CH2CH2CH(CH3)CH2CH2CH3), 2,2-dimethylhexane (CH3C(CH3)2(CH2)4CH3), 2,3-dimethylhexane (CH3CH(CH3)CH2CH2CH(CH3)CH3), 2,4-dimethylhexane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH3), 3,3-dimethylhexane (CH3CH2CH(CH3)2CH2CH2CH3), 3,4-dimethylhexane (CH3CH2CH(CH3)CH2CH(CH3)CH3), 2,2,4-trimethylpentane (isooctane, CH3CH(CH3)2CH2CH(CH3)2), 2-ethylhexane (CH3CH2CH(CH2CH3)CH2CH3), n-nonane (CH3(CH2)7CH3), 2-methyloctane (CH3CH2CH2CH2CH2CH2CH(CH3)CH3),3-Methyloctane (CH3CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-dimethylheptane (CH3C(CH3)2(CH2)5CH3), 2,3-dimethylheptane (CH3CH(CH3)CH2CH2CH2CH2CH(CH3)CH3), 2,4-dimethylheptane (CH3CH(CH3)CH2CH2CH(CH3)CH2CH3), 2,2,4-trimethylhexane (CH3C(CH3)2CH2CH(CH3)2CH2CH2CH3), 3,3-dimethylheptane (CH3CH2CH(CH3)2CH2CH2CH2CH3), 3-ethylheptane (CH3CH2CH2CH(CH2CH3)CH2CH3), n-decane (CH3(CH2)8CH3), 2-Methylnonane (CH3CH2CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-Methylnonane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-Dimethyloctane (CH3C(CH3)2(CH2)6CH3), 2,3-Dimethyloctane (CH3CH(CH3)CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 2,4-Dimethyloctane (CH3CH(CH3)CH2CH2CH2CH(CH3)CH2CH3), 2,5-Dimethyloctane (CH3CH2CH(CH3)CH2CH2CH2CH2CH2CH3), 3,3-Dimethyloctane (CH3CH2CH(CH3)2CH2CH2CH(CH3)CH2CH3), 2-Ethyloctane (CH3CH2CH(CH2CH3)CH2CH2CH3), n-undecane (C, 11 H 24 ) and its branched isomers, n-dodecane (C 12 H 26 ) and its branched isomer, n-tridecane (C 13 H 28 ) and its branched isomer, n-tetradecane (C 14 H 30 ) and its branched isomer, n-pentadecane (C 15 H 32 ) and its branched isomers, n-hexadecane (C 16 H 34 ) and its branched isomer, n-heptadecane (C 17 H 36 ) and its branched isomer, n-octadecane (C 18 H 38 ) and its branched isomer, n-nonadecane (C 19 H 40 ) and its branched isomers, n-eicosane (C 20 H 42 ) and its branched isomers, and a substituted or unsubstituted C3-C20 alkane group selected from the group consisting of combinations thereof, When B is a substituted C3-C20 alkane group, B is fluoro (-F), chloro (-Cl), bromo (-Br), iodo (-I), hydroxyl (-OH), ether (-OR), aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxide (-OO-), amino (-NH2), secondary amine (-NHR), tertiary amine (-NR2), nitro (-NO2), cyanide (-CN), amide (-CONH2), substituted amide (-CONHR, -CONR2), thiol (-SH), sulfide (-SR), sulfonyl (-SO2R), sulfate (-SO4R), phosphate (-PO4R2), phosphine (-PR2); Containing a substituent selected from the group consisting of alkyl (-R), alkylene (-R=R), cycloalkyl (-R), aryl (-Ar), benzyl (-C6H5CH2), alkenyl (-C=C-), alkynyl (-C≡C-), aromatic ring, acyl (-COR); sulfonyl (-SO2R); carbamoyl (-CONH2); isonitrile (-NC); azide (-N3), perfluoroalkyl (-CF3) and other fluoroalkyl chains, acetal (-RCH(OR)2), ketal (-RC(OR)2R), organometallic groups, and combinations thereof, C is phosphate, or sodium (Na), potassium (K), lithium (Li), rubidium (Rb), cesium (Cs), calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba), iron (II) (Fe II), iron (III) (Fe III), copper (I) (Cu I), copper (II) (Cu II), zinc (Zn), manganese (Mn), ammonium (NH4), methylammonium (CH3NH3), dimethylammonium ((CH3)2NH2), trimethylammonium ((CH3)3N + ), pyridinium (C5H5NH + ), lead(II)(Pb), mercury(II)(Hg), cadmium(Cd), lanthanum(La), cerium(Ce), uranium(U), sodium-calcium(Na-Ca), potassium-magnesium(K-Mg), tetramethylammonium(N(CH3)4 + ), imidazolium (C3H4NH2 + ), phosphonium (P + (CH3)4), guanidinium (C(NH2)3 + ), and a phosphate salt selected from the group consisting of combinations thereof, Solid state batteries.

2. In paragraph 1, A solid battery, wherein at least a portion of the additive material is in contact with the surface of one of the two adjacent particles.

3. In paragraph 2, A solid battery, wherein at least a portion of said additive material contacts the surface of one of said two neighboring particles by at least one of a covalent bond or a non-covalent attachment.

4. In paragraph 1, The above additive material is a solid battery, not in particle form.

5. In paragraph 1, A solid-state battery, wherein the solid-state battery is configured to operate at a pressure of less than 10 MPa, which is lower than the pressure required when the additive material is absent in the solid electrolyte layer.

6. In paragraph 1, A solid-state battery, wherein the sulfide-containing material comprises lithium phosphorus sulfur chloride (LPSCl).

7. In paragraph 1, The above additive material is selected from the group consisting of the following, solid battery: (Chemical formula 2) ; (Chemical formula 3) ; (Chemical Formula 4) ; (Chemical formula 5) ; (Chemical formula 6) ; (Chemical formula 7) ; (Chemical formula 8) ; (Chemical formula 9) ; (Chemical formula 10) ; (Chemical formula 11) ; (Chemical formula 12) ; (Chemical formula 13) ; (Chemical Formula 14) ; (Chemical Formula 15) ; (Chemical formula 16) ; (Chemical formula 17) ; (Chemical formula 18) ; (Chemical Formula 19) ; (Chemical formula 20) ; (Chemical formula 21) ; (Chemical formula 22) ; (Chemical formula 23) ; (Chemical formula 24) ; (Chemical formula 25) ; and A combination of these.

8. In paragraph 1, A solid battery, wherein the sulfide-containing material has a first hardness of 0.1 to 1 GPa obtained from a nanoindentation test, and the additive material has a second hardness of 0.001 to 0.01 GPa obtained from a nanoindentation test.

9. In paragraph 1, A solid battery, wherein the solid electrolyte layer comprises the sulfide-containing material and the additive material in a weight ratio of 1:1 to 25:

1.

10. In paragraph 1, A solid-state battery, wherein the solid-state battery is configured to operate under a pressure of less than 5 MPa.

11. In paragraph 1, The above solid-state battery is a solid-state battery having a specific capacity exceeding 100 mAh / g.

12. In paragraph 1, A solid battery wherein the above additive material is in powder form.

13. In paragraph 1, A solid battery, wherein the solid electrolyte layer has a porosity of 5% to 15%.

14. In paragraph 1, A solid battery, wherein the solid electrolyte layer has a density increased by more than 10% compared to that without the additive material.

15. A method for manufacturing a solid battery according to paragraph 1, A method for manufacturing a solid battery, comprising the step of providing the solid electrolyte layer, wherein the step comprises ball milling the particles and the additive material together.

16. In paragraph 15, The above ball milling is a manufacturing method in which A interacts with sulfur of the sulfide-containing material of the particles so that at least a portion of the additive material is attached to the surface of the particles.

17. Bipolar; cathode; A solid battery comprising a solid electrolyte layer positioned between the positive electrode and the negative electrode and configured to enable transport of lithium ions between the positive electrode and the negative electrode; The above solid electrolyte layer Particles comprising a sulfide-containing material; and An additive material selected from the group consisting of: Solid-state batteries: (Chemical formula 2) ; (Chemical formula 3) ; (Chemical Formula 4) ; (Chemical formula 5) ; (Chemical formula 6) ; (Chemical formula 7) ; (Chemical formula 8) ; (Chemical formula 9) ; (Chemical formula 10) ; (Chemical formula 11) ; (Chemical formula 12) ; (Chemical formula 13) ; (Chemical Formula 14) ; (Chemical Formula 15) ; (Chemical formula 16) ; (Chemical formula 17) ; (Chemical formula 18) ; (Chemical Formula 19) ; (Chemical formula 20) ; (Chemical formula 21) ; (Chemical formula 22) ; (Chemical formula 23) ; (Chemical formula 24) ; (Chemical formula 25) ; and A combination of these.

18. In paragraph 17, A solid-state battery, wherein said additive material is configured to interact with sulfur of the sulfide-containing material of said particles, and wherein at least a portion of said additive material is interposed between two immediately adjacent particles of said particles and contacts a surface of one of said two adjacent particles by covalent bonding and / or non-covalent attachment.

19. An electric vehicle comprising a solid-state battery of paragraph 1.

20. An electric vehicle comprising a solid-state battery of Article 17.

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