Solid-state battery and method of manufacturing the same

Abstract

The present invention provides an additive material for adding to a sulfide-containing solid electrolyte material for a solid-state battery, a solid-state battery using the additive material in its solid electrolyte material, and a manufacturing method of the solid-state battery. The additive material provided in the present application allows the solid-state battery using the additive material to operate at a relatively low pressure compared to a solid-state battery not using the additive material.

Description

[0001] Any reference to priority claims is included.

[0002] This application claims priority to U.S. Provisional Application No. 63 / 554,077, filed February 15, 2024, and U.S. Non-Provisional Application No. 18 / 972,543, filed December 6, 2024, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention relates to solid-state batteries and methods for manufacturing solid-state batteries. Background Technology

[0004] Secondary batteries

[0005] Rechargeable batteries have become an increasingly ideal power source for a wide range of electronic devices, including automobiles, computers, mobile phones, tools, scooters, bicycles, electric vehicles, energy storage systems, drones, and other equipment. Among rechargeable batteries, lithium-ion batteries are particularly valued for their ability to provide an ideal balance between voltage and energy density. In addition to their performance advantages, lithium-ion rechargeable batteries contribute to addressing 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 energy sources such as solar and wind power. Furthermore, the long cycle life and high energy density of lithium-ion batteries can support the development of smart grids and distributed energy systems, potentially improving overall energy efficiency and reducing dependence on fossil fuels. Traditionally, lithium rechargeable batteries contain liquid electrolytes, which typically contain lithium salts dissolved in organic solvents. However, the development of all-solid-state lithium rechargeable batteries as an alternative to traditional liquid electrolyte systems has received increasing attention. Solid-state batteries offer potential advantages in terms of safety, stability, and energy density. Despite these potential advantages, the development of practical all-solid-state lithium rechargeable batteries still faces several significant challenges.

[0006] Challenges of all-solid-state rechargeable batteries

[0007] One challenge in solid-state battery design is achieving and maintaining sufficient lithium-ion diffusion within the solid electrolyte material. Furthermore, during battery charging and discharging, volume changes (e.g., expansion and contraction) can occur in certain battery components, such as electrodes. These volume changes can lead to mechanical stress or contact failures between various components within the battery structure. Contact failures between battery components can cause degradation of charge-discharge characteristics and overall battery capacity. Researchers and engineers in the energy storage field are actively working to address these challenges. The focus is on developing novel materials and battery designs that can achieve ideal lithium-ion diffusion while also accommodating the mechanical stresses associated with battery cycling. Improving the stability of interfaces within solid-state batteries remains a research area. Overcoming the existing limitations of solid-state battery systems promises significant advancements in energy storage capabilities for widespread applications.

[0008] Non-existent technology recognition

[0009] The discussion in this section is intended to provide background information related to the present invention and does not constitute an admission of prior art. Summary of the Invention

[0010] Additives for solid electrolytes

[0011] This invention relates to additive materials for use in solid electrolyte materials containing sulfides in solid-state batteries. The additive materials provided in this application allow solid-state batteries using these materials to operate at relatively lower pressures compared to solid-state batteries without them.

[0012] solid-state batteries

[0013] One aspect of the present invention provides a solid-state battery comprising: a positive electrode; a negative electrode; and a solid electrolyte layer disposed between the positive electrode and the negative electrode and configured to enable lithium ion transport between the positive electrode and the negative electrode, wherein the solid electrolyte layer comprises: particles containing a sulfide-containing material; and an additive material represented by A-B-C (Chemical Formula 1), wherein A is a mercapto (SH) or a leaving group, B is a C3-C20 perfluoroalkane group having or not having a substituent, and C is a sulfonate, a phosphate, or a salt thereof, wherein A is configured to interact with the sulfide-containing material in the particles, and at least a portion of the additive material is sandwiched between two directly adjacent particles in the particles.

[0014] Solid-state batteries – on the other hand

[0015] Another aspect of the present invention provides a solid-state battery comprising: a positive electrode; a negative electrode; and a solid electrolyte layer disposed between the positive electrode and the negative electrode and configured to enable lithium ion transport between the positive electrode and the negative electrode, wherein the solid electrolyte layer comprises: particles containing a sulfide-containing material; and an additive material represented by A-B-C (Chemical Formula 1), wherein A is a thiol (SH) or a leaving group, wherein A is configured to interact with sulfur in the sulfide-containing material of the particles, at least a portion of the additive material being sandwiched between two directly adjacent particles in the particles, wherein... In the given form, when A is a leaving group, A is selected from the group consisting of chlorine, bromine, iodine, toluenesulfonate (p-toluenesulfonate) or methanesulfonate (methanesulfonate), acetate or trifluoroacetate, phosphate or phosphonate, carboxylic acid, alkoxide, amino, cyano(CN) group, azide (N3) group, sulfonate, triethoxysilyl, trimethoxysilyl, and combinations thereof. B is a C3-C20 perfluoroalkane group with or without substituents, including those selected from propane, n-butane (CH3CH2CH2CH3), isobutane (CH3CH(CH3)2), and n-pentane (CH3(CH2)3CH2CH2CH3). 3) 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 (CH3CH2C) H2CH2CH(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)CH2CH2CH 2CH(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)2CH2CH3), 3,3-Dimethylheptane (CH3CH2CH(CH3)2CH2CH2CH2CH3), 3-Ethylheptane (CH3CH2CH2CH(CH2CH3)CH2CH3), n-Decane (CH3(CH2)8CH 3), 2-Methylnonane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-Methylnonane (CH3CH2CH2CH2CH2CH2CH(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)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 isomers, n-tetane (C 13 H 28 ) and its branched isomers, n-tetradecane (C 14 H 30 ) and its branched isomers, n-pentadecane (C 15 H 32 ) and its branched isomers, n-hexadecane (C 16 H 34 ) and its branched isomers, n-heptadecane (C 17 H 36 ) and its branched isomers, n-octadecane (C 18 H 38 ) and its branched isomers, n-nonadecane (C 19 H 40 ) and its branched isomers, n-eicosane (C 20 H 42) and its branched isomers and combinations thereof, wherein when B is a C3-C20 perfluoroalkane group with substituents, B comprises alkyl groups selected from fluorine (-F), chlorine (-Cl), bromine (-Br), iodine (-I), hydroxyl (-OH), ether (-OR), aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxy (-OO-), amino (-NH2), secondary amino (-NHR), tertiary amino (-NR2), nitro (-NO2), cyano (-CN), amide (-CONH2), substituted amide (-CONHR, -CONR2), mercapto (-SH), thioether (-SR), sulfonyl (-SO2R), sulfate ester (-SO4R), phosphate ester (-PO4R2), phosphin (-PR) 2) Substituents in the group consisting of alkyl (-R), alkenyl (-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 a sulfonate, phosphate ester or selected from sodium (Na), potassium (K), lithium (Li), rubidium (Rb), cesium (Cs), calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba), iron(II) (FeII), 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) + ), imidazolyl (C3H4NH2) + ), Phosphorus (P) + (CH3)4), guanidine (C(NH2)3) + Sulfonates or phosphates and combinations thereof are sulfonates or phosphates in the group consisting of sulfonates or phosphates and combinations thereof.

[0016] Surface adhesion

[0017] In some embodiments, at least a portion of the additive material is in contact with the surface of either of two adjacent particles. In some embodiments, at least a portion of the additive material is in contact with the surface of either of two adjacent particles through at least one of covalent bonding or non-covalent adhesion.

[0018] In some embodiments, the contact between at least a portion of the additive material and adjacent particles provides a pathway for the diffusion of lithium ions within the solid electrolyte layer. In some embodiments, the solid-state battery is configured to operate at a pressure of less than 10 MPa, substantially lower than the pressure required in the solid electrolyte layer without the additive material. In some embodiments, the solid-state battery is configured to operate at a pressure of less than 5 MPa. In some embodiments, the specific capacity of the solid-state battery is greater than 100 mAh / g.

[0019] Materials containing sulfides

[0020] In some embodiments, the sulfide-containing material comprises lithium phosphorus sulfide chloride (LPSCl). In some embodiments, the volume-based average particle size of the sulfide-containing material, as measured by laser diffraction particle size distribution measurement, is 0.1 μm to 50 μm. In some embodiments, the first hardness of the sulfide-containing material, as determined by nanoindentation testing, is 0.1 to 1 GPa, and the second hardness of the additive material, as determined by nanoindentation testing, is 0.001 to 0.01 GPa. In some embodiments, the sulfide-containing material has a first hardness, and the additive material has a second hardness, the second hardness being 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 particulate form. In some embodiments, the leaving group is triethoxysilyl or trimethoxysilyl. In some embodiments, the additive material is selected from the group consisting of: (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); (Chemical Formula 26); (Chemical Formula 27); (Chemical Formula 28); (Chemical Formula 29); (Chemical Formula 30); (Chemical Formula 31); (Chemical Formula 32); (Chemical Formula 33); (Chemical Formula 34); (Chemical Formula 35); (Chemical Formula 36); (Chemical Formula 37); and Their combination.

[0023] solid electrolyte

[0024] In some embodiments, the solid electrolyte comprises the sulfide-containing material and the additive material in a weight ratio of 1:1 to 25:1. In some embodiments, the porosity of the solid electrolyte is 5% to 15%. In some embodiments, the density of the solid electrolyte is increased by more than 10% compared to the density without the additive material.

[0025] Solid-state battery manufacturing method

[0026] Another aspect of the present invention provides a method for manufacturing a solid-state battery. The method includes providing the solid electrolyte layer, comprising ball milling the particles together with an additive material provided in this application. In some embodiments, the ball milling causes A to interact with a sulfide-containing material in the particles, such that at least a portion of the additive material adheres to the surface of the particles.

[0027] Attachment

[0028] In some embodiments, at least a portion of the additive material is attached to the surface of the particles via non-covalent adhesion. In some embodiments, the non-covalent adhesion is chemisorption, 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 particles via covalent bonds. In some embodiments, the covalent bonds are sulfur bonds or disulfide bonds.

[0029] Solid-state batteries – additional aspects

[0030] Another aspect of the present invention provides a solid-state battery comprising: a positive electrode; a negative electrode; and a solid electrolyte layer disposed between the positive electrode and the negative electrode and configured to enable lithium ion transport between the positive electrode and the negative electrode, wherein the solid electrolyte layer comprises: particles comprising a material containing a sulfide; and an additive material selected from the group consisting of: (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); (Chemical Formula 26); (Chemical Formula 27); (Chemical Formula 28); (Chemical Formula 29); (Chemical Formula 30); (Chemical Formula 31); (Chemical Formula 32); (Chemical Formula 33); (Chemical Formula 34); (Chemical Formula 35); (Chemical Formula 36); (Chemical formula 37); and its combinations.

[0031] interaction

[0032] In some embodiments, the additive material is configured to interact with sulfur in the sulfide-containing material of the particles, and at least a portion of the additive material is sandwiched between two directly adjacent particles in the particles and contacts the surface of either of the two adjacent particles by covalent bonding and / or non-covalent attachment.

[0033] Solid-state batteries – different aspects

[0034] Another aspect of the present invention provides a solid-state battery comprising: a positive electrode; a negative electrode; and a solid electrolyte layer disposed between the positive electrode and the negative electrode and configured to enable the transport of lithium ions between the positive electrode and the negative electrode, wherein the solid electrolyte layer comprises: particles containing a sulfide-containing material; and an additive material represented by A-B-C (Chemical Formula 1), wherein A is a mercapto (SH), B is a C3-C10 perfluoroalkane group having or not having a substituent, and C is a sulfonate, a phosphate, or a salt thereof, wherein A is configured to interact with sulfur in the sulfide-containing material in the particles, and at least a portion of the additive material is sandwiched between two directly adjacent particles in the particles.

[0035] Substituents

[0036] In some embodiments, B is a C3-C10 perfluoroalkane group comprising a substituent selected from the group consisting of: fluorine (-F), chlorine (-Cl), bromine (-Br), iodine (-I), hydroxyl (-OH), ether (-OR), aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxy (-OO-), amino (-NH2), secondary amine (-NHR), tertiary amine (-NR2), nitro (-NO2), cyano (-CN), amide (-CONH2), substituted amide (-CONHR, -CONR2), mercapto (-SH), and thioether (-SR). , sulfonyl (-SO2R), sulfate ester (-SO4R), phosphate ester (-PO4R2), phosphin (-PR2), alkyl (-R), alkenyl (-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.

[0037] Salt

[0038] In some embodiments, C is selected from 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) + ), imidazolyl (C3H4NH2) + ), Phosphorus (P) + (CH3)4), guanidine (C(NH2)3) + Sulfonates or phosphates and combinations thereof are sulfonates or phosphates in the group consisting of sulfonates or phosphates and combinations thereof.

[0039] Example Implementation

[0040] These and other features of the invention will become clear from the following detailed description and will be further understood by exemplary embodiments of the invention. Furthermore, it will be readily understood that the objects and advantages of the invention can be achieved by the means shown in the appended claims and combinations thereof.

[0041] Summary rather than limitation

[0042] It should be understood that the invention is not limited to the examples summarized in this summary description. Various other aspects are also described and illustrated in this application. Attached Figure Description

[0043] Figure 1 This is an example of a solid-state battery according to one implementation method.

[0044] Examples, not limitations

[0045] The examples set forth in this application illustrate specific non-limiting implementations in one form, and such examples should not be construed as limiting the scope of the appended claims in any way. Detailed Implementation

[0046] Examples and Implementation

[0047] The subject matter of this disclosure will now be described and discussed in more detail with reference to the accompanying drawings, which illustrate some, but not all, of the embodiments of the invention, as well as some specific embodiments and examples. Unless otherwise stated, the same reference numerals always refer to the same elements or parts. The subject matter of this disclosure can be embodied in many different forms and should not be construed as being limited to the specific embodiments set forth in this application. Rather, these embodiments are provided to enable this disclosure to meet the requirements of applicable law. In fact, many modifications and other embodiments of the subject matter of this disclosure will arise in the mind of one skilled in the art to which the subject matter of this disclosure pertains. Therefore, it should be understood that the subject matter of this 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.

[0048] definition

[0049] singular form

[0050] Unless the context clearly indicates otherwise, the singular form of words used in this application also includes the plural form. The plural encompasses the singular, and vice versa. Therefore, references in the singular form generally include the plural form of the corresponding term. For example, although this disclosure describes layers, substrates, and cells, etc., in the singular form, more than one of these and other components, including combinations, may also be used.

[0051] "about"

[0052] The term “about” indicates and covers a specified numerical value and the range above and below that value.

[0053] "Contains", "Basically consists of", and "Composed of"

[0054] The terms “comprising” and “containing” should be interpreted inclusively rather than exclusively. Similarly, the terms “including” and “or” should be interpreted inclusively unless the context explicitly prohibits such an interpretation. Disclosure of embodiments using the term “comprising” as defined is also disclosure of embodiments “substantially constitute” and “compose” of the disclosed ingredients. The phrase “composed of” …… The term "composition" excludes any elements, steps, or components that are not explicitly specified.

[0055] "and / or"

[0056] The term “and / or” used in the context of “X and / or Y” should be interpreted as “X”, “Y”, or “X and Y”.

[0057] "Up" and "above"

[0058] As used in this application, the terms “on,” “applied to,” “formed on,” “deposited on,” “set on,” etc., mean to apply, form, cover, deposit, or set on a surface that is below or above it. Conversely, the terms “above,” “applied above,” “formed above,” “deposited above,” “covered above,” “set above,” etc., mean to apply, form, cover, deposit, or set on or above it, but not necessarily in contact with a surface. For example, a forming layer “applied above” a substrate layer may contact the substrate without intermediate material; however, this expression does not preclude the presence of one or more other layers of the same or different composition located between the forming layer and the substrate layer.

[0059] Markush Group

[0060] As used in any Markush-type representation, the term "combination thereof" means a combination of one or more elements selected from a group of elements disclosed in the Markush-type representation, and refers to the presence of one or more elements selected from that group. The term "combination thereof" includes every possible combination of the elements referred to by the term.

[0061] "between"

[0062] The term "between" as used in this application includes endpoints.

[0063] Numerical range

[0064] Furthermore, all numerical ranges in this application should be understood to include all integers, natural numbers, or fractions within that range. Moreover, any numerical range referred to in this application is intended to include all subranges it covers, and these numerical ranges should be interpreted as supporting claims relating to any numerical value or subset of numerical values ​​within that range. For example, the disclosure of 1 to 10 should be interpreted as supporting ranges such as 1 to 8, 3 to 7, 1 to 9, 3.6 to 4.6, 3.5 to 9.9, etc. When ranges are given, any endpoints of these ranges and / or numbers within these ranges may be combined with the ranges of this disclosure.

[0065] "Including", "such as", and "for example"

[0066] The terms “including,” “such as,” “for example,” etc., as used in this application, mean “including / such as / for example but not limited to.”

[0067] Combination of implementation methods

[0068] The term "example" as used in this application, especially when followed by a series of terms, is illustrative only and should not be considered exclusive or exhaustive. Unless otherwise expressly stated, any embodiment disclosed in this application may be combined with any other embodiment disclosed in this application.

[0069] Particle size

[0070] The particle size used in this application refers to the average particle size (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 The particle size can be the diameter of a spherical particle, or the length along the direction of its maximum size for an ellipsoidal or other irregularly shaped particle. The particle size used in this application has a "D" value. 50 This refers to the diameter of 50% of the particles being smaller than this value.

[0071] Operating pressure

[0072] Operating pressure

[0073] 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 a solid electrolyte instead of the liquid electrolyte found in traditional lithium-ion batteries. As a result, they can potentially operate at different pressures compared to liquid electrolyte batteries.

[0074] Factors determining operating pressure

[0075] Solid-state batteries are typically designed to operate at atmospheric pressure or slightly above that. The exact operating pressure can depend on factors such as the specific materials used in 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 battery's operating pressure. For instance, some ceramic electrolytes may require higher pressures to maintain good contact between components and ensure efficient ion transport. In contrast, some polymer electrolytes may allow operation at lower pressures due to their flexibility.

[0076] Higher operating pressure

[0077] Some solid-state battery designs aim to operate under environmental pressures similar to those of conventional lithium-ion batteries. However, there are also solid-state battery concepts that could benefit from operating at higher pressures. Compared to liquid electrolytes, solid electrolytes often have spaces within the material, leading to poor contact between solid electrolyte materials, such as particles, and between lithium ions and the solid electrolyte materials. This results in poor ionic conductivity and lithium-ion diffusion in the solid electrolyte layer. Increased pressure could potentially enhance the contact between the solid electrolyte and electrode materials, thereby improving overall battery performance.

[0078] Challenges of high operating pressure

[0079] Despite the numerous advantages of solid-state batteries, including potentially improved safety and energy density, high operating stress can present challenges.

[0080] Mechanical stress

[0081] High voltage within a battery cell can cause mechanical stress on materials including the solid electrolyte and electrodes. This stress can cause components to deform, crack, or fail over time, thereby compromising the battery's structural integrity.

[0082] Sealing Challenge

[0083] Maintaining a high-voltage environment may require effective sealing of the battery cells. Achieving and maintaining a reliable seal under high voltage can be challenging, as any leakage can allow contaminants or air to enter, impairing battery performance and safety.

[0084] Manufacturing complexity

[0085] Designing and manufacturing batteries that can operate under high voltage can be more complex and expensive. Ensuring reliable sealing, preventing leaks, and preventing mechanical failures require meticulous engineering and manufacturing processes.

[0086] Material compatibility

[0087] The materials used in solid-state batteries (including solid electrolytes and electrodes) may be compatible with high-voltage conditions. Some materials may degrade or undergo undesirable chemical reactions under high voltage, affecting the overall performance and cycle life of the battery.

[0088] Energy density trade-off

[0089] While high voltage can enhance certain aspects of battery performance, it may also lead to a trade-off in energy density.

[0090] Temperature effect

[0091] High pressure can affect the thermal behavior of the battery. Thermal management becomes preferred to prevent overheating and ensure the safe operation of solid-state batteries under elevated pressure.

[0092] New additive materials

[0093] Additives attached to solid electrolytes

[0094] This invention addresses key challenges in solid-state battery technology by introducing novel additive materials designed to enhance the performance of sulfide-containing solid electrolytes. Aspects of this disclosure relate to additives for addition to sulfide-containing solid electrolyte materials for solid-state batteries, solid-state batteries using these additive materials in their solid electrolyte materials, 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, forming a unique adhesion mechanism in which at least a portion of the additive material bonds to or adheres to the surface of the sulfide-containing solid electrolyte material.

[0095] Lithium-ion diffusion

[0096] This surface adhesion plays several key functions. It improves the overall conductivity or diffusion of lithium ions within the solid electrolyte layer. By establishing a network of conductive paths between adjacent electrolyte particles through contact between at least a portion of the additive material and adjacent solid electrolyte material, the additive facilitates more efficient transport of lithium ions through the battery structure.

[0097] Contact between components

[0098] Furthermore, the attached additive material acts as a flexible or formable interface between rigid electrolyte particles. This additive material may not be in particulate form, but rather in the form of individual molecules. These additive material molecules can each be flexible, capable of bending or moving without breaking, and retaining their original shape after deformation. Alternatively, these additive material molecules can each be formable, capable of being shaped, molded, or deformed without breaking or losing their integrity. This flexibility or formability helps accommodate volume changes that may occur during battery cycling, maintaining critical contacts between components.

[0099] stability

[0100] Furthermore, by enhancing interparticle contact and overall electrolyte cohesion, the additive material provided in this application achieves improved performance at relatively lower pressures compared to solid-state batteries without this additive material. Utilizing the enhanced interparticle contact, the solid electrolyte material remains together, ensuring a continuous path for the effective movement of lithium ions between electrodes, improving the stability of the solid electrolyte, and preventing degradation over time or cracking under stress.

[0101] Advantages of reduced operating pressure

[0102] The ability to operate solid-state batteries at reduced pressure represents a significant advancement in the field. Traditional solid-state batteries typically require high pressure to maintain adequate contact between components, which can lead to mechanical stress, potential safety issues, and manufacturing complexity. By enabling low-pressure operation, the additive materials disclosed herein offer a range of advantages, 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 expanded range of possible applications for solid-state battery technology.

[0103] Manufacturing process

[0104] Furthermore, the method for introducing additive materials into solid-state batteries is designed to be compatible with existing manufacturing processes, which is beneficial for manufacturers to use in mass production.

[0105] Additive materials

[0106] The additive material provided in this application can be represented by the following chemical formula 1: A—B—C (Chemical Formula 1) Where A is a mercapto (SH) group or a leaving group; B is a C3-C20 perfluoroalkane group with or without substituents; and C is a sulfonate, phosphate, or its salt. The alkane group consists entirely of single-bonded carbon and hydrogen atoms, and has the general formula C1. n H2n+2 .

[0107] covalent bond

[0108] In some embodiments, A in the additive material A-B-C (Chemical Formula 1) provided in this application 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 sulfur bond or a disulfide bond. This covalent bond causes at least a portion of the additive material to adhere to the surface of the solid electrolyte material particles. In some embodiments, if the sulfide-containing material contains metal ions, a metal-sulfur covalent bond may be formed, establishing a strong anchoring point for the additive material.

[0109] Multiple covalent bonds

[0110] Furthermore, the formation of multiple covalent bonds between individual additive molecules 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 connected through cross-linking between additive molecules and multiple sulfur atoms to form a three-dimensional network, improving the strength, toughness, and / or elasticity of the electrolyte material. This results in a more stable electrolyte material with enhanced durability and mechanical strength, making it more resistant to deformation or volume changes.

[0111] Redox reaction

[0112] In some cases, covalent attachment may also be accompanied by redox reactions, in which thiol groups undergo oxidation to form disulfide bonds, potentially contributing to the electrochemical properties of solid-state batteries.

[0113] Strength and properties of covalent bonds

[0114] The strength and properties of these covalent bonds can be influenced by factors such as local pH, applied voltage, and the presence of other ions in the solid electrolyte system, thus allowing for potential tuning of interfacial properties to optimize battery performance.

[0115] Non-covalent attachment

[0116] In some embodiments, the additive material having thiol groups can be adsorbed onto the surface of sulfide-containing material particles in the solid electrolyte layer, such that at least a portion of the additive material is attached to the surface of the sulfide-containing material particles via non-covalent adhesion. Non-covalent adhesion can be chemisorption, van der Waals interactions, ionic interactions, hydrogen bonding, π-π stacking, dipole-dipole interactions, and electrostatic interactions.

[0117] Chemisorption

[0118] Chemisorption refers to the formation of chemical bonds between the adsorbate and the surface. It may be higher than that of typical physisorption, but weaker than that of covalent bonds.

[0119] van der Waals

[0120] Van der Waals forces are weak attractive forces between molecules or atoms that arise from temporary fluctuations in electron distribution.

[0121] Adjusting non-covalent adhesion

[0122] The strength and properties of these adhesions can be controlled by modifying the chemical structure of the additive material. For example, changing the number and position of hydrogen bond donors / acceptors can alter hydrogen bond interactions. Introducing different aromatic ring systems or heteroatoms can affect 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 groups can enhance electrostatic interactions and potentially improve the ionic conductivity of the particle-additive interface.

[0123] Leaving group

[0124] In some embodiments, A in the additive material A-B-C (Chemical Formula 1) provided in this application may be a leaving group. The term "leaving group" can be understood as defined by IUPAC, for example, it may be an atom or group of atoms that detaches from the major or residual portion of the substrate during a reaction or in a fundamental step of the reaction. For example, a leaving group may be a fragment that detaches along with an electron pair during heterolytic bond breaking.

[0125] Examples of leaving groups

[0126] Other examples of leaving groups include: halogen (such as chlorine, bromine, or iodine); toluenesulfonate (p-toluenesulfonate) or methanesulfonate (methanesulfonate) group; acetate or trifluoroacetate group; phosphate or phosphonate group; carboxylic acid ester group (such as formate or benzoate); alkoxide group (such as methoxy or ethoxy); amino group (such as dimethylamino or diethylamino); cyano (CN); azide (N3) group; and sulfonate group (such as trifluoromethanesulfonate (trifluoromethanesulfonate)).

[0127] Other examples of leaving groups

[0128] In some respects, the leaving group can be an anionic or neutral species that detaches from a neutral or cationic substrate. Suitable leaving groups compatible with solid electrolyte materials can be used. In some embodiments, the leaving group may include a "triethoxysilyl" group (…). For example, Origin HSi(OC2H5)3) or "trimethoxysilyl" group ( For example Origin HSi(OCH3)3).

[0129] Choice of leaving group

[0130] According to various aspects of the invention, the selection of the leaving group can be customized to optimize reactivity with sulfide-containing solid electrolyte materials or to enhance specific properties of the resulting solid-state battery. The leaving group can also be selected based on factors such as stability, ease of synthesis, or compatibility with battery manufacturing processes.

[0131] covalent bond

[0132] 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 sulfur bond or a disulfide bond. This covalent bond causes at least a portion of the additive material to adhere to the surface of the solid electrolyte material particles. The covalent bond formed between the leaving group and the sulfur in the sulfide-containing solid electrolyte material may involve a variety of chemical interactions, including sulfur bonds, disulfide bonds, metal-sulfide bonds, or multiple covalent bonds forming a cross-linked network.

[0133] Adjusting covalent adhesion

[0134] The strength and properties of covalent adhesion can be tuned by modifying the chemical structure of the leaving group, for example by using different electron-withdrawing or electron-donating substituents, sterically hindered groups, or multifunctional leaving groups.

[0135] Covalent attachment process

[0136] This covalent attachment process can be initiated or enhanced by thermal activation, photochemical activation, mechanical force or chemical catalysts during ball milling or pressing.

[0137] The degree and distribution of covalent adhesion

[0138] The degree and distribution of covalent adhesion on solid electrolyte particles can be controlled by adjusting the ratio of additives to solid electrolyte materials, utilizing preferential adhesion to specific crystal planes or surface features, or utilizing reversible adhesion under certain conditions for dynamic reorganization of the additive layer.

[0139] Non-covalent attachment

[0140] In some embodiments, the additive material having leaving groups can interact with sulfide-containing particles in the solid electrolyte layer. In some embodiments, the additive material is adsorbed onto the particle surface such that at least a portion of the additive material is attached to the particle surface of the sulfide-containing solid electrolyte material via non-covalent adhesion. Non-covalent adhesion can be chemisorption, van der Waals interactions, ionic interactions, hydrogen bonding, π-π stacking, dipole-dipole interactions, and electrostatic interactions.

[0141] Perfluoroalkane group without substituents

[0142] In some embodiments, the B in the additive material ABC (Chemical Formula 1) provided in this application may be a C3-C20 perfluoroalkane group without substituents. For example, B may be a C3-C5 perfluoroalkane group without substituents, a C6-C16 perfluoroalkane group without substituents, a C16-C20 perfluoroalkane group without substituents, or a perfluoroalkane group without substituents having any other number of carbons from 3 to 20.

[0143] Perfluoroalkane group with substituents

[0144] In some embodiments, the B in the additive material ABC (Chemical Formula 1) provided in this application can be a C3-C20 perfluoroalkane group containing substituents selected from the group consisting of: halogens [fluorine (-F), chlorine (-Cl), bromine (-Br), iodine (-I)]; oxygen-containing substituents [hydroxyl (-OH), ether (-OR), carbonyl [aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR)], peroxy (-OO-)]; nitrogen-containing substituents [amino (-NH2), N-substituted amines [secondary amine (-NHR), tertiary amine (-NR2)], nitro (-NO2), cyano (-CN), amide (-CONH2) or substituted amides (-CONHR, -CONR2)]; sulfur-containing substituents [thiol (-SH), thioether (-SR), sulfonyl (-SO2R)] Sulfate ester group (-SO4R)]; phosphorus-containing substituents [phosphate ester group (-PO4R2), phosphine group (-PR2)]; hydrocarbon substituents [alkyl (-R), alkenyl (-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 substituents [organometallic groups (e.g., methyllithium (-CH3Li), Grignard reagent (-RMgX))]; and combinations thereof. For example, B may be a substituent C3-C5 perfluoroalkane group, a substituent C6-C16 perfluoroalkane group, a substituent C16-C20 perfluoroalkane group, or a substituent perfluoroalkane group having any other number of carbons from 3 to 20, including substituents that can be chlorine, bromine, ester, ketone, or any combination thereof.

[0145] Perfluoroalkane group

[0146] In some embodiments, B in the additive material ABC (Chemical Formula 1) provided in this application may be a C3-C20 perfluoroalkane group with or without substituents. For example, B may be a perfluoroC3 alkane group, C4 alkane group, C5 alkane group, C6 alkane group, C7 alkane group, C8 alkane group, C9 alkyl group, C10 alkane group, C3-C4 alkane group, C3-C5 alkane group, C3-C6 alkane group, C3-C7 alkane group, C3-C8 alkane group, C3-C9 alkane group, C3-C10 alkane group, C4-C5 alkane group, C4-C6 alkane group, C4-C7 alkane group, C4-C20 ... C8 alkane group, C4-C9 alkane group, C4-C10 alkane group, C5-C6 alkane group, C5-C7 alkane group, C5-C8 alkane group, C5-C9 alkane group, C5-C10 alkane group, C6-C7 alkane group, C6-C8 alkane group, C6-C9 alkane group, C6-C10 alkane group, C7-C8 alkane group, C7-C9 alkane group, C7-10 alkane group, C8-C9 alkane group, C8-10 alkane group, C9-C10 alkane group, etc.

[0147] Examples of perfluoroalkane groups

[0148] Non-limiting examples of B in the additive materials ABC (Chemical Formula 1) provided in this application include, but are not limited to: perfluoropropane with or without substituents, 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)CH3), etc. 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)2CH2CH3), 3,3-dimethylheptane (CH3CH2CH(CH3)2CH2CH2CH2CH3), 3-ethylheptane (CH3CH2) CH2CH(CH2CH3)CH2CH3), n-decane (CH3(CH2)8CH3), 2-methylnonane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-methylnonane (CH3CH2CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-dimethyloctane (CH3C(CH3)2(CH2)6CH3), 2,3-dimethyloctane (CH3CH(CH3)CH2CH2CH2CH2C) H2CH(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 isomers, n-tetane (C 13 H 28 ) and its branched isomers, n-tetradecane (C 14 H 30 ) and its branched isomers, n-pentadecane (C 15 H 32 ) and its branched isomers, n-hexadecane (C 16 H 34 ) and its branched isomers, n-heptadecane (C 17 H36 ) and its branched isomers, n-octadecane (C 18 H 38 ) and its branched isomers, n-nonadecane (C 19 H 40 ) and its branched isomers, n-eicosane (C 20 H 42 ) and its branched isomers.

[0149] Salt

[0150] In some embodiments, C may be a sulfonate or a phosphate. For example, C may include alkali metal salts [sodium (Na), potassium (K), lithium (Li), rubidium (Rb) and / or cesium (Cs) sulfonates / phosphates], alkaline earth metal salts [calcium (Ca), magnesium (Mg), strontium (Sr) and / or barium (Ba) sulfonates / phosphates], transition metal salts [iron (II)(Fe II), iron (III)(Fe III), copper (I)(Cu I), copper (II)(Cu II), zinc (Zn) and / or manganese (Mn) sulfonates / phosphates], ammonium salts, and organic amine salts [ammonium (NH4), methylammonium (CH3NH3), dimethylammonium ((CH3)2NH2), trimethylammonium ((CH3)3N)], [ammonium salts ... + ) and / or pyridinium (C5H5NH + Sulfonates / phosphates, heavy metal salts [lead(II)(Pb), mercury(II)(Hg) and / or cadmium(Cd) sulfonates / phosphates], lanthanides and actinides [lanthanum(La), cerium(Ce) and / or uranium(U) sulfonates / phosphates], mixed cation salts [sodium-calcium (Na-Ca) and / or potassium-magnesium (K-Mg) sulfonates / phosphates], special and polyatomic cation salts [tetramethylammonium(N(CH3)4)4] + ), imidazolyl (C3H4NH2) + ), Phosphorus (P) + (CH3)4) and / or guanidine (C(NH2)3) + )sulfonates / phosphates.

[0151] Examples of additive materials

[0152] Non-limiting examples of additive materials provided in this application include, but are not limited to, chemical formulas 2 to 37: (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); (Chemical Formula 26); (Chemical Formula 27); (Chemical Formula 28); (Chemical Formula 29); (Chemical Formula 30); (Chemical Formula 31); (Chemical Formula 32); (Chemical Formula 33); (Chemical Formula 34); (Chemical Formula 35); (Chemical Formula 36); (Chemical formula 37).

[0153] Additive material form

[0154] Additive materials can be in any suitable form to be added to and / or mixed with sulfide-containing solid electrolyte materials for solid-state batteries. The physical form of the additive can significantly affect its interaction with the sulfide-containing solid electrolyte and its overall effectiveness in improving battery performance.

[0155] powder form

[0156] In some embodiments, the additive material may be in powder form. Powder form can provide advantages such as increased surface area for interaction and improved dispersibility in a solid electrolyte matrix.

[0157] Other forms

[0158] However, depending on the specific manufacturing process of the final solid-state battery and the desired characteristics, other forms of additive materials can also be suitable. For example, the additive material can be provided as a liquid, a gel, or even as a gas that can be deposited onto solid electrolyte particles. In some cases, the additive material can be introduced into the solid electrolyte through a solution-based process in which it is first dissolved in a suitable solvent and then mixed with a sulfide-containing material.

[0159] Choice of form

[0160] The choice of form can also 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.

[0161] solid electrolyte layer

[0162] Overview of solid electrolyte layers

[0163] The solid electrolyte layer provided in this application is suitable for and enables lithium-ion diffusion between the positive and negative electrodes. This solid electrolyte layer is electrically connected to both the positive and negative electrodes and provides a conductive path for the movement of charge carriers between them. In some embodiments, the solid electrolyte layer may be formed above and in direct contact with the positive or negative electrode. In other embodiments, other functional layers may be disposed between the solid electrolyte layer and the positive and / or negative electrode.

[0164] Overview of materials used in solid electrolyte layers

[0165] Generally, there are no particular restrictions on the material of the solid electrolyte layer, as long as it can adhere to adjacent layers, has suitable conductivity, and does not cause significant chemical changes in the solid-state battery within its voltage range. For example, the solid electrolyte layer can contain various inorganic solid electrolytes, polymer solid electrolytes, and / or polymer gel electrolytes, but is not limited to these.

[0166] Overview of solid electrolyte materials containing sulfides

[0167] In the solid-state battery provided in this application, the solid electrolyte is a sulfide-containing material, which can also be referred to as a "sulfide-based material." The term "sulfide-containing electrolyte" as used in this application refers to an electrolyte containing conductive ions (…). For example Li + This invention relates to electrolytes containing sulfur (S) that electrically insulate the positive and negative electrodes of an electrochemical cell. The sulfide-based / sulfide-containing solid electrolyte contains sulfur (S) and exhibits ionic conductivity characteristic of metals belonging to Group 1 or Group 2 of the periodic table. It may include Li-PS-type glasses or Li-PS-type glass ceramics. For example, the sulfide-based / sulfide-containing solid electrolyte materials used in this application may include lithium sulfide, silicon sulfide, germanium sulfide, and boron sulfide. Non-limiting examples of inorganic solid electrolytes include: x Li2S.yP2S5 (x+y=1), 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, 3+y PO 4-x N x ), thio-LISICON (Li 3.25 Ge 0.25 P 0.75S4), Li2O-Al2O3-TiO2-P2O5 (LATP), Li2S-P2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5, L i2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2, Li2S-GeS2-ZnS, etc. or their combinations.

[0168] Specific solid electrolyte materials containing sulfides

[0169] In some embodiments of the solid-state battery provided in this application, the sulfide-containing solid electrolyte material may include inorganic solid electrolyte materials. In some embodiments, the sulfide-containing solid electrolyte material may include inorganic solid electrolyte materials. In some embodiments, the sulfide-containing solid electrolyte material may include Li3P7S. 11 Li 10 GeP2S 12 Na3PS4, Li 6-y PS 5-y Cl 1+y (y < 1) and / or at least one of Li6PS5X (X is Cl, Br or I).

[0170] lithium, phosphorus, sulfur, and chlorine

[0171] In some embodiments, sulfide-containing solid electrolyte materials include Li6PS5Cl (lithium phosphorus sulfide chloride, "LPSCl"). LPSCl is known for its high ionic conductivity, a key characteristic of solid electrolyte materials. High ionic conductivity allows lithium ions to move efficiently within the material, thereby facilitating the charge-discharge process in solid-state batteries. LPSCl also exhibits good chemical and thermal stability, which is important for the long-term performance and safety of solid-state batteries. Stability is particularly critical in high-temperature and high-voltage applications. Furthermore, LPSCl has a wide electrochemical stability window, capable of withstanding a wide voltage range without undergoing undesirable reactions. This is essential for supporting a variety of positive and negative electrode materials.

[0172] Particle size of solid electrolyte materials

[0173] In the solid-state battery provided in this application, the solid electrolyte material is provided in particulate form. In some embodiments, the volume-based average particle size of the sulfide-containing material, as measured by laser diffraction-based particle size distribution measurement, is, 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 50μm, 5μm to 40μm, 5μm to 30μm, 5μm to 20μm, 5μm to 10μm, 10μm to 50μm, 10μm to 40μm, 10μm to 30μm, 10μm to 20μm, 20μm to 50μm, 20μm to 40μm, 20μm to 30μm, 20μm to 50μm, 20μm to 40μm, 20μm to 30μm, 30μm to 50μm, 30μm to 40μm, 40μm to 50μm, etc. In embodiments, the average particle size of the sulfide-containing solid electrolyte material can be from 0.1 μm to 50 μm, for example, any value 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 embodiments, the particle size of the positive electrode active material can be within a range formed by selecting any two values ​​listed above or any two values ​​within the range of 0.1 μm to 50 μm.

[0174] Lithium, phosphorus, sulfur, and chlorine particles that form covalent bonds

[0175] In some embodiments using LPSCl as a solid electrolyte material, LPSCl is provided in particulate form. In some of these embodiments where the additive material provided in this application comprises thiol groups, the thiol groups can interact with the sulfur in the LPSCl particles to form sulfur bonds or disulfide bonds, causing at least a portion of the additive material to adhere to the surface of the LPSCl particles.

[0176] Interaction between additive materials and solid electrolyte particles

[0177] The interaction between the thiol or leaving groups of the additive material provided in this application and the solid electrolyte particles causes at least a portion of the thiol or leaving group ends of the additive material to adhere to the surface of the solid electrolyte particles. Due to this adhesion, at least a portion of the additive material adhered to the surface of the solid electrolyte particles can remain in and fill the space formed between directly adjacent solid electrolyte particles. The hydrophobic tail of the other end of the additive material adhered to the surface of the solid electrolyte particles also contacts the adjacent solid electrolyte particles. Using the additive material provided in this application, the materials in the solid electrolyte layer generally have better mutual contact, and the solid electrolyte layer has a higher density.

[0178] Benefits of the interaction between additive materials and solid electrolyte particles

[0179] Furthermore, additive materials can be softer and have better flowability than solid electrolyte particles, making them easier to expand and contract. During the charge and discharge process of a solid-state battery, as the solid electrolyte particles expand or contract in size, the additive materials attached to the surface of the solid electrolyte particles correspondingly change their own size (e.g., the length of the additive material molecules or the particle size in granular form), while still remaining in the spaces between the solid electrolyte material particles and keeping these spaces filled. This helps prevent contact failure between solid electrolyte particles, which is the case without additives, thus maintaining the contact between the solid electrolyte particles themselves and their contact with the additive materials. This better contact thus improves the conductivity of lithium ions in the solid electrolyte layer and maintains the conductivity of lithium ions in the solid electrolyte layer during the charge and discharge process of the solid-state battery.

[0180] hardness

[0181] The additive material provided in this application can be softer than solid electrolyte particles. In some embodiments, the hardness of the sulfide-containing solid electrolyte material, as determined by nanoindentation testing, can be 0.1 to 1 GPa, while the hardness of the additive material, as determined by nanoindentation testing, can be 0.001 to 0.01 GPa. In some embodiments, the hardness of the additive material can be up to 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%, which can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 0.01% to 10%.

[0182] weight ratio

[0183] In some embodiments, the solid electrolyte comprises a sulfide-containing material in a weight 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 within the range of 1:1 to 25:1 or 1:1 to 25:1. In this embodiment, the weight ratio of the sulfide-containing material to the additive material can be in the range of 1:1 to 25:1, for example, 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 this embodiment, the weight ratio of the sulfide-containing material to the additive material can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 1:1 to 25:1.

[0184] Porosity

[0185] Although the additive material fills the spaces between the solid electrolyte material particles, the solid electrolyte layer still maintains a suitable porosity for lithium ions to move through it. In some embodiments, the porosity of the solid electrolyte layer provided in this application is greater than 5%, for example, 5% to 15%, 5% to 14%, 5% to 13%, 5% to 12%, 5% to 11%, 5% to 10%, 5% to 9%, 5% to 8%, 5% to 7%, 5% to 6%, or any other percentage in the range greater than 5%, such as any other percentage in the range of 5% to 15% or 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%.

[0186] density

[0187] Additive materials, added to solid electrolyte materials and filling the spaces between solid electrolyte material particles, increase the density of the solid electrolyte layer. In some embodiments, the density of the solid electrolyte layer increases by more than 10% compared to the density without the additive material. For example, the density of the solid electrolyte layer can increase by 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any other percentage exceeding 10%. In embodiments, the density of the solid electrolyte layer can increase by any value within a range formed by selecting any two values ​​listed above or by selecting any two values ​​exceeding 10%.

[0188] Lower operating pressure

[0189] As provided in this application, by utilizing additive materials in the solid electrolyte layer, the interaction between the additive materials and the solid electrolyte material particles causes at least a portion of the additive materials to adhere to the surface of the solid electrolyte material particles, thereby creating better and / or tighter contact between materials in the solid electrolyte layer (such as between at least a portion of the additive materials and adjacent solid electrolyte material particles, and between solid electrolyte material particles). This interaction and adhesion also maintain this improved contact during the charge and discharge of the solid-state battery. This improved contact facilitates the conductivity of lithium ions in the solid electrolyte layer, enabling the solid-state battery provided in this application to operate at pressures substantially lower than 10 MPa than would be required without additive materials in the solid electrolyte layer. In some embodiments, the solid-state battery can operate at pressures such as 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 at pressures within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within a range less than 10 MPa.

[0190] Specific capacity

[0191] Lower operating pressure can prevent, reduce, and / or eliminate the problems described herein associated with higher operating pressures typically applied to solid-state batteries. For example, it can improve the stability and specific capacity of the solid-state battery. In some embodiments, the specific capacity of the solid-state battery is 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, etc. In implementation, 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 ​​within a range greater than 100 mAh / g.

[0192] Solid-state battery manufacturing

[0193] Solid-state battery manufacturing method

[0194] Another aspect of this disclosure provides a method for manufacturing a solid-state battery according to this application. The method for preparing a solid-state battery according to this application includes providing a solid electrolyte, including ball milling a mixture of particles of a sulfide-containing solid electrolyte material and an additive material provided in this application. Although ball milling is used as an example in this application, other known methods for mixing or combining solid electrolyte materials and additive materials can also be implemented. Examples of such known methods include planetary mixing, high-shear mixing, ultrasonic mixing, mechanical alloying, or solution-based techniques such as co-precipitation, sol-gel treatment, or spray drying utilizing heat treatment.

[0195] weight ratio

[0196] In some embodiments, the mixture comprises a sulfide-containing solid electrolyte material to an additive material in a weight ratio of, for example, 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, etc. 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 within the range of 1:1 to 25:1 or 1:1 to 25:1. In this embodiment, the weight ratio of the sulfide-containing material to the additive material can be in the range of 1:1 to 25:1, for example, 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 this embodiment, the weight ratio of the sulfide-containing material to the additive material can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 1:1 to 25:1.

[0197] Ball Mill Overview

[0198] Ball milling is an important technique for mixing and preparing materials for solid-state batteries. It is a widely used mechanical technique for grinding powders into fine particles and mixing materials in various applications, including the fabrication of solid-state battery components. In the case of solid-state batteries, ball milling is commonly used to mix and blend electrode materials, solid electrolytes, and other components. Example ball milling apparatuses can include planetary ball mills, stirred ball mills, and vibratory ball mills. These apparatuses typically consist of a rotating or vibrating chamber containing grinding balls made of materials such as steel, ceramic, or zirconium oxide.

[0199] homogeneous mixing

[0200] Ball milling can effectively achieve homogeneous mixtures of different powders. This is crucial for ensuring the uniform distribution of components in electrode materials and solid electrolytes, which in turn affects the overall performance of the battery.

[0201] Reduce particle size

[0202] Ball milling can reduce the particle size of related materials, leading to increased surface area and improved reactivity. Smaller particle sizes can enhance the kinetics of electrochemical reactions, contributing to better battery performance.

[0203] Enhanced electrode-electrolyte interface

[0204] Ball milling can help form a well-defined interface between the electrode and the solid electrolyte. This is important for promoting efficient ion transport and minimizing interfacial resistance within solid-state batteries.

[0205] Promote solid-state reaction

[0206] Ball milling can induce solid-state reactions between different components, promoting the formation of desired phases and structures in the material. This is particularly relevant for the synthesis of composite electrode materials or the preparation of the composite electrolyte materials provided in this application.

[0207] Optimize conductivity

[0208] 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) in the composite or in the solid electrolyte provided in this application.

[0209] Controlling morphology

[0210] The grinding process can also affect the morphology of the material, including particle shape and size distribution. Controlling these aspects is important for achieving the desired electrochemical properties and the overall performance of solid-state batteries.

[0211] Energy considerations

[0212] Ball milling is an energy-intensive process that requires careful control of the milling time and speed to avoid overheating that could lead to unwanted reactions or material damage.

[0213] speed

[0214] In some embodiments, the ball milling is performed at speeds such as: 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 7 ... 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 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, 350 RPM, 400 RPM, 450 RPM, 500 RPM, 550 RPM, 600 RPM, 650 RPM, 700 RPM, 750 RPM, etc.In this implementation, the ball milling speed can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 250 RPM to 750 RPM.

[0215] Duration

[0216] In some embodiments, the ball milling is carried out 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... The timeframes are 16 hours, 1 to 15 hours, 1 to 14 hours, 1 to 13 hours, 1 to 12 hours, 1 to 11 hours, 1 to 10 hours, 1 to 9 hours, 1 to 8 hours, 1 to 7 hours, 1 to 6 hours, 1 to 5 hours, 1 to 4 hours, 1 to 3 hours, 1 to 2 hours, 0.1 hours, 0.5 hours, 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 an embodiment, the ball milling can be performed for a time range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 1 minute to 20 hours.

[0217] The effect of ball milling

[0218] In some embodiments, ball milling causes thiol groups or leaving groups to interact with sulfur in the sulfide-containing solid electrolyte material, resulting in at least a portion of the additive material adhering to the particle surface. In some embodiments, at least a portion of the additive material adheres to the particle surface via non-covalent adhesion. In some embodiments, the non-covalent adhesion is chemisorption, van der Waals interaction, or ionic interaction. In some embodiments, at least a portion of the additive material adheres to the particle surface via covalent bonds. In some embodiments, the covalent bonds are sulfur bonds or disulfide bonds.

[0219] The conductivity or diffusivity of lithium ions

[0220] At least a portion of the additive material adheres to the surface of the sulfide-containing solid electrolyte particles, forming a network of conductive paths between adjacent electrolyte particles through contact between at least a portion of the additive material and adjacent solid electrolyte materials. This network of conductive paths facilitates more efficient lithium-ion transport through the battery structure. Furthermore, the enhanced interparticle contact keeps the solid electrolyte materials together, ensuring a continuous path for more efficient movement of lithium ions between electrodes.

[0221] Lower operating pressure

[0222] A solid electrolyte layer is manufactured by ball milling an additive material and a sulfide-containing solid electrolyte material. The interaction between the additive material and the solid electrolyte material particles causes at least a portion of the additive material to adhere to the surface of the solid electrolyte material particles, thereby creating better and / or tighter contact between materials in the solid electrolyte layer (e.g., between at least a portion of the additive material and adjacent solid electrolyte material particles, and between solid electrolyte material particles themselves). This interaction and adhesion also maintain this improved contact during the charge and discharge of the solid-state battery. This improved contact facilitates the conductivity of lithium ions in the solid electrolyte layer, enabling the solid-state battery provided by this application to operate at pressures substantially lower than 10 MPa, which is required when the additive material is absent from the solid electrolyte layer. In some embodiments, the solid-state battery can operate at pressures such as 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 at pressures within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within a range less than 10 MPa.

[0223] Specific capacity

[0224] Lower operating pressure can prevent, reduce, or eliminate the problems described herein associated with higher operating pressures typically applied to solid-state batteries. For example, it can improve the stability and specific capacity of solid-state batteries. In some embodiments, the specific capacity of the solid-state battery is 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 implementation, 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 ​​within a range greater than 100 mAh / g.

[0225] Reaction and testing environment

[0226] Because materials containing sulfides are sensitive to air and moisture, they may decompose to produce toxic gases such as H2S. The manufacturing and testing steps of the solid-state battery provided in this application can be carried out in a closed device filled with inert gases such as argon. For example The test was conducted in MBraun MB 200B (H2O <0.5 ppm, O2 <0.5 ppm).

[0227] Other aspects

[0228] Other aspects of this disclosure are provided below. Other features, implementations, and embodiments described below apply to all aspects of the invention described above. However, in the event of any conflict between the information discussed above and the information described below, the information in the foregoing sections shall prevail.

[0229] Solid-state lithium-ion batteries

[0230] Solid-state batteries can withstand multiple charge-discharge cycles to an electrical load. A solid-state battery consists of electrodes, namely a positive and a negative electrode, and an electrolyte that allows lithium ions to move between the electrodes. Unlike traditional liquid electrolyte batteries, solid-state batteries do not contain any flowing liquid. Forming a circuit between the electrodes allows current to flow between them. During the charging process of a lithium-ion rechargeable battery, lithium ions are released from the positive electrode and inserted into the active material of the negative electrode. During the discharging process, lithium ions are released from the negative electrode and inserted into the active material of the positive electrode. Energy is transferred as lithium ions reciprocate between the electrodes.

[0231] Solid-state battery composition

[0232] The present invention provides a solid-state battery 100, which includes a positive electrode 102, a negative electrode 104, and a solid electrolyte layer 106 between the positive electrode 102 and the negative electrode 104. Although illustrated by way of example, the solid-state battery 100 does not require all of these components. For example, in some configurations such as an anode-free system, the negative electrode 104 may be omitted.

[0233] Optional additional layers

[0234] The solid-state battery 100 may optionally include additional layers such as a separator layer, a protective layer, a suppression layer, a solid electrolyte interface layer, or a combination thereof.

[0235] protective layer

[0236] For example, a protective layer can be introduced between electrodes 102 and 104 and the solid electrolyte layer 106. The protective layer can also mitigate dendrite formation (especially on the negative electrode side), thereby improving the overall cycle life and safety of the battery. In some cases, the protective layer can help improve the interfacial stability between the electrode and the electrolyte, potentially reducing undesirable side reactions. Furthermore, the protective layer can enhance the mechanical properties of the electrode-electrolyte interface, which can help maintain good contact during cycling.

[0237] Protective layer material

[0238] This protective layer may contain materials such as lithium phosphate, lithium titanate, or lithium lanthanum zirconium oxide (LLZO), which helps prevent unwanted side reactions at the electrode-electrolyte interface. Other options for protective layer materials 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.

[0239] membrane layer

[0240] In some configurations of the solid-state battery 100, a separator layer may also be included. These separator layers can provide additional mechanical support to the battery structure while still allowing efficient ion transport. The separator layer can also be designed with a gradient structure having properties optimized for contact with both the positive and negative electrode materials. Such a gradient structure can involve, for example, altering the porosity, composition, or surface properties of the separator thickness. In some aspects, the separator surface can be functionalized with ion-conducting groups or coatings to enhance lithium-ion transport at the electrode-separator interface. The separator layer can also be designed as a multilayer by integrating different materials optimized for specific functions, such as a mechanically strong core layer sandwiched between ion-conducting outer layers. The separator layer can also be designed to self-heal, for example, by reforming bonds after mechanical stress, thereby helping to prevent short circuits caused by dendrite growth.

[0241] Diaphragm material

[0242] While traditional liquid electrolyte batteries often employ porous polymer membranes, solid-state batteries can utilize thin ceramic or glass-ceramic layers as membranes. Materials such as LLZO, LATP (lithium aluminum titanium phosphate), or LAGP (lithium aluminum germanium phosphate) can be used for this purpose. Other membrane layer materials suitable for solid-state batteries include lithium oxynitride phosphate (LiPON), lithium lanthanum titanate (LLTO), and lithium garnet-type materials (such as Li6BaLa2Ta2O). 12 ), sulfide materials (such as Li) 10 GeP2S 12 ) as well as polymer-ceramic composites that combine materials such as polyethylene oxide (PEO) with ceramic fillers.

[0243] Solid-state battery cells

[0244] Figure 1 A cell 101 of a solid-state battery 100 according to one embodiment is shown. The cell 101 includes a positive electrode 102, a negative electrode 104, and a solid electrolyte layer 106 between the positive electrode 102 and the negative electrode 104. The cell 101 may optionally include additional layers such as a separator layer, a protective layer, a suppression layer, a solid electrolyte interface layer, or a combination thereof.

[0245] Cell composition

[0246] like Figure 1 As shown, the solid-state battery 100 may include a single cell 101. In other examples, the solid-state battery 100 may include multiple cells, such as at least two cells, at least three cells, or at least four cells. Connecting cells in series can increase the voltage of the solid-state battery 100, and connecting cells in parallel can increase the ampere-hour capacity of the solid-state battery 100.

[0247] Cell size

[0248] The battery cell 101 may have a width w1, a length l1, and a thickness t1.

[0249] Cell thickness

[0250] The thickness t1 of cell 101 can be any value in the range of 100 μm to 5000 μm, such as 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, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 3000, 4000, or 5000 μm. In some embodiments, the thickness t1 of the cell 101 can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​in the range of 100 μm to 5000 μm, for example, between 100 μm and 5000 μm or between 100 μm and 1000 μm.

[0251] Aspect Ratio of Width

[0252] The width w1 of the battery cell 101 may be substantially greater than the thickness t1 of the battery cell 101. In some embodiments, the aspect ratio of the width w1 to the thickness t1 may be 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, or even higher. 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 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.

[0253] Aspect Ratio of Length

[0254] The length l1 of the battery cell 101 may be substantially greater than the thickness t1 of the battery cell 101. In some embodiments, the aspect ratio of the length l1 to the thickness t1 may be 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, or even higher. 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 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.

[0255] positive electrode

[0256] The positive electrode 102 is associated with one polarity (e.g., positive polarity) of the solid-state battery 100. During the discharge process of the solid-state battery 100, the positive electrode 102 is configured as the positive electrode. 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 electrically connected to the current collector 108.

[0257] Positive position

[0258] In one embodiment, the positive electrode 102 is formed above the current collector 108 and is in direct contact with the current collector 108. In other embodiments, other functional layers may be inserted between the positive electrode 102 and the current collector 108.

[0259] Positive electrode materials

[0260] The positive electrode 102 can be capable of reversibly inserting and deintercalating lithium ions. For example, the positive electrode 102 may contain only a positive electrode active material. In other examples, the positive electrode 102 may optionally contain one or more of conductive carbon, solid electrolyte material, and binder. Optionally, the positive electrode 102 may also contain additives, such as oxidation stabilizers, reduction stabilizers, flame retardants, heat stabilizers, antifogging agents, thickeners, plasticizers, ion conductivity enhancers, binders (described in detail below), dispersants, wetting agents, adhesion promoters, crosslinking agents, colorants, etc., or combinations thereof.

[0261] Examples of additives

[0262] Examples of such additives may include: butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT) as oxidative stabilizers; ascorbic acid or sodium sulfite as reducing 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 ion conductivity enhancers; polyvinylpyrrolidone or sodium dodecyl sulfate as dispersants; polysorbate or poloxamer as wetting agents; silanes or titanates as adhesion promoters; peroxides or aziridines as crosslinking agents; and carbon black or metal oxides as colorants.

[0263] Positive electrode active material

[0264] Positive electrode active materials may include: lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and Li[Ni a Co b Mn c M 1 d O2 (where M) 1 For any element selected from the group consisting of Al, Ga, In, or combinations thereof, 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 2f-e-f M 3 f′ )O 2-g A g (where 0≤e≤0.2, 0.6≤f≤1, 0≤f′≤0.2, 0≤g≤0.2, M) 2 It contains manganese and at least one element selected from the group consisting of Ni, Co, Fe, Cr, V, Cu, Zn, and Ti. 3 Compounds containing at least one element selected from the group consisting of Al, Mg, and B, and A being at least one element selected from the group consisting of P, F, S, and N, or those substituted by one or more transition metals; lithium manganese oxides, such as those with the chemical formula Li 1+h Mn 2-h Those represented by O4 (0≤h≤0.33), LiMnO3, LiMn2O3, LiMnO2, etc.; lithium copper oxide (Li2CuO2); vanadium oxides, such as LiV3O8, V2O5, or Cu2V2O7; chemical formula LiNi 1-i M 4 i O2 (where M) 4 =Ni-type lithium nickel oxides represented by Co, Mn, Al, Cu, Fe, Mg, B or Ga, and 0.01≤y≤0.3); chemical formula LiMn 2-j M 5 j O2 (where M) 5 =Co, Ni, Fe, Cr, Zn or Ta, and 0.01≤y≤0.1) or Li2Mn3M 6 O8 (where M) 6 Lithium manganese composite oxides represented by Fe, Co, Ni, Cu or Zn; LiMn2O4 in which Li is partially substituted by alkaline earth metal ions; disulfide compounds; LiFe3O4, Fe2(MoO4)3, etc.; or combinations thereof.

[0265] Phosphate materials

[0266] Besides the aforementioned positive electrode active materials, the positive electrode can also contain other types of materials. For example, lithium iron phosphate (LiFePO4) can be used as a positive electrode active material due to its excellent thermal stability and long cycle life. Another example is lithium manganese iron phosphate (LiMn). x Fe 1-x Fluorophosphates such as lithium vanadium phosphate (LiVOPO4), lithium titanium phosphate (LiTi2(PO4)3), lithium nickel phosphate (LiNiPO4), LiVPO4F or LiFeSO4F, as well as other phosphate materials such as lithium cobalt phosphate (LiCoPO4), are also suitable.

[0267] Layered oxide materials

[0268] Positive electrode active materials can also include layered oxide materials with various compositions, such as Li(Ni) 1-x- y Co x Mn y O2 (NCM) or Li (Ni) 1-x-y Co x Al y O2 (NCA), in which the ratio of Ni, Co, Mn, and Al can be adjusted to optimize performance characteristics. For example, NCM811 (LiNi) can be used. 0.8 Co 0.1 Mn 0.1 Higher energy density can be achieved using NCM materials with high nickel content, such as O2. 0.5 Mn 1.5 Spinel structures such as O4 can provide high-voltage operation. Alternatively, materials with ideal structures, such as LiFeSO4F or LiVPO4F, can be used due to their potential for high energy density and good thermal stability.

[0269] Composite or hybrid cathode materials

[0270] Composite or hybrid cathode materials combining two or more active materials can also be used. For example, a mixture of layered oxides and spinel materials can be used to balance energy density and power performance. As another example, lithium iron phosphate can be mixed with one or more of the aforementioned cathode active materials. In some embodiments, the cathode active material may comprise a surface-modified form of the aforementioned compounds, wherein the surface modification is intended to improve stability, conductivity, or other performance indicators.

[0271] Emerging materials category

[0272] Cathode active materials can also include emerging material categories such as disordered rock salt structures (e.g., Li3NbO4-type materials), lithium-rich anti-perovskites (e.g., Li3OCl), cationic disordered oxides (e.g., Li-Mn-VO systems), or high-entropy oxides, which can provide an ideal combination of high capacity and structural stability. In some cases, dopants or substitution elements can be introduced into cathode active materials to further modulate their electrochemical properties.

[0273] Particle properties of positive electrode active materials

[0274] The positive electrode active material can be in particle shape. The particle size of the positive electrode active material can range from 1 nm to 1000 μm, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 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, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm. nm, 480 nm, 490 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850nm, 900 nm, 950 nm, 1000 nm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, 400 μm, 410 μm, 420 Any of µm, 430 µm, 440 µm, 450 µm, 460 µm, 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 this embodiment, the particle size of the positive electrode active material can be within a range formed by selecting any two values ​​listed above or any two values ​​in the range of 1 nm to 1,000 μm, for example, 10 nm to 1,000 μm. The gaps between the positive electrode active material particles in the positive electrode 102 can be filled with a solid electrolyte material.

[0275] The amount of positive electrode active material in the positive electrode

[0276] The amount of positive electrode active material in 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 can be included in the positive electrode 102. For example, based on the total weight of the positive electrode 102, the positive electrode 102 may contain approximately or more of the positive electrode active material at or above 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99% by weight. In embodiments, the positive electrode active material in the positive electrode 102 can be within a range formed by selecting any two values ​​listed above or any two values ​​within the range of 0 to 100% by weight, for example, 40% to 98% by weight.

[0277] Conductive material in the positive electrode

[0278] There are no specific restrictions on the conductive material in the positive electrode 102, as long as it is conductive and does not cause chemical changes in the corresponding 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, Ketjen black, channel black, furnace black, lamp black, or thermally cracked carbon black; conductive fibers, such as carbon fibers or metal fibers; carbon nanotubes (CNTs), including single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs); fluorinated carbon; metal powder, such as aluminum powder or nickel powder; conductive whiskers, such as zinc oxide or potassium titanate; conductive metal oxides, such as titanium oxide; conductive polymers, such as polyphenylene derivatives; 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), etc., or combinations thereof.

[0279] The amount of conductive material in the positive electrode

[0280] Based on the total weight of the positive electrode 102, the positive electrode 102 contains 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% by weight of conductive material. In an embodiment, the content of conductive material in the positive electrode 102 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from 1% by weight to 30% by weight.

[0281] Adhesive materials

[0282] Adhesives may contain various types of adhesive polymers, such as: vinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene propylene diene monomer (EPDM), sulfonated ethylene propylene diene monomer (EPDM), styrene-butadiene rubber (SBR), fluororubber, polyacrylic acid, polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), poly(ethylene-vinyl acetate) (PEVA), polyvinyl acetate (PVA), chitosan, guar gum (GG), xanthan gum, carrageenan, pectin, water-soluble polymers, lignin, polymers whose hydrogen atoms are replaced by Li, Na, or Ca, various copolymers thereof, or combinations thereof.

[0283] Other adhesive materials

[0284] In addition to the aforementioned adhesive materials, other types of adhesive materials can be used in the positive electrode to improve its performance and stability. For example, water-soluble adhesives such as sodium alginate, gelatin, or polyacrylamide can be used to improve the environmental friendliness of the electrode manufacturing process. These adhesives can also provide advantages in terms of electrode flexibility and adhesion strength. In some cases, conductive adhesives such as poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) or polyaniline (PANI) can be used to simultaneously improve the mechanical integrity and conductivity of the electrode.

[0285] Novel adhesive system

[0286] Novel adhesive systems, such as self-healing polymers or supramolecular assemblies, can be introduced to enhance the long-term stability and cycle life of batteries. Furthermore, composite adhesives that combine or incorporate multiple polymers with inorganic nanoparticles can be used to customize the mechanical, thermal, and electrochemical properties of the electrodes. In some embodiments, bio-derived or biodegradable adhesives, such as cellulose derivatives or chitosan, can be used to reduce the environmental impact of battery production and disposal.

[0287] Amount of binder in the positive electrode

[0288] Based on the total weight of the positive electrode 102, the positive electrode 102 may contain 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% by weight of binder. In an embodiment, the binder content in the positive electrode 102 may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from 1% by weight to 30% by weight.

[0289] solid electrolyte materials

[0290] The solid electrolyte material in the positive electrode 102 may be configured to be the same as the material of the solid electrolyte layer 106 described below. The solid electrolyte material in the positive electrode 102 may be the same as or different from the material of the solid electrolyte layer 106.

[0291] The amount of solid electrolyte material in the positive electrode

[0292] Based on the total weight of the positive electrode 102, the positive electrode 102 may contain 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% by weight of solid electrolyte material. In an embodiment, the amount of solid electrolyte material in the positive electrode 102 may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from 1% by weight to 30% by weight.

[0293] Positive electrode thickness

[0294] The thickness t2 of the positive electrode 102 can be any value in the range of 0 to 1000 μm, such as 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, 50 0, 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 μm. In an implementation, the thickness t2 of the positive electrode 102 can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​in the range greater than 0 to 1000 μm, for example, 10 μm to 1000 μm.

[0295] Positive electrode porosity

[0296] Based on the total volume of the positive electrode 102, the porosity of the positive electrode 102 can be any value in the range of 0 to 20 volume %, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 volume %, or any other volume % in the range of 0 to 20 volume %. In an embodiment, the porosity of the positive electrode 102 can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​in the range of 0 to 20 volume %, for example, 0 volume % to 18 volume %.

[0297] Lithium-ion diffusion in the positive electrode

[0298] The positive electrode 102 can be contained in a range greater than 0 to 1 × 10 -7 cm 2 Lithium-ion diffusivity of any value in the range of / s or around it, for example, 1×10 -14 cm 2 / s, 1×10 -13 cm 2 / s, 1×10 -12 cm2 / s, 1×10 -11 cm 2 / s, 1×10 -10 cm 2 / s, 1×10 -9 cm 2 / s, 1×10 -8 cm 2 / s or 1×10 -7 cm 2 / s. In an implementation, the lithium-ion diffusion of the positive electrode 102 can be achieved by selecting any two values ​​listed above or selecting values ​​greater than 0 to 1 × 10⁻⁶. -7 cm 2 The range formed by any two values ​​within the range of / s, for example, 1×10 -14 cm 2 / s to 1×10 -7 cm 2 / s.

[0299] Positive current collector

[0300] The current collector 108 collects the electrical energy generated at the positive electrode 102 and supports the positive electrode 102.

[0301] Materials used for current collectors at the positive electrode

[0302] The material of the current collector 108 is not particularly limited, as long as it can adhere to the positive electrode 102, has suitable conductivity, and does not cause significant chemical changes in the solid-state battery 100 within the voltage range of the corresponding solid-state battery 100. For example, the current collector 108 can be made of or contain various materials, such as metals, conductive carbon, or conductive ceramics, but is not limited thereto. The metal of the current collector 108 may include one or more of the following groups, but is not limited thereto: 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.

[0303] Current collector geometry

[0304] The current collector 108 can also be configured in various other geometries to optimize its performance and integration with the positive electrode 102, and its size can be adjusted for specific shape factors such as pouch, cylindrical and / or prismatic shape factors.

[0305] The shape of the current collector at the positive electrode

[0306] By forming fine surface irregularities on the surface of the current collector 108, the adhesion of the positive electrode 102 to the current collector 108 can be improved. The current collector 108 can have various shapes, such as a film, sheet, foil, mesh, porous body, foam, nonwoven mesh, or a combination thereof.

[0307] Examples of the shape and size of current collectors

[0308] For example, the current collector 108 can be configured as a mesh or grid, which can provide enhanced mechanical support while maintaining the high surface area required for electrode adhesion. In some embodiments, the current collector 108 can be designed with a corrugated or wavy pattern, which potentially increases the contact area with the positive electrode material and improves overall conductivity. The current collector 108 can also be fabricated as a perforated sheet, allowing for better electrolyte permeation and ion transport. In some cases, the current collector 108 can be formed as a three-dimensional structure, such as a fiber interconnect network or a honeycomb configuration, which can enhance the structural integrity of the electrode assembly while promoting efficient current harvesting.

[0309] Thickness of the current collector at the positive electrode

[0310] The thickness t3 of the current collector 108 can be any value in the range of 0 to 500 μm, such as 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, 430, 440, 450, 460, 470, 480, 490, or 500 μm. In an implementation, the thickness t3 of the current collector 108 can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​in the range greater than 0 to 500 μm, for example, 5 μm to 500 μm.

[0311] Method for manufacturing positive electrode

[0312] Positive electrode 102 can be obtained through various methods.

[0313] Dry powder coating process

[0314] For example, a dry powder coating process can be used, in which the positive electrode active material, conductive additives, and binder are mixed in a dry state and then directly coated onto the current collector 108 using electrostatic deposition or mechanical compression. This method can reduce environmental impact by reducing solvent usage.

[0315] 3D printing

[0316] In some cases, the positive electrode 102 can be fabricated using additive manufacturing techniques such as 3D printing. This method allows for precise control of the electrode structure and porosity, potentially improving electrode performance and energy density. Depending on the specific material and desired electrode properties, various 3D printing methods can be employed, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW).

[0317] electrospinning

[0318] Another method for manufacturing the positive electrode 102 involves electrospinning. In this process, a solution containing a positive electrode active material, conductive additives, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be directly collected on the current collector 108 to form a highly porous electrode structure with an increased surface area.

[0319] Casting

[0320] In some embodiments, the positive electrode 102 can be prepared using a casting process. 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 strip can then be laminated onto the current collector 108.

[0321] Spraying

[0322] Alternatively, the positive electrode 102 can be prepared using a spray coating technique. In this method, compressed air or ultrasonic atomization is used to spray a micro-mist of the electrode slurry onto the current collector 108. This process can achieve the formation of a thin and uniform electrode layer, and is particularly suitable for large-scale production.

[0323] Cryogenic casting

[0324] In some cases, the positive electrode 102 can be prepared using a cryogenic casting method. This process involves freezing a slurry of electrode material and then sublimating the ice to form a porous structure. The resulting porous electrode can then be sintered and attached to the current collector 108.

[0325] Sol-gel method

[0326] For some applications, the positive electrode 102 can be prepared using a sol-gel method. This method involves forming a colloidal suspension (sol), which is then transformed into a gel-like network containing the positive electrode active material and other components. This gel can be coated onto the current collector 108 and then heat-treated to form the final electrode structure.

[0327] Slurry-based processes

[0328] For example, the positive electrode active material can be mixed with a solvent and optionally a binder, conductive material and dispersant and stirred to form a slurry. The slurry can then be coated (e.g., coated) onto the current collector 108, followed by pressing and drying to obtain the positive electrode 102.

[0329] Coating method for positive electrode slurry

[0330] Applying the slurry to the positive electrode 102 may include using techniques selected from the group consisting of: slot coating, gravure coating, spin coating, spray coating, roller coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, heat transfer printing, letterpress printing, intaglio printing, offset printing, and combinations thereof.

[0331] Double-layer slot coating

[0332] In some embodiments, the positive electrode 102 can be prepared using a double-slit coating (DLD) technique. This method involves simultaneously applying two different electrode materials to the current collector 108 in a single operation. The DLD process enables the creation of a gradient structure within the electrode, potentially optimizing both the electrochemical performance and mechanical properties of the positive electrode. Furthermore, this technique allows for the introduction of functional intermediate layers or protective coatings as part of the electrode fabrication process, potentially improving overall battery performance and lifespan.

[0333] Solvent for positive electrode slurry

[0334] The solvent used for forming the positive electrode 102 may contain water and / or organic solvents, such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, dimethylacetamide, dimethyl sulfoxide (DMSO), isopropanol, etc., or combinations thereof. Considering factors such as slurry coating thickness, productivity, etc., or combinations thereof, the solvent may be used in an amount sufficient to dissolve and disperse electrode components such as positive electrode active materials, binders, and conductive materials. Other solvents that may be used include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0335] Solvent-free method

[0336] In some aspects of this disclosure, the cathode 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 benefits.

[0337] Dispersant for cathode slurry

[0338] The dispersant forming the positive electrode 102 may include aqueous or organic dispersants, such as 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 polysorbate or poloxamer.

[0339] Drying technology for cathode slurry

[0340] The slurry for cathode 102 can be dried by irradiation with heat, electron beam (E-beam), gamma rays, or ultraviolet light (G / H / I lines), or a combination thereof, causing the solvent to vaporize. For example, the slurry can be vacuum dried at room temperature. Although the solvent is removed by evaporation through the drying step, other components do not evaporate and remain intact to form cathode 102.

[0341] Other drying techniques

[0342] In addition to the drying technology described above, the positive electrode 102 can also be dried using other methods such as infrared (IR) drying, microwave drying, or freeze drying.

[0343] Combination of drying technologies

[0344] In some implementations, a combination of drying techniques may be used, 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.

[0345] Negative electrode overview

[0346] The negative electrode 104 is associated with a polarity (e.g., negative) of the solid-state battery 100, which is different from the polarity of the positive electrode 102. During the discharge process of the solid-state battery 100, the negative electrode 104 is configured as the negative electrode. The negative electrode 104 is suitable for lithium-ion diffusion between the current collector 110 and the solid electrolyte layer 106.

[0347] Negative electrode position

[0348] The negative electrode 104 is electrically connected to the current collector 110. In one embodiment, the negative electrode 104 is formed above the current collector 110 and is in direct contact with the current collector 110. In other embodiments, other functional layers may be inserted between the negative electrode 104 and the current collector 110.

[0349] Anode-free electrode system

[0350] In some embodiments, as described above, the solid-state battery 100 may employ an anode-less electrode system. In such a configuration, the negative electrode 104 can be omitted, and lithium metal can be directly deposited onto the current collector 110 during charging. This method can potentially increase the energy density of the battery, eliminate the need for a separate negative electrode material, and also potentially reduce the overall thickness of the battery structure.

[0351] negative electrode materials

[0352] The negative electrode 104 can be capable of reversibly inserting and deintercalating lithium ions. For example, the negative electrode 104 may contain only the negative electrode active material. In other examples, the negative electrode 104 may contain conductive particles, binders, etc., or combinations thereof.

[0353] Additives for negative electrodes

[0354] Optionally, the negative electrode 104 may also contain additives, such as oxidation stabilizers (e.g., butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tert-butylhydroquinone), reduction stabilizers (e.g., ascorbic acid, sodium sulfite, isoascorbic 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, glycerin, sorbitol), thickeners (e.g., carboxymethyl cellulose, xanthan gum), etc., or combinations thereof.

[0355] Other additives for the negative electrode

[0356] In addition, conductive additives such as carbon black, graphene, or carbon nanotubes can be incorporated to enhance conductivity, while adhesive modifiers such as styrene-butadiene rubber or polyacrylic acid can improve adhesion and mechanical stability. Functional additives such as fluoroethylene carbonate or vinylene carbonate may also be included to promote the formation of a stable solid electrolyte interface layer on the negative electrode surface.

[0357] Materials for negative electrode active materials

[0358] The negative electrode active material is made of or contains various materials, such as alkali metals, alkaline earth metals, group 3B metals, transition metals, metalloids, their alloys, conductive carbon, or combinations thereof, but is not limited thereto. In embodiments, the negative electrode active material may contain silicon, silicon alloys, lithium, lithium alloys, conductive carbon, or combinations thereof, but is not limited thereto. In embodiments, the lithium alloy is made of or contains a lithium alloy containing silicon, chlorine, or a combination thereof. A lithium metal thin film can be used as the negative electrode active material.

[0359] Other materials for negative electrode active materials

[0360] The negative electrode active material may include: carbon materials such as artificial graphite, natural graphite, graphitized carbon fiber or amorphous carbon; metal compounds capable of alloying with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys, etc.; metal oxides capable of doping and de-doping lithium ions, such as SiO x (0 < x < 2), SnO2, vanadium oxides or lithium vanadium oxides; or composites containing metal compounds and carbon materials, such as Si-C composites or Sn-C composites.

[0361] carbon materials

[0362] The carbon materials may include low-crystalline carbon, high-crystalline carbon, etc. or combinations thereof. Representative examples of low-crystalline carbon are soft carbon and hard carbon, and representative examples of high-crystalline carbon are amorphous, plate-like, flaky, spherical or fibrous natural graphite or artificial graphite, Kish graphite, pyrolytic carbon, mesophase pitch-based carbon fiber, mesophase carbon microspheres, mesophase pitch and high-temperature calcined carbon such as coke derived from petroleum or coal tar pitch, etc. or combinations thereof.

[0363] Metal-carbon composite materials

[0364] Alternatively, according to some aspects of the present disclosure, the negative electrode 104 may comprise a negative electrode active material having a metal-carbon composite material, such as a silver-carbon mixture or composite, wherein silver particles are composite between amorphous and / or crystalline carbon particles. Here silver is taken as an example, and other metals may also be used, including for example tin and / or zinc. Silicon may be used to replace silver.

[0365] The negative electrode active material uses another material.

[0366] In addition to the foregoing materials, the negative electrode active material may also comprise titanium-based compounds, such as lithium titanate (Li4Ti5O 12 ) or titanium dioxide (TiO2), which can provide excellent cycle stability and high rate performance. Other potential materials may include transition metal oxides, such as molybdenum oxides (MoO x ), iron oxides (FeO x ) or nickel oxides (NiO x ), which can provide high theoretical capacity. In some cases, composite active materials combining different active materials, such as Si-graphite composites or Sn-carbon composites, may be employed to utilize the advantages of multiple materials while alleviating their individual limitations.

[0367] Dendrite formation

[0368] When the negative electrode 104 is made of or contains lithium or a lithium alloy, dendrites may form on the negative electrode 104. Dendrites are metallic lithium structures formed 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 major challenge for lithium-ion 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 affected by factors such as current density, temperature, and the properties of the electrolyte-electrode interface.

[0369] Advantages of solid electrolytes in mitigating dendrite formation

[0370] Solid electrolytes offer several advantages over liquid electrolytes in mitigating dendrite formation. The mechanical strength of solid electrolytes helps suppress dendrite growth by providing a physical barrier to lithium metal penetration. Furthermore, the uniform ion distribution in solid electrolytes promotes more uniform lithium deposition, reducing the likelihood of localized dendrite nucleation. Some solid electrolytes can also form stable interfaces with lithium metal anodes, further suppressing dendrite formation. However, while solid electrolytes can significantly reduce the risk of dendrite growth, they cannot completely eliminate it. Current research focuses on developing advanced solid electrolyte materials with enhanced dendrite suppression capabilities.

[0371] Shape of negative electrode active material

[0372] The negative electrode active material can be in particulate form or in a continuous single form (e.g., thin film or sheet).

[0373] Particle size

[0374] In embodiments where the negative electrode active material is in particulate form, the particle size of the negative electrode active material can be any value within the range of 10 nm to approximately 1000 μm, such as 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, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, etc. nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560nm, 570 nm, 580 nm, 590 nm, 600 nm, 610 nm, 620 nm, 630 nm, 640 nm, 650 nm, 660 nm, 670nm, 680 nm, 690 nm, 700 nm, 710 nm, 720 nm, 730 nm, 740 nm, 750 nm, 760 nm, 770 nm, 780nm, 790 nm, 800 nm, 810 nm, 820 nm, 830 nm, 840 nm, 850 nm, 860 nm, 870 nm, 880 nm, 890nm, 900 nm, 910 nm, 920 nm, 930 nm, 940nm, 950 nm, 960 nm, 970 nm, 980 nm, 990 nm, 1000nm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, 400 μm, 410 μm, 420 μm, 430 μm, 440 μm, 450 μm, 460 μm, 470 μm, 480 μm, 490 μm, 500 μm, 510 μm, 520 μm, 530 μm, 540 μm, 550 μm, 560 μm, 570 μm, 580 μm, 590 μm, 600 μm, 610 μm, 620 μm, 630 μm, 640 μm, 650 μm, 660 μm, 670 μm, 680 μm, 690 μm, 700 μm, 710 μm, 720 μm, 730 μm, 740 μm, 750 μm, 760 μm, 770 μm, 780 μm, 790 μm, 800 μm, 810 μm, 820 μm, 830 μm, 840 μm, 850 μm, 860 μm, 870 μm, 880 μm, 890 μm, 900 μm, 910 μm, 920 μm, 930 μm, 940 μm, 950 μm, 960 μm, 970 μm, 980μm, 990 μm or 1,000 μm. In an embodiment, the particle size of the negative 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 10 nm to 1,000 μm, for example, 10 nm to 1,000 μm.

[0375] The amount of negative electrode active material in the negative electrode

[0376] The amount of negative electrode active material in the solid-state battery 100 affects the charge / discharge capacity of the solid-state battery 100. To manufacture a high-capacity negative electrode 104, a high level of negative electrode active material can be included in the negative electrode 104. For example, based on the total weight of the negative electrode 104, the negative electrode 104 contains approximately or more of 70, 80, 90, 95, 98, 99, or 100% by weight of negative electrode active material. In embodiments, the content of negative electrode active material in the negative electrode 104 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from 70% by weight to 100% by weight.

[0377] Adhesive material in negative electrode

[0378] Adhesives may include various types of adhesive polymers, such as vinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene propylene diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, polyacrylic acid, polymers in which hydrogen atoms are substituted by Li, Na or Ca, various copolymers thereof, or combinations thereof.

[0379] Examples of binder materials used in negative electrodes

[0380] In addition to the aforementioned adhesives, other suitable adhesives for the negative electrode may include polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), poly(ethylene-co-vinyl acetate) (PEVA), polyvinyl acetate (PVA), alginate, chitosan, guar gum, xanthan gum, carrageenan, pectin, gelatin, lignin, and various water-soluble polymers or their derivatives. In some cases, conductive polymers such as polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene) (PEDOT) may also be used as adhesives to simultaneously improve adhesion and conductivity within the negative electrode.

[0381] The amount of binder in the negative electrode

[0382] Based on the total weight of the negative electrode 104, the negative electrode 104 may contain 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% by weight, or any other percentage by weight within the range of 0 to 30% by weight. In an embodiment, the adhesive in the negative electrode 104 may be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within the range of 0 to 30% by weight, for example, 0% to 30% by weight.

[0383] negative electrode thickness

[0384] The thickness of the negative electrode 104 can be 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 μm. In an embodiment, the thickness t4 of the negative electrode 104 can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 10 μm to 100 μm, for example, 10 μm to 100 μm or 10 μm to 20 μm.

[0385] Negative electrode porosity

[0386] Based on the total volume of the negative electrode 104, the porosity of the negative electrode 104 can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 volume%, or any other volume% within the range of 0 to 18 volume%. In an embodiment, the porosity of the negative electrode 104 can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within the range of 0 to 18 volume%.

[0387] Lithium-ion diffusion of the negative electrode

[0388] The negative electrode 104 can have 1×10 -14 cm 2 / s, 1×10 -13 cm 2 / s, 1×10 -12 cm 2 / s, 1×10 -11 cm 2 / s, 1×10 -10 cm 2 / s, 1×10 -9 cm 2 / s, 1×10 -8 cm 2 / s or 1×10 -7 cm 2 / s of lithium-ion diffusion. In an embodiment, the lithium-ion diffusion of the negative electrode 104 can be determined by selecting any two values ​​listed above or selecting 1×10. -14 cm 2 / s to 1×10 -7 cm 2 The range formed by any two values ​​within the range of / s.

[0389] negative current collector

[0390] The current collector 110 collects the electrical energy generated by the negative electrode 104 and supports the negative electrode 104.

[0391] Materials for current collectors of negative electrode

[0392] The material of the current collector 110 is not particularly limited, as long as it can adhere to the negative electrode 104, has suitable conductivity, and does not cause significant chemical changes in the solid-state battery 100 within the voltage range of the corresponding solid-state battery 100. For example, the current collector 110 may be made of or contain metal or conductive carbon, but is not limited to these materials.

[0393] metal for current collector

[0394] The metal of the current collector 110 may include, but is not limited to, one or more of 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.

[0395] The shape of the current collector at the negative electrode

[0396] 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 improved. The current collector 110 can have various shapes, such as films, sheets, foils, meshes, porous bodies, foams, nonwoven meshes, or combinations thereof. In addition to the shapes mentioned above, the current collector 110 can also be configured as a honeycomb structure, perforated sheet, manufactured / unmanufactured mesh, sintered porous body, or three-dimensional interconnect network. These various shapes can be customized to optimize the surface area, mechanical strength, and current collection efficiency of the current collector 110.

[0397] Design of the current collector for the negative electrode

[0398] In addition, the current collector 110 can be designed to adapt to different shape factors of solid-state batteries such as pouch cells, cylindrical cells or prismatic cells, each of which can provide advantages in terms of packaging efficiency, thermal management and overall battery performance.

[0399] Thickness of the current collector of the negative electrode

[0400] The thickness t5 of the current collector 110 can be 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, or 85 mm. The thickness t5 of the current collector 110 can be 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. In an embodiment, the thickness t5 of the current collector 110 can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​in the range of 1 μm to 500 μm, for example, 5 μm to 500 μm.

[0401] Method for manufacturing the negative electrode

[0402] The negative electrode 104 can be obtained by various methods, such as atomic deposition, extrusion, rolling, slurry processing, or combinations thereof. In addition to the methods described above, the negative electrode 104 can also be manufactured using a variety of other technologies, including dry electrode processes. These alternative methods offer advantages in terms of environmental impact, cost-effectiveness, and scalability.

[0403] Dry powder coating

[0404] Dry powder coating can be used as an alternative to the slurry method. In this method, the negative electrode active material, conductive additives, and binder are mixed in a dry state and then directly coated onto the current collector 110 using electrostatic deposition or mechanical compression. This method can reduce solvent use, potentially reducing environmental impact and processing time.

[0405] 3D printing

[0406] The negative electrode 104 can be fabricated using additive manufacturing technologies such as 3D printing. Depending on the specific material and desired electrode properties, various 3D printing methods can be employed, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW). This method allows for precise control of the electrode structure and porosity.

[0407] electrospinning

[0408] Electrospinning is another potential method for manufacturing the negative electrode 104. In this process, a solution containing the negative electrode active material, conductive additives, and polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be directly collected on the current collector 110 to form a highly porous electrode structure with increased surface area.

[0409] Casting

[0410] The negative electrode 104 can be prepared by tape casting. 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 strip can then be laminated onto the current collector 110.

[0411] Spraying

[0412] The negative electrode 104 can be prepared using a spray coating technique. Compressed air or ultrasonic atomization is used to spray a micro-mist of the electrode slurry onto the current collector 110. This process allows for the formation of a thin and uniform electrode layer, and is particularly suitable for large-scale production.

[0413] Cryogenic casting

[0414] Cryogenic casting is another potential method for manufacturing the negative electrode 104. This process involves freezing a slurry of electrode material, followed by sublimation of the ice to form a porous structure. The resulting porous electrode can then be sintered and attached to the current collector 110.

[0415] Sol-gel method

[0416] In some cases, the sol-gel method can be used to prepare the negative electrode 104. This method involves forming a colloidal suspension (sol), which is then transformed into a gel-like network containing the negative electrode active material and other components. This gel can be coated onto the current collector 110 and then heat-treated to form the final electrode structure.

[0417] vapor deposition

[0418] For specific applications, thin-film anodes can be directly formed on the current collector 110 using physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques. These methods can produce highly uniform and dense electrode layers, which are particularly advantageous for certain types of solid-state batteries.

[0419] Alloying and ball milling

[0420] Mechanical alloying and high-energy ball milling can be used to prepare composite anode materials, which can then be pressed into electrodes or coated onto current collector 110 using one of the aforementioned methods. This technique is particularly suitable for preparing nanostructured or amorphous anode materials with enhanced electrochemical performance.

[0421] Slurry method

[0422] For example, the negative electrode active material can be mixed with a solvent and optionally a binder and dispersant and stirred to form a slurry. The slurry can then be coated (e.g., coated) onto the current collector 110, followed by pressing and drying to obtain the negative electrode 104.

[0423] Coating method for negative electrode slurry

[0424] The coating of the negative electrode 104 slurry may include techniques selected from the group consisting of: slot coating, gravure coating, spin coating, spray coating, roller coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer, letterpress printing, intaglio printing, offset printing, and combinations thereof. In addition to the above techniques, other methods for coating the negative electrode slurry onto the current collector may include doctor blade coating, dip coating, and meniscus coating.

[0425] Double-layer slot coating

[0426] Alternatively, a double-slit coating method can be used, which allows two different electrode materials to be simultaneously coated onto the current collector in a single operation. This method could potentially enable the construction of gradient structures within the electrode, thereby simultaneously optimizing electrochemical properties and mechanical performance.

[0427] Solvent for negative electrode slurry

[0428] The solvent used for forming the negative electrode 104 may contain water and / or organic solvents such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, dimethylacetamide, dimethyl sulfoxide (DMSO), isopropanol, etc., or combinations thereof. Considering factors such as slurry coating thickness, productivity, etc., or combinations 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. Other usable organic solvents include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0429] Solvent-free method

[0430] In some embodiments, the negative electrode 104 may be prepared using solvent-free methods, such as dry powder processing or melt extrusion, which eliminates the need for liquid solvents and provides environmental and cost benefits.

[0431] Dispersant for negative electrode slurry

[0432] The dispersant forming the negative electrode 104 may include aqueous dispersants or organic dispersants, such as N-methyl-2-pyrrolidone. Other examples of aqueous dispersants may include sodium dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP), and carboxymethyl cellulose (CMC), while other organic dispersants may include Triton X-100, polyethylene glycol (PEG), and various surfactants such as polysorbate or poloxamer.

[0433] Dispersant-free method

[0434] In some embodiments, the negative electrode 104 may be prepared using methods that do not require dispersants, such as dry powder processing or specific additive manufacturing techniques.

[0435] Drying technology for negative electrode slurry

[0436] The slurry for the negative electrode 104 can be dried by irradiation with heat, an electron beam (E-beam), gamma rays, or ultraviolet light (G / H / I lines), or a combination thereof, causing the solvent to vaporize. For example, the slurry can be vacuum dried at room temperature. Although the solvent is removed by evaporation through the drying step, other components do not evaporate and remain intact to form the negative electrode 104.

[0437] Other drying techniques

[0438] In addition to the drying techniques mentioned above, a variety of other methods can be used to dry the negative electrode slurry. Depending on the specific materials, production requirements, and desired electrode characteristics, these other techniques can offer various advantages.

[0439] Infrared (IR) drying

[0440] 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.

[0441] Microwave drying

[0442] Microwave drying is another option, which can provide volumetric heating of the electrode material, potentially producing more uniform drying across the entire electrode thickness. In some cases, a combination of convection and microwave drying can be used to simultaneously optimize drying speed and uniformity.

[0443] freeze-drying

[0444] For specific electrode formulations, freeze-drying (also known as lyophilization) can be used. 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 facilitate electrolyte permeation and ion transport.

[0445] Supercritical carbon dioxide drying

[0446] Supercritical CO2 drying is an advanced technique applicable to specialized electrode materials. This method involves replacing the solvent with liquid CO2, subsequently bringing it to a supercritical state, and then evacuating it. This process can help preserve the fine nanostructure within the electrode and is particularly suitable for aerogel electrodes.

[0447] Two-step drying

[0448] In some cases, a two-step drying method can be used. For example, the initial drying can be carried out at a lower temperature to remove most of the solvent, followed by a high-temperature step to remove the residual solvent and potentially initiate any desired chemical reactions within the electrode material.

[0449] Ultrasonic drying

[0450] For specific electrode formulations, ultrasonic drying can also be considered. This technique utilizes high-frequency sound waves to agitate solvent molecules, potentially accelerating the drying process and improving solvent removal from the porous structure within the electrode.

[0451] Overview of solid electrolyte layers

[0452] 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 a conductive path for the movement of charge carriers between the positive electrode 102 and the negative electrode 104. The solid electrolyte layer 106 is electrically connected to the positive electrode 102 and the negative electrode 104.

[0453] solid electrolyte position

[0454] In one embodiment, a solid electrolyte layer 106 is formed above and in direct contact with the positive electrode 102 or the negative electrode 104. In another embodiment, the solid electrolyte layer 106 is in direct contact with both the positive and negative electrodes 102 and 104. In other embodiments, other functional layers may be disposed between the solid electrolyte layer 106 and the positive and / or negative electrodes 104.

[0455] Materials for solid electrolyte layers

[0456] The solid electrolyte layer 106 is capable of transporting lithium ions. The material of the solid electrolyte layer 106 is not particularly limited, as long as it can adhere to adjacent layers, has suitable conductivity, and does not cause significant chemical changes in the solid-state battery 100 within the voltage range of the corresponding solid-state battery 100. For example, the solid electrolyte layer 106 may comprise various inorganic solid electrolytes, polymer solid electrolytes, and / or polymer gel electrolytes, but is not limited thereto. Additionally or alternatively, the solid electrolyte layer 106 may comprise ceramic electrolytes, glass electrolytes, organic-inorganic hybrid electrolytes, and nanostructured electrolytes, but is not limited to these types.

[0457] Inorganic solid electrolytes

[0458] Inorganic solid electrolytes can include, but are not limited to, crystalline solid electrolytes, amorphous solid electrolytes, glass-ceramic solid electrolytes, or combinations thereof. Inorganic solid electrolytes can be sulfide-based, oxide-based, or combinations thereof. Besides sulfide and oxide-based inorganic solid electrolytes, other types of inorganic solid electrolytes may also include halide electrolytes, nitride electrolytes, and borate electrolytes. For example, lithium-rich anti-perovskites such as Li3OCl and Li3OBr (LiRAP), lithium nitride (Li3N), and lithium borohydride (LiBH4) have been studied as potential solid electrolyte materials for lithium-ion batteries.

[0459] Sulfide solid electrolytes

[0460] Sulfide solid electrolytes contain sulfur (S) and have the ionic conductivity of metals belonging to Group 1 or Group 2 of the periodic table. They can include Li-PS type glasses or Li-PS type glass ceramics.

[0461] Examples of sulfide solid electrolytes

[0462] For example, sulfide-based solid electrolytes may include lithium sulfide, silicon sulfide, germanium sulfide, and boron sulfide. Specific examples of inorganic solid electrolytes may 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, 3+y PO 4-x N x ), thiolated 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, 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 combinations thereof.

[0463] Doped variants

[0464] In some cases, doped variants of these materials, such as Al-doped Li, can also be used. 10 GeP2S 12 Alternatively, Sb can be doped into Li6PS5Cl to further enhance ionic conductivity or stability.

[0465] Oxide solid electrolytes

[0466] Oxide-based solid electrolyte materials contain oxygen (O) and have the ionic conductivity of metals belonging to Group I or Group II of the periodic table.

[0467] Examples of oxide-based solid electrolytes

[0468] Oxide-based solid electrolyte materials may include at least one selected from the group consisting of: LLTO compounds, Li6La2CaTa2O 12 Li6La2ANb2O 12 (A is Ca or Sr), Li2Nd3TeSbO 12 Li3BO 2.5 N 0.5 Li9SiAlO8, 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-type compounds, LIPON-type compounds, perovskite-type compounds, NASICON-type compounds, and LLZO-type compounds or derivatives (such as Al-doped Li7La3Zr2O). 12 Ta-doped Li7La3Zr2O 12 Lithium-rich anti-perovskites such as Li3OCl and Li3OBr have been studied as potential oxide-based solid electrolytes.

[0469] Composite oxide electrolyte

[0470] In some cases, composite oxide electrolytes that combine multiple oxide materials, such as the LLZO-LATP complex, can be used to take advantage of the advantages of different oxide systems.

[0471] Polymer solid electrolyte

[0472] Polymer solid electrolytes are complexes of electrolyte salts and polymer resins, exhibiting lithium-ion conductivity. Polymer solid electrolytes may include polyether polymers, polycarbonate polymers, acrylate polymers, polysiloxane polymers, phosphazene polymers, polyethylene derivatives, olefin oxide derivatives, phosphate ester polymers, polyaziridinium, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, polymers containing ionically dissociable groups, polyethyleneimine (PEI), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene succinate (PES), chitosan, and cellulose derivatives, as well as other biopolymers or combinations thereof.

[0473] Polymer resin for solid polymer electrolytes

[0474] Solid polymer electrolytes may contain polymer resins, such as branched copolymers of the polyethylene oxide (PEO) backbone containing comonomers copolymerized with amorphous polymers such as PMMA, polycarbonate, polysiloxane (PDMS) and / or phosphazene, comb polymers, crosslinked polymer resins, polyethylene glycol (PEG), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), ethylene oxide-propylene oxide copolymer (PEO-PPO), polyethyleneimine (PEI), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), various block copolymers or graft copolymers containing these materials, or combinations thereof.

[0475] Polymer gel electrolyte

[0476] Polymer gel electrolytes can be formed by incorporating organic electrolytes containing organic solvents and electrolyte salts, ionic liquids, monomers or oligomers into polymer resins or combinations thereof. Polymer resins used for polymer gels may include polyether polymers, PVC polymers, PMMA polymers, polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), or combinations thereof.

[0477] Examples of polymer gel electrolytes

[0478] Examples of polymeric gel electrolytes suitable for solid-state batteries include polyethylene oxide (PEO), methyl methacrylate-ethyl acrylate copolymer (PMMA-EA), acrylonitrile-methyl methacrylate copolymer (PAN-MMA), polyvinyl acetate (PVAc), polyethylene glycol diacrylate (PEGDA), polyvinylpyrrolidone (PVP), polyethylene glycol methyl ether acrylate (PEGMEA), polyethylene glycol methyl ether methacrylate (PEGMEMA), polyionic liquid (PIL), ethylene glycol-propylene glycol copolymer (PEG-PPG), ethylene alcohol-ethylene copolymer (PVA-PE), polyacrylamide (PAM), poly(2-hydroxyethyl methacrylate) (PHEMA), ethylene glycol-ethylene oxide copolymer (PEG-PEO), and polymethacrylic acid (PMAA) gel electrolytes to optimize the electrochemical and physical properties of solid electrolytes.

[0479] Electrolyte salts

[0480] Electrolyte salts are ionizable lithium salts, which can be converted from Li... + X - Indicates. X - It can include the option 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 - Anions in the group composed of, etc.

[0481] Examples of lithium salts

[0482] For example, the lithium salt can be selected from LiTFSI, LiCl, LiBr, LiI, LiClO4, lithium tetrafluoroborate (LiBF4), LiB 10 Cl 10 The electrolyte salt may be any one of the following groups: lithium hexafluorophosphate (LiPF6), LiAsF6, LiSbF6, LiAlCl4, LiSCN, LiCF3CO2, LiCH3SO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC4F9SO3, LiC(CF3SO2)3, (CF3SO2)2NLi, lithium chloroborate, lower aliphatic carboxylic acids, lithium 4-phenylborate imide, lithium dioxolane borate (LiBOB), lithium difluorooxolane borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 4,5-dicyano-2-(trifluoromethyl)imazole (LiTDI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), etc. The electrolyte salt may comprise any combination of the salts described in this application.

[0483] Amount of electrolyte salts

[0484] Based on the total weight of the solid electrolyte layer 106, 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 of electrolyte salt. In an embodiment, based on the total weight of the solid electrolyte layer 106, the electrolyte salt in the solid electrolyte layer 106 may be within a range formed by selecting any two values ​​listed above or selecting any two values ​​between 0 and 400 parts or between 60 and 400 parts.

[0485] Ion conductivity of solid electrolyte layers

[0486] The solid electrolyte layer 106 may possess suitable reduction stability and / or ionic conductivity. Since the solid electrolyte layer 106 primarily functions to transport lithium ions between electrodes, it may possess, for example, 10... -7 S / cm, 10 -6 S / cm, 10 -5 S / cm or 10 -4 S / cm, which is around or exceeds its ideal ionic conductivity.

[0487] Thickness of solid electrolyte layer

[0488] The thickness t6 of the solid electrolyte layer 106 can be 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, 44 0, 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. 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 by selecting any two values ​​in the range of 0 μm to 1000 μm, for example, 5 μm to 1000 μm, 30 μm to 100 μm, or 30 μm to 50 μm.

[0489] Unfinished products

[0490] Figure 1 The cell 101 shown may be provided as an unfinished product. In one embodiment, the cell 101 may be stored, transported, and / or delivered to a distributor, customer, etc., for whom the manufacture of a battery assembly or product incorporating the cell 101 is completed. In other embodiments, the cell 101 is a finished battery assembly or product.

[0491] Sealed battery

[0492] The solid-state battery casing 112 can be sealed to complete the manufacture of the solid-state battery 100, enabling it to function as a battery. The sealing process can be designed with various techniques to ensure that internal components are protected from external environmental factors and to maintain the integrity of the battery structure. For example, methods such as laser welding, ultrasonic welding, or adhesive bonding can be used to achieve an airtight seal for the casing 112. In some cases, the sealing process may also include introducing a protective atmosphere or removing air to create a vacuum within the casing. This sealing step can help prevent the intrusion of moisture that could potentially degrade the performance of sulfide-based solid electrolytes. Furthermore, the encapsulation process can incorporate safety features such as pressure relief mechanisms to manage any potential gas buildup during battery operation.

[0493] After the battery is sealed

[0494] After proper sealing, the solid-state battery 100 can undergo final quality control checks, including electrical testing, leak detection, and visual inspection. Following these checks, the solid-state battery 100 can be packaged and sold as a finished product, and then integrated into various electronic devices, electric vehicles, energy storage systems, etc.

[0495] Battery composition

[0496] Solid-state battery 100 is provided in various configurations to suit different applications and device requirements. In some cases, the battery can be manufactured in a cylindrical shape, which can be advantageous for certain types of portable electronic devices or automotive applications. Alternatively, solid-state battery 100 can be manufactured in a prismatic shape, which allows for more efficient space utilization within devices with a rectangular form factor. In other cases, a pouch shape can be adopted, providing flexibility in form and potentially reducing the overall weight of the battery. Pouch shapes are further particularly suitable for solid-state batteries because it is easier to apply and control uniform pressure within the battery.

[0497] Choice of composition

[0498] The choice of configuration can depend on factors such as intended use, space constraints, thermal management requirements, and manufacturing considerations. In some implementations, hybrid or custom configurations combining different forms of elements may be utilized, if necessary. The diversity of battery form factors enables the integration of solid-state batteries into a wide range of products, from small wearable devices to large energy storage systems.

[0499] Voltage

[0500] The solid-state battery 100 is configured to output 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. Voltages of 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. In an embodiment, the output voltage of the solid-state battery 100 can be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within the range of 0 to 500 V, for example, 1 V DC to 500 V DC.

[0501] capacity

[0502] 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, or greater than such a capacity. In an embodiment, the output voltage of the solid-state battery 100 can have a capacity formed by selecting any two values ​​listed above or by selecting any two values ​​in the range of 0 to 300 mAh / g, for example, 100 mAh / g to 300 mAh / g.

[0503] Volume expansion calculation

[0504] The solid-state battery 100 can be configured to have an ideal volumetric expansion rate. The volumetric expansion rate can be calculated from the change in thickness after the first charge-discharge cycle compared to the initial thickness. The volumetric expansion rate can be the ratio of the thickness change to the initial thickness. The first charge-discharge cycle is performed by charging the battery at 0.1 C CC-CV and cutting off at 4.25 to 4.4 V and 0.02 C, and then discharging the battery at 0.1 C CC and cutting off at 3 V. The volumetric expansion rate is calculated using the following mathematical formula 1, where A can represent the thickness before charge-discharge, and B can represent the thickness after charge-discharge. The thickness can be measured using a Mauser micrometer or a scanning electron microscope (SEM).

[0505] Mathematical formula 1: Volume expansion rate = [( BA ) / A ]×100

[0506] C-fold

[0507] The C-rate used in this application refers to the rate of discharge of a battery relative to its maximum capacity. For example, a 1C rate means that the discharge current will discharge the entire battery in one hour. That is, for a 20 Ah battery, a 1C discharge current is 20 Amps.

[0508] Other examples of volume expansion

[0509] Other methods for measuring and calculating the volume expansion rate of solid-state batteries may include volume expansion measurement methods (such as gas gravity method), in-situ expansion measurement methods, X-ray tomography, strain gauge measurement methods, optical methods (such as digital image correlation or laser interferometry), pressure-based methods, and electrochemical strain microscopy.

[0510] Example

[0511] Embodiments will be described more fully below to facilitate a better understanding of this disclosure. However, the following embodiments are for illustrative purposes only, and the scope of this disclosure is not limited thereto.

[0512] Example 1: Solid Electrolyte Materials

[0513] Example 1.1: LPSCl

[0514] Powdered LPSCl was obtained. The particle size ranged from 0.1 μm to 50 μm.

[0515] Example 1.2: LPSBr

[0516] Powdered LPSBr was obtained. The particle size ranged from 0.1 μm to 50 μm.

[0517] Example 1.3: LPSI

[0518] Powdered LPSI was obtained. The particle size ranged from 0.1 μm to 50 μm.

[0519] Example 2: Additive materials

[0520] Example 2.1: Additive material represented by chemical formula 2

[0521] Obtain the additive material represented by chemical formula 2 in powder form: (Chemical formula 2).

[0522] Example 2.2: Additive material represented by chemical formula 5

[0523] Obtain the additive material represented by chemical formula 5 in powder form: (Chemical formula 5).

[0524] Example 2.3: Additive material represented by chemical formula 8

[0525] Obtain the additive material represented by chemical formula 8 in powder form: (Chemical formula 8).

[0526] Example 2.4: Additive material represented by chemical formula 11

[0527] Obtain the additive material represented by chemical formula 11 in powder form: (Chemical formula 11).

[0528] Example 2.5: Additive material represented by chemical formula 14

[0529] Obtain the additive material represented by chemical formula 14 in powder form: (Chemical formula 14).

[0530] Example 2.6: Additive material represented by chemical formula 17

[0531] Obtain the additive material represented by chemical formula 17 in powder form: (Chemical formula 17).

[0532] Example 2.7: Additive material represented by chemical formula 20

[0533] Obtain the additive material represented by chemical formula 20 in powder form: (Chemical formula 20).

[0534] Example 2.8: Additive material represented by chemical formula 23

[0535] To obtain the additive material represented by chemical formula 23 in powder form: (Chemical formula 23).

[0536] Example 2.9: Additive material represented by chemical formula 26

[0537] Obtain the additive material represented by chemical formula 26 in powder form: (Chemical formula 26).

[0538] Example 2.10: Additive material represented by chemical formula 29

[0539] To obtain the additive material represented by chemical formula 29 in powder form: (Chemical formula 29).

[0540] Example 2.11: Additive material represented by chemical formula 32

[0541] To obtain the additive material represented by chemical formula 32 in powder form: (Chemical formula 32).

[0542] Example 2.12: Additive material represented by chemical formula 35

[0543] To obtain the additive material represented by chemical formula 35 in powder form: (Chemical formula 35).

[0544] Example 3: Formation of a mixture for solid electrolytes

[0545] Example 3.1.1

[0546] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.1 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0547] Example 3.1.2

[0548] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.2 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0549] Example 3.1.3

[0550] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.3 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0551] Example 3.1.4

[0552] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.4 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0553] Example 3.1.5

[0554] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.5 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0555] Example 3.1.6

[0556] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.6 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0557] Example 3.1.7

[0558] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.7 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0559] Example 3.1.8

[0560] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.8 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0561] Example 3.1.9

[0562] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.9 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0563] Example 3.1.10

[0564] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.10 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling the mixture.

[0565] Example 3.1.11

[0566] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.11 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0567] Example 3.1.12

[0568] A mixture was obtained by mixing LPSCl from Example 1.1 with the additive material from Example 2.12 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling the mixture.

[0569] Example 3.2.1

[0570] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.1 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0571] Example 3.2.2

[0572] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.2 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0573] Example 3.2.3

[0574] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.3 at a weight ratio of 1:1. A solid electrode layer was prepared by ball milling the mixture.

[0575] Example 3.2.4

[0576] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.4 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0577] Example 3.2.5

[0578] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.5 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0579] Example 3.2.6

[0580] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.6 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0581] Example 3.2.7

[0582] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.7 at a weight ratio of 1:1. Solid electrode materials were then prepared by ball milling the mixture.

[0583] Example 3.2.8

[0584] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.8 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0585] Example 3.2.9

[0586] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.9 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0587] Example 3.2.10

[0588] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.10 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0589] Example 3.2.11

[0590] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.11 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0591] Example 3.2.12

[0592] A mixture was obtained by mixing LPSBr from Example 1.2 with the additive material from Example 2.12 at a weight ratio of 1:1. Solid electrode materials were prepared by ball milling this mixture.

[0593] Example 3.3.1

[0594] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.1 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0595] Example 3.3.2

[0596] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.2 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0597] Example 3.3.3

[0598] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.3 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0599] Example 3.3.4

[0600] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.4 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0601] Example 3.3.5

[0602] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.5 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0603] Example 3.3.6

[0604] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.6 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0605] Example 3.3.7

[0606] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.7 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0607] Example 3.3.8

[0608] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.8 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0609] Example 3.3.9

[0610] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.9 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0611] Example 3.3.10

[0612] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.10 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0613] Example 3.3.11

[0614] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.11 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0615] Example 3.3.12

[0616] A mixture was obtained by mixing LPSI from Example 1.3 with additive material from Example 2.12 at a weight ratio of 1:1. Solid electrode material was prepared by ball milling the mixture.

[0617] Example 4: Battery Assembly

[0618] [If any preferred specific positive and negative electrodes exist, they may be used in the embodiments]

[0619] Example 4.1.1

[0620] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.1 between the positive and negative electrodes to prepare a battery.

[0621] Example 4.1.2

[0622] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.2 between the positive and negative electrodes to prepare a battery.

[0623] Example 4.1.3

[0624] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.3 between the positive and negative electrodes to prepare a battery.

[0625] Example 4.1.4

[0626] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.4 between the positive and negative electrodes to prepare a battery.

[0627] Example 4.1.5

[0628] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.5 between the positive and negative electrodes to prepare a battery.

[0629] Example 4.1.6

[0630] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.6 between the positive and negative electrodes to prepare a battery.

[0631] Example 4.1.7

[0632] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.7 between the positive and negative electrodes to prepare a battery.

[0633] Example 4.1.8

[0634] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.8 between the positive and negative electrodes to prepare a battery.

[0635] Example 4.1.9

[0636] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.9 between the positive and negative electrodes to prepare a battery.

[0637] Example 4.1.10

[0638] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.10 between the positive and negative electrodes to prepare a battery.

[0639] Example 4.1.11

[0640] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.11 between the positive and negative electrodes to prepare a battery.

[0641] Example 4.1.12

[0642] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.12 between the positive and negative electrodes to prepare a battery.

[0643] Example 4.2.1

[0644] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.1 between the positive and negative electrodes to prepare a battery.

[0645] Example 4.2.2

[0646] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.2 between the positive and negative electrodes to prepare a battery.

[0647] Example 4.2.3

[0648] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.3 between the positive and negative electrodes to prepare a battery.

[0649] Example 4.2.4

[0650] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.4 between the positive and negative electrodes to prepare a battery.

[0651] Example 4.2.5

[0652] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.5 between the positive and negative electrodes to prepare a battery.

[0653] Example 4.2.6

[0654] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.6 between the positive and negative electrodes to prepare a battery.

[0655] Example 4.2.7

[0656] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.7 between the positive and negative electrodes to prepare a battery.

[0657] Example 4.2.8

[0658] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.8 between the positive and negative electrodes to prepare a battery.

[0659] Example 4.2.9

[0660] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.9 between the positive and negative electrodes to prepare a battery.

[0661] Example 4.2.10

[0662] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.10 between the positive and negative electrodes to prepare a battery.

[0663] Example 4.2.11

[0664] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.2.11 between the positive and negative electrodes to prepare a battery.

[0665] Example 4.2.12

[0666] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.1.12 between the positive and negative electrodes to prepare a battery.

[0667] Example 4.3.1

[0668] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.1 between the positive and negative electrodes to prepare a battery.

[0669] Example 4.3.2

[0670] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.2 between the positive and negative electrodes to prepare a battery.

[0671] Example 4.3.3

[0672] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.3 between the positive and negative electrodes to prepare a battery.

[0673] Example 4.3.4

[0674] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.4 between the positive and negative electrodes to prepare a battery.

[0675] Example 4.3.5

[0676] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.5 between the positive and negative electrodes to prepare a battery.

[0677] Example 4.3.6

[0678] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.6 between the positive and negative electrodes to prepare a battery.

[0679] Example 4.3.7

[0680] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.7 between the positive and negative electrodes to prepare a battery.

[0681] Example 4.3.8

[0682] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.8 between the positive and negative electrodes to prepare a battery.

[0683] Example 4.3.9

[0684] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.9 between the positive and negative electrodes to prepare a battery.

[0685] Example 4.3.10

[0686] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.10 between the positive and negative electrodes to prepare a battery.

[0687] Example 4.3.11

[0688] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.11 between the positive and negative electrodes to prepare a battery.

[0689] Example 4.3.12

[0690] Obtain the positive electrode. Obtain the negative electrode. Place a solid electrolyte layer containing the solid electrolyte material from Example 3.3.12 between the positive and negative electrodes to prepare a battery.

[0691] Example 5: Measurement of Lithium-ion Diffusion

[0692] Example 5.1.1.1

[0693] The battery from Example 4.1.1 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0694] Example 5.1.1.2

[0695] The battery from Example 4.1.2 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0696] Example 5.1.1.3

[0697] The battery from Example 4.1.3 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0698] Example 5.1.1.4

[0699] The battery from Example 4.1.4 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0700] Example 5.1.1.5

[0701] The battery from Example 4.1.5 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0702] Example 5.1.1.6

[0703] The battery from Example 4.1.6 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0704] Example 5.1.1.7

[0705] The battery from Example 4.1.7 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0706] Example 5.1.1.8

[0707] The battery from Example 4.1.8 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0708] Example 5.1.1.9

[0709] The battery from Example 4.1.9 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0710] Example 5.1.1.10

[0711] The battery from Example 4.1.10 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0712] Example 5.1.1.11

[0713] The battery from Example 4.1.11 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0714] Example 5.1.1.12

[0715] The battery from Example 4.1.12 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0716] Example 5.1.2.1

[0717] The battery from Example 4.2.1 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0718] Example 5.1.2.2

[0719] The battery from Example 4.2.2 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0720] Example 5.1.2.3

[0721] The battery from Example 4.2.3 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0722] Example 5.1.2.4

[0723] The battery from Example 4.2.4 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0724] Example 5.1.2.5

[0725] The battery from Example 4.2.5 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0726] Example 5.1.2.6

[0727] The battery from Example 4.2.6 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0728] Example 5.1.2.7

[0729] The battery from Example 4.2.7 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0730] Example 5.1.2.8

[0731] The battery from Example 4.2.8 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0732] Example 5.1.2.9

[0733] The battery from Example 4.2.9 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0734] Example 5.1.2.10

[0735] The battery from Example 4.2.10 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0736] Example 5.1.2.11

[0737] The battery from Example 4.2.11 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0738] Example 5.1.2.12

[0739] The battery from Example 4.2.12 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0740] Example 5.1.3.1

[0741] The battery from Example 4.3.1 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0742] Example 5.1.3.2

[0743] The battery from Example 4.3.2 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0744] Example 5.1.3.3

[0745] The battery from Example 4.3.3 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0746] Example 5.1.3.4

[0747] The battery from Example 4.3.4 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0748] Example 5.1.3.5

[0749] The battery from Example 4.3.5 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0750] Example 5.1.3.6

[0751] The battery from Example 4.3.6 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0752] Example 5.1.3.7

[0753] The battery from Example 4.3.7 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0754] Example 5.1.3.8

[0755] The battery from Example 4.3.8 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0756] Example 5.1.3.9

[0757] The battery from Example 4.3.9 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0758] Example 5.1.3.10

[0759] The battery from Example 4.3.10 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0760] Example 5.1.3.11

[0761] The battery from Example 4.3.11 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0762] Example 5.1.3.12

[0763] The battery from Example 4.3.12 was operated at a pressure of 1 MPa. The lithium-ion diffusion of the battery was measured.

[0764] Example 5.2.1.1

[0765] The battery from Example 4.1.1 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0766] Example 5.2.1.2

[0767] The battery from Example 4.1.2 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0768] Example 5.2.1.3

[0769] The battery from Example 4.1.3 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0770] Example 5.2.1.4

[0771] The battery from Example 4.1.4 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0772] Example 5.2.1.5

[0773] The battery from Example 4.1.5 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0774] Example 5.2.1.6

[0775] The battery from Example 4.1.6 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0776] Example 5.2.1.7

[0777] The battery from Example 4.1.7 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0778] Example 5.2.1.8

[0779] The battery from Example 4.1.8 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0780] Example 5.2.1.9

[0781] The battery from Example 4.1.9 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0782] Example 5.2.1.10

[0783] The battery from Example 4.1.10 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0784] Example 5.2.1.11

[0785] The battery from Example 4.1.11 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0786] Example 5.2.1.12

[0787] The battery from Example 4.1.12 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0788] Example 5.2.2.1

[0789] The battery from Example 4.2.1 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0790] Example 5.2.2.2

[0791] The battery from Example 4.2.2 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0792] Example 5.2.2.3

[0793] The battery from Example 4.2.3 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0794] Example 5.2.2.4

[0795] The battery from Example 4.2.4 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0796] Example 5.2.2.5

[0797] The battery from Example 4.2.5 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0798] Example 5.2.2.6

[0799] The battery from Example 4.2.6 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0800] Example 5.2.2.7

[0801] The battery from Example 4.2.7 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0802] Example 5.2.2.8

[0803] The battery from Example 4.2.8 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0804] Example 5.2.2.9

[0805] The battery from Example 4.2.9 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0806] Example 5.2.2.10

[0807] The battery from Example 4.2.10 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0808] Example 5.2.2.11

[0809] The battery from Example 4.2.11 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0810] Example 5.2.2.12

[0811] The battery from Example 4.2.12 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0812] Example 5.2.3.1

[0813] The battery from Example 4.3.1 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0814] Example 5.2.3.2

[0815] The battery from Example 4.3.2 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0816] Example 5.2.3.3

[0817] The battery from Example 4.3.3 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0818] Example 5.2.3.4

[0819] The battery from Example 4.3.4 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0820] Example 5.2.3.5

[0821] The battery from Example 4.3.5 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0822] Example 5.2.3.6

[0823] The battery from Example 4.3.6 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0824] Example 5.2.3.7

[0825] The battery from Example 4.3.7 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0826] Example 5.2.3.8

[0827] The battery from Example 4.3.8 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0828] Example 5.2.3.9

[0829] The battery from Example 4.3.9 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0830] Example 5.2.3.10

[0831] The battery from Example 4.3.10 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0832] Example 5.2.3.11

[0833] The battery from Example 4.3.11 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0834] Example 5.2.3.12

[0835] The battery from Example 4.3.12 was operated at a pressure of 2 MPa. The lithium-ion diffusion of the battery was measured.

[0836] Example 5.3.1.1

[0837] The battery from Example 4.1.1 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0838] Example 5.3.1.2

[0839] The battery from Example 4.1.2 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0840] Example 5.3.1.3

[0841] The battery from Example 4.1.3 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0842] Example 5.3.1.4

[0843] The battery from Example 4.1.4 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0844] Example 5.3.1.5

[0845] The battery from Example 4.1.5 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0846] Example 5.3.1.6

[0847] The battery from Example 4.1.6 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0848] Example 5.3.1.7

[0849] The battery from Example 4.1.7 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0850] Example 5.3.1.8

[0851] The battery from Example 4.1.8 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0852] Example 5.3.1.9

[0853] The battery from Example 4.1.9 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0854] Example 5.3.1.10

[0855] The battery from Example 4.1.10 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0856] Example 5.3.1.11

[0857] The battery from Example 4.1.11 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0858] Example 5.3.1.12

[0859] The battery from Example 4.1.12 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0860] Example 5.3.2.1

[0861] The battery from Example 4.2.1 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0862] Example 5.3.2.2

[0863] The battery from Example 4.2.2 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0864] Example 5.3.2.3

[0865] The battery from Example 4.2.3 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0866] Example 5.3.2.4

[0867] The battery from Example 4.2.4 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0868] Example 5.3.2.5

[0869] The battery from Example 4.2.5 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0870] Example 5.3.2.6

[0871] The battery from Example 4.2.6 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0872] Example 5.3.2.7

[0873] The battery from Example 4.2.7 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0874] Example 5.3.2.8

[0875] The battery from Example 4.2.8 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0876] Example 5.3.2.9

[0877] The battery from Example 4.2.9 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0878] Example 5.3.2.10

[0879] The battery from Example 4.2.10 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0880] Example 5.3.2.11

[0881] The battery from Example 4.2.11 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0882] Example 5.3.2.12

[0883] The battery from Example 4.2.12 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0884] Example 5.3.3.1

[0885] The battery from Example 4.3.1 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0886] Example 5.3.3.2

[0887] The battery from Example 4.3.2 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0888] Example 5.3.3.3

[0889] The battery from Example 4.3.3 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0890] Example 5.3.3.4

[0891] The battery from Example 4.3.4 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0892] Example 5.3.3.5

[0893] The battery from Example 4.3.5 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0894] Example 5.3.3.6

[0895] The battery from Example 4.3.6 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0896] Example 5.3.3.7

[0897] The battery from Example 4.3.7 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0898] Example 5.3.3.8

[0899] The battery from Example 4.3.8 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0900] Example 5.3.3.9

[0901] The battery from Example 4.3.9 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0902] Example 5.3.3.10

[0903] The battery from Example 4.3.10 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0904] Example 5.3.3.11

[0905] The battery from Example 4.3.11 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0906] Example 5.3.3.12

[0907] The battery from Example 4.3.12 was operated at a pressure of 3 MPa. The lithium-ion diffusion of the battery was measured.

[0908] Example 5.4.1.1

[0909] The battery from Example 4.1.1 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0910] Example 5.4.1.2

[0911] The battery from Example 4.1.2 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0912] Example 5.4.1.3

[0913] The battery from Example 4.1.3 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0914] Example 5.4.1.4

[0915] The battery from Example 4.4.1.4 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0916] Example 5.4.1.5

[0917] The battery from Example 4.1.5 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0918] Example 5.4.1.6

[0919] The battery from Example 4.1.6 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0920] Example 5.4.1.7

[0921] The battery from Example 4.1.7 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0922] Example 5.4.1.8

[0923] The battery from Example 4.1.8 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0924] Example 5.4.1.9

[0925] The battery from Example 4.1.9 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0926] Example 5.4.1.10

[0927] The battery from Example 4.1.10 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0928] Example 5.4.1.11

[0929] The battery from Example 4.1.11 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0930] Example 5.4.1.12

[0931] The battery from Example 4.1.12 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0932] Example 5.4.2.1

[0933] The battery from Example 4.2.1 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0934] Example 5.4.2.2

[0935] The battery from Example 4.2.2 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0936] Example 5.4.2.3

[0937] The battery from Example 4.2.3 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0938] Example 5.4.2.4

[0939] The battery from Example 4.2.4 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0940] Example 5.4.2.5

[0941] The battery from Example 4.2.5 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0942] Example 5.4.2.6

[0943] The battery from Example 4.2.6 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0944] Example 5.4.2.7

[0945] The battery from Example 4.2.7 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0946] Example 5.4.2.8

[0947] The battery from Example 4.2.8 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0948] Example 5.4.2.9

[0949] The battery from Example 4.2.9 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0950] Example 5.4.2.10

[0951] The battery from Example 4.2.10 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0952] Example 5.4.2.11

[0953] The battery from Example 4.2.11 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0954] Example 5.4.2.12

[0955] The battery from Example 4.2.12 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0956] Example 5.4.3.1

[0957] The battery from Example 4.3.1 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0958] Example 5.4.3.2

[0959] The battery from Example 4.3.2 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0960] Example 5.4.3.3

[0961] The battery from Example 4.3.3 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0962] Example 5.4.3.4

[0963] The battery from Example 4.3.4 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0964] Example 5.4.3.5

[0965] The battery from Example 4.3.5 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0966] Example 5.4.3.6

[0967] The battery from Example 4.3.6 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0968] Example 5.4.3.7

[0969] The battery from Example 4.3.7 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0970] Example 5.4.3.8

[0971] The battery from Example 4.3.8 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0972] Example 5.4.3.9

[0973] The battery from Example 4.3.9 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0974] Example 5.4.3.10

[0975] The battery from Example 4.3.10 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0976] Example 5.4.3.11

[0977] The battery from Example 4.3.11 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0978] Example 5.4.3.12

[0979] The battery from Example 4.3.12 was operated at a pressure of 4 MPa. The lithium-ion diffusion of the battery was measured.

[0980] Example 5.5.1.1

[0981] The battery from Example 4.1.1 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0982] Example 5.5.1.2

[0983] The battery from Example 4.1.2 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0984] Example 5.5.1.3

[0985] The battery from Example 4.1.3 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0986] Example 5.5.1.4

[0987] The battery from Example 4.1.4 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0988] Example 5.5.1.5

[0989] The battery from Example 4.1.5 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0990] Example 5.5.1.6

[0991] The battery from Example 4.1.6 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0992] Example 5.5.1.7

[0993] The battery from Example 4.1.7 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0994] Example 5.5.1.8

[0995] The battery from Example 4.1.8 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0996] Example 5.5.1.9

[0997] The battery from Example 4.1.9 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[0998] Example 5.5.1.10

[0999] The battery from Example 4.1.10 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1000] Example 5.5.1.11

[1001] The battery from Example 4.1.11 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1002] Example 5.5.1.12

[1003] The battery from Example 4.1.12 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1004] Example 5.5.2.1

[1005] The battery from Example 4.2.1 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1006] Example 5.5.2.2

[1007] The battery from Example 4.2.2 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1008] Example 5.5.2.3

[1009] The battery from Example 4.2.3 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1010] Example 5.5.2.4

[1011] The battery from Example 4.2.4 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1012] Example 5.5.2.5

[1013] The battery from Example 4.2.5 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1014] Example 5.5.2.6

[1015] The battery from Example 4.2.6 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1016] Example 5.5.2.7

[1017] The battery from Example 4.2.7 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1018] Example 5.5.2.8

[1019] The battery from Example 4.2.8 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1020] Example 5.5.2.9

[1021] The battery from Example 4.2.9 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1022] Example 5.5.2.10

[1023] The battery from Example 4.2.10 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1024] Example 5.5.2.11

[1025] The battery from Example 4.2.11 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1026] Example 5.5.2.12

[1027] The battery from Example 4.2.12 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1028] Example 5.5.3.1

[1029] The battery from Example 4.3.1 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1030] Example 5.5.3.2

[1031] The battery from Example 4.3.2 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1032] Example 5.5.3.3

[1033] The battery from Example 4.3.3 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1034] Example 5.5.3.4

[1035] The battery from Example 4.3.4 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1036] Example 5.5.3.5

[1037] The battery from Example 4.3.5 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1038] Example 5.5.3.6

[1039] The battery from Example 4.3.6 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1040] Example 5.5.3.7

[1041] The battery from Example 4.3.7 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1042] Example 5.5.3.8

[1043] The battery from Example 4.3.8 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1044] Example 5.5.3.9

[1045] The battery from Example 4.3.9 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1046] Example 5.5.3.10

[1047] The battery from Example 4.3.10 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1048] Example 5.5.3.11

[1049] The battery from Example 4.3.11 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1050] Example 5.5.3.12

[1051] The battery from Example 4.3.12 was operated at a pressure of 5 MPa. The lithium-ion diffusion of the battery was measured.

[1052] Example 6: Measurement of specific capacity

[1053] Example 6.1.1.1

[1054] The battery from Example 4.1.1 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1055] Example 6.1.1.2

[1056] The battery from Example 4.1.2 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1057] Example 6.1.1.3

[1058] The battery from Example 4.1.3 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1059] Example 6.1.1.4

[1060] The battery from Example 4.1.4 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1061] Example 6.1.1.5

[1062] The battery from Example 4.1.5 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1063] Example 6.1.1.6

[1064] The battery from Example 4.1.6 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1065] Example 6.1.1.7

[1066] The battery from Example 4.1.7 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1067] Example 6.1.1.8

[1068] The battery from Example 4.1.8 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1069] Example 6.1.1.9

[1070] The battery from Example 4.1.9 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1071] Example 6.1.1.10

[1072] The battery from Example 4.1.10 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1073] Example 6.1.1.11

[1074] The battery from Example 4.1.11 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1075] Example 6.1.1.12

[1076] The battery from Example 4.1.12 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1077] Example 6.1.2.1

[1078] The battery from Example 4.2.1 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1079] Example 6.1.2.2

[1080] The battery from Example 4.2.2 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1081] Example 6.1.2.3

[1082] The battery from Example 4.2.3 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1083] Example 6.1.2.4

[1084] The battery from Example 4.2.4 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1085] Example 6.1.2.5

[1086] The battery from Example 4.2.5 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1087] Example 6.1.2.6

[1088] The battery from Example 4.2.6 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1089] Example 6.1.2.7

[1090] The battery from Example 4.2.7 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1091] Example 6.1.2.8

[1092] The battery from Example 4.2.8 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1093] Example 6.1.2.9

[1094] The battery from Example 4.2.9 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1095] Example 6.1.2.10

[1096] The battery from Example 4.2.10 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1097] Example 6.1.2.11

[1098] The battery from Example 4.2.11 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1099] Example 6.1.2.12

[1100] The battery from Example 4.2.12 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1101] Example 6.1.3.1

[1102] The battery from Example 4.3.1 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1103] Example 6.1.3.2

[1104] The battery from Example 4.3.2 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1105] Example 6.1.3.3

[1106] The battery from Example 4.3.3 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1107] Example 6.1.3.4

[1108] The battery from Example 4.3.4 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1109] Example 6.1.3.5

[1110] The battery from Example 4.3.5 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1111] Example 6.1.3.6

[1112] The battery from Example 4.3.6 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1113] Example 6.1.3.7

[1114] The battery from Example 4.3.7 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1115] Example 6.1.3.8

[1116] The battery from Example 4.3.8 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1117] Example 6.1.3.9

[1118] The battery from Example 4.3.9 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1119] Example 6.1.3.10

[1120] The battery from Example 4.3.10 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1121] Example 6.1.3.11

[1122] The battery from Example 4.3.11 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1123] Example 6.1.3.12

[1124] The battery from Example 4.3.12 was operated at a pressure of 1 MPa. The specific capacity of the battery was measured.

[1125] Example 6.2.1.1

[1126] The battery from Example 4.1.1 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1127] Example 6.2.1.2

[1128] The battery from Example 4.1.2 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1129] Example 6.2.1.3

[1130] The battery from Example 4.1.3 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1131] Example 6.2.1.4

[1132] The battery from Example 4.1.4 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1133] Example 6.2.1.5

[1134] The battery from Example 4.1.5 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1135] Example 6.2.1.6

[1136] The battery from Example 4.1.6 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1137] Example 6.2.1.7

[1138] The battery from Example 4.1.7 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1139] Example 6.2.1.8

[1140] The battery from Example 4.1.8 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1141] Example 6.2.1.9

[1142] The battery from Example 4.1.9 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1143] Example 6.2.1.10

[1144] The battery from Example 4.1.10 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1145] Example 6.2.1.11

[1146] The battery from Example 4.1.11 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1147] Example 6.2.1.12

[1148] The battery from Example 4.1.12 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1149] Example 6.2.2.1

[1150] The battery from Example 4.2.1 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1151] Example 6.2.2.2

[1152] The battery from Example 4.2.2 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1153] Example 6.2.2.3

[1154] The battery from Example 4.2.3 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1155] Example 6.2.2.4

[1156] The battery from Example 4.2.4 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1157] Example 6.2.2.5

[1158] The battery from Example 4.2.5 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1159] Example 6.2.2.6

[1160] The battery from Example 4.2.6 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1161] Example 6.2.2.7

[1162] The battery from Example 4.2.7 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1163] Example 6.2.2.8

[1164] The battery from Example 4.2.8 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1165] Example 6.2.2.9

[1166] The battery from Example 4.2.9 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1167] Example 6.2.2.10

[1168] The battery from Example 4.2.10 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1169] Example 6.2.2.11

[1170] The battery from Example 4.2.11 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1171] Example 6.2.2.12

[1172] The battery from Example 4.2.12 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1173] Example 6.2.3.1

[1174] The battery from Example 4.3.1 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1175] Example 6.2.3.2

[1176] The battery from Example 4.3.2 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1177] Example 6.2.3.3

[1178] The battery from Example 4.3.3 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1179] Example 6.2.3.4

[1180] The battery from Example 4.3.4 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1181] Example 6.2.3.5

[1182] The battery from Example 4.3.5 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1183] Example 6.2.3.6

[1184] The battery from Example 4.3.6 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1185] Example 6.2.3.7

[1186] The battery from Example 4.3.7 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1187] Example 6.2.3.8

[1188] The battery from Example 4.3.8 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1189] Example 6.2.3.9

[1190] The battery from Example 4.3.9 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1191] Example 6.2.3.10

[1192] The battery from Example 4.3.10 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1193] Example 6.2.3.11

[1194] The battery from Example 4.3.11 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1195] Example 6.2.3.12

[1196] The battery from Example 4.3.12 was operated at a pressure of 2 MPa. The specific capacity of the battery was measured.

[1197] Example 6.3.1.1

[1198] The battery from Example 4.1.1 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1199] Example 6.3.1.2

[1200] The battery from Example 4.1.2 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1201] Example 6.3.1.3

[1202] The battery from Example 4.1.3 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1203] Example 6.3.1.4

[1204] The battery from Example 4.1.4 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1205] Example 6.3.1.5

[1206] The battery from Example 4.1.5 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1207] Example 6.3.1.6

[1208] The battery from Example 4.1.6 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1209] Example 6.3.1.7

[1210] The battery from Example 4.1.7 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1211] Example 6.3.1.8

[1212] The battery from Example 4.1.8 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1213] Example 6.3.1.9

[1214] The battery from Example 4.1.9 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1215] Example 6.3.1.10

[1216] The battery from Example 4.1.10 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1217] Example 6.3.1.11

[1218] The battery from Example 4.1.11 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1219] Example 6.3.1.12

[1220] The battery from Example 4.1.12 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1221] Example 6.3.2.1

[1222] The battery from Example 4.2.1 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1223] Example 6.3.2.2

[1224] The battery from Example 4.2.2 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1225] Example 6.3.2.3

[1226] The battery from Example 4.2.3 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1227] Example 6.3.2.4

[1228] The battery from Example 4.2.4 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1229] Example 6.3.2.5

[1230] The battery from Example 4.2.5 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1231] Example 6.3.2.6

[1232] The battery from Example 4.2.6 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1233] Example 6.3.2.7

[1234] The battery from Example 4.2.7 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1235] Example 6.3.2.8

[1236] The battery from Example 4.2.8 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1237] Example 6.3.2.9

[1238] The battery from Example 4.2.9 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1239] Example 6.3.2.10

[1240] The battery from Example 4.2.10 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1241] Example 6.3.2.11

[1242] The battery from Example 4.2.11 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1243] Example 6.3.2.12

[1244] The battery from Example 4.2.12 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1245] Example 6.3.3.1

[1246] The battery from Example 4.3.1 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1247] Example 6.3.3.2

[1248] The battery from Example 4.3.2 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1249] Example 6.3.3.3

[1250] The battery from Example 4.3.3 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1251] Example 6.3.3.4

[1252] The battery from Example 4.3.4 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1253] Example 6.3.3.5

[1254] The battery from Example 4.3.5 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1255] Example 6.3.3.6

[1256] The battery from Example 4.3.6 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1257] Example 6.3.3.7

[1258] The battery from Example 4.3.7 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1259] Example 6.3.3.8

[1260] The battery from Example 4.3.8 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1261] Example 6.3.3.9

[1262] The battery from Example 4.3.9 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1263] Example 6.3.3.10

[1264] The battery from Example 4.3.10 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1265] Example 6.3.3.11

[1266] The battery from Example 4.3.11 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1267] Example 6.3.3.12

[1268] The battery from Example 4.3.12 was operated at a pressure of 3 MPa. The specific capacity of the battery was measured.

[1269] Example 6.4.1.1

[1270] The battery from Example 4.1.1 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1271] Example 6.4.1.2

[1272] The battery from Example 4.1.2 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1273] Example 6.4.1.3

[1274] The battery from Example 4.1.3 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1275] Example 6.4.1.4

[1276] The battery from Example 4.4.1.4 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1277] Example 6.4.1.5

[1278] The battery from Example 4.1.5 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1279] Example 6.4.1.6

[1280] The battery from Example 4.1.6 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1281] Example 6.4.1.7

[1282] The battery from Example 4.1.7 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1283] Example 6.4.1.8

[1284] The battery from Example 4.1.8 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1285] Example 6.4.1.9

[1286] The battery from Example 4.1.9 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1287] Example 6.4.1.10

[1288] The battery from Example 4.1.10 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1289] Example 6.4.1.11

[1290] The battery from Example 4.1.11 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1291] Example 6.4.1.12

[1292] The battery from Example 4.1.12 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1293] Example 6.4.2.1

[1294] The battery from Example 4.2.1 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1295] Example 6.4.2.2

[1296] The battery from Example 4.2.2 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1297] Example 6.4.2.3

[1298] The battery from Example 4.2.3 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1299] Example 6.4.2.4

[1300] The battery from Example 4.2.4 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1301] Example 6.4.2.5

[1302] The battery from Example 4.2.5 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1303] Example 6.4.2.6

[1304] The battery from Example 4.2.6 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1305] Example 6.4.2.7

[1306] The battery from Example 4.2.7 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1307] Example 6.4.2.8

[1308] The battery from Example 4.2.8 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1309] Example 6.4.2.9

[1310] The battery from Example 4.2.9 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1311] Example 6.4.21.10

[1312] The battery from Example 4.2.10 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1313] Example 6.4.2.11

[1314] The battery from Example 4.2.11 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1315] Example 6.4.2.12

[1316] The battery from Example 4.2.12 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1317] Example 6.4.3.1

[1318] The battery from Example 4.3.1 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1319] Example 6.4.3.2

[1320] The battery from Example 4.3.2 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1321] Example 6.4.3.3

[1322] The battery from Example 4.3.3 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1323] Example 6.4.3.4

[1324] The battery from Example 4.3.4 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1325] Example 6.4.3.5

[1326] The battery from Example 4.3.5 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1327] Example 6.4.3.6

[1328] The battery from Example 4.3.6 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1329] Example 6.4.3.7

[1330] The battery from Example 4.3.7 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1331] Example 6.4.3.8

[1332] The battery from Example 4.3.8 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1333] Example 6.4.3.9

[1334] The battery from Example 4.3.9 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1335] Example 6.4.3.10

[1336] The battery from Example 4.3.10 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1337] Example 6.4.3.11

[1338] The battery from Example 4.3.11 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1339] Example 6.4.3.12

[1340] The battery from Example 4.3.12 was operated at a pressure of 4 MPa. The specific capacity of the battery was measured.

[1341] Example 6.5.1.1

[1342] The battery from Example 4.1.1 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1343] Example 6.5.1.2

[1344] The battery from Example 4.1.2 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1345] Example 6.5.1.3

[1346] The battery from Example 4.1.3 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1347] Example 6.5.1.4

[1348] The battery from Example 4.1.4 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1349] Example 6.5.1.5

[1350] The battery from Example 4.1.5 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1351] Example 6.5.1.6

[1352] The battery from Example 4.1.6 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1353] Example 6.5.1.7

[1354] The battery from Example 4.1.7 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1355] Example 6.5.1.8

[1356] The battery from Example 4.1.8 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1357] Example 6.5.1.9

[1358] The battery from Example 4.1.9 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1359] Example 6.5.1.10

[1360] The battery from Example 4.1.10 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1361] Example 6.5.1.11

[1362] The battery from Example 4.1.11 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1363] Example 6.5.1.12

[1364] The battery from Example 4.1.12 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1365] Example 6.5.2.1

[1366] The battery from Example 4.2.1 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1367] Example 6.5.2.2

[1368] The battery from Example 4.2.2 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1369] Example 6.5.2.3

[1370] The battery from Example 4.2.3 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1371] Example 6.5.2.4

[1372] The battery from Example 4.2.4 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1373] Example 6.5.2.5

[1374] The battery from Example 4.2.5 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1375] Example 6.5.2.6

[1376] The battery from Example 4.2.6 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1377] Example 6.5.2.7

[1378] The battery from Example 4.2.7 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1379] Example 6.5.2.8

[1380] The battery from Example 4.2.8 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1381] Example 6.5.2.9

[1382] The battery from Example 4.2.9 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1383] Example 6.5.2.10

[1384] The battery from Example 4.2.10 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1385] Example 6.5.2.11

[1386] The battery from Example 4.2.11 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1387] Example 6.5.2.12

[1388] The battery from Example 4.2.12 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1389] Example 6.5.3.1

[1390] The battery from Example 4.3.1 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1391] Example 6.5.3.2

[1392] The battery from Example 4.3.2 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1393] Example 6.5.3.3

[1394] The battery from Example 4.3.3 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1395] Example 6.5.3.4

[1396] The battery from Example 4.3.4 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1397] Example 6.5.3.5

[1398] The battery from Example 4.3.5 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1399] Example 6.5.3.6

[1400] The battery from Example 4.3.6 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1401] Example 6.5.3.7

[1402] The battery from Example 4.3.7 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1403] Example 6.5.3.8

[1404] The battery from Example 4.3.8 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1405] Example 6.5.3.9

[1406] The battery from Example 4.3.9 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1407] Example 6.5.3.10

[1408] The battery from Example 4.3.10 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1409] Example 6.5.3.11

[1410] The battery from Example 4.3.11 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1411] Example 6.5.3.12

[1412] The battery from Example 4.3.12 was operated at a pressure of 5 MPa. The specific capacity of the battery was measured.

[1413] Included combinations and features

[1414] This specification describes various features and characteristics to provide an understanding of the composition, structure, production, function, and / or operation of this disclosure, including the disclosed compositions, coatings, and methods. It should be understood that the various features and characteristics of this disclosure described herein can be combined in any suitable manner, whether or not such features and characteristics are explicitly described as combinations herein. The inventors and the applicant expressly intend that combinations of such features and characteristics be included within the scope of this disclosure as set forth in this specification. Therefore, the claims may be modified to state any feature and characteristic expressly or inherently recited or otherwise expressly or inherently supported in this specification in any combination. Furthermore, the applicant reserves the right to amend the claims to expressly waive features and characteristics that may be present in the prior art (even if such features and characteristics are not expressly described in this specification). Therefore, any such amendment will not add new information to this specification or the claims and will comply with the requirements of written description, sufficient disclosure, and addition.

[1415] References merged

[1416] Any patent, publication, or other document mentioned in this specification is incorporated herein in its entirety, unless otherwise stated, but only to the extent that the incorporated material does not contradict any existing descriptions, definitions, statements, illustrations, or other disclosures expressly set forth in this specification. Therefore, to the extent necessary, the explicit disclosures set forth in this specification shall supersede any contradictory material incorporated by reference. Any material or portion thereof incorporated by reference that contradicts any existing definitions, statements, or other disclosures set forth in this application shall be incorporated only to the extent that the incorporated material does not contradict existing disclosures. The applicant reserves the right to amend this specification to expressly represent any incorporated subject matter or portion thereof. Modifications to this specification incorporating such incorporated subject matter will comply with the requirements of written description, full disclosure, and addition.

[1417] Explanation from all aspects

[1418] While this disclosure provides descriptions of various specific aspects to illustrate different aspects of this disclosure and / or its potential applications, it should be understood that various changes and modifications can be made by those skilled in the art. Therefore, this disclosure should be understood as having the broad scope defined at least as claimed, and not as narrowly limited as the specific exemplary aspects provided in this application.

Claims

1. A solid-state battery, comprising: positive electrode; negative electrode; A solid electrolyte layer is disposed between the positive electrode and the negative electrode, and is configured to enable lithium ion transport between the positive electrode and the negative electrode. in, The solid electrolyte layer comprises: Particles containing sulfide-containing materials; and Additive materials represented by A—B—C (chemical formula 1), Where A is a thiol group (SH) or a leaving group. A is configured to interact with sulfur in the sulfide-containing material within the particles, and at least a portion of the additive material is sandwiched between two directly adjacent particles within the particles. Wherein, when A is a leaving group, A is selected from the group consisting of chlorine, bromine, iodine, toluenesulfonate (p-toluenesulfonate) or methanesulfonate (methanesulfonate) group, acetate group or trifluoroacetate group, phosphate group or phosphonate group, carboxylic acid ester group, alkoxide group, amino group, cyano (CN) group, azide (N3) group, sulfonate group, triethoxysilyl, trimethoxysilyl and combinations thereof. Wherein, B is a C3-C20 perfluoroalkane group with or without substituents, selected from 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), and 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 Alkane (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)2CH2CH3), 3,3-dimethylheptane (CH3CH2CH(CH3)2CH2CH2CH2CH3), 3-ethylheptane (CH3CH2) CH2CH(CH2CH3)CH2CH3), n-decane (CH3(CH2)8CH3), 2-methylnonane (CH3CH2CH2CH2CH2CH2CH2CH(CH3)CH3), 3-methylnonane (CH3CH2CH2CH2CH2CH2CH(CH3)CH2CH3), 2,2-dimethyloctane (CH3C(CH3)2(CH2)6CH3), 2,3-dimethyloctane (CH3CH(CH3)CH2CH2CH2CH2C) H2CH(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 isomers, n-tetane (C 13 H 28 ) and its branched isomers, n-tetradecane (C 14 H 30 ) and its branched isomers, n-pentadecane (C 15 H 32 ) and its branched isomers, n-hexadecane (C 16 H 34 ) and its branched isomers, n-heptadecane (C 17 H 36 ) and its branched isomers, n-octadecane (C 18 H 38 ) and its branched isomers, n-nonadecane (C 19 H 40 ) and its branched isomers, n-eicosane (C 20 H 42 ) and its branched isomers and their combinations, comprising the alkane group, When B is a C3-C20 perfluoroalkane group with substituents, B includes groups selected from fluorine (-F), chlorine (-Cl), bromine (-Br), iodine (-I), hydroxyl (-OH), ether (-OR), aldehyde (-CHO), ketone (-CO), carboxyl (-COOH), ester (-COOR), peroxy (-OO-), amino (-NH2), secondary amine (-NHR), tertiary amine (-NR2), nitro (-NO2), cyano (-CN), amide (-CONH2), substituted amide (-CONHR, -CONR2), mercapto (-SH), thioether (-SR), and sulfonyl (-SO2R). Substituents in the group consisting of sulfate ester (-SO4R), phosphate ester (-PO4R2), phosphin (-PR2), alkyl (-R), alkenyl (-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, etc. Wherein, C is a sulfonate, phosphate, or selected from 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) + ), imidazolyl (C3H4NH2) + ), Phosphorus (P) + (CH3)4), guanidine (C(NH2)3) + Sulfonates or phosphates and combinations thereof are sulfonates or phosphates in the group consisting of sulfonates or phosphates and combinations thereof.

2. The solid-state battery as described in claim 1, wherein, At least a portion of the additive material is in contact with the surface of either of the two adjacent particles.

3. The solid-state battery as described in claim 2, wherein, At least a portion of the additive material is in contact with the surface of either of the two adjacent particles via at least one of covalent bonding or non-covalent attachment.

4. The solid-state battery as described in claim 1, wherein, The additive material is not in particulate form.

5. The solid-state battery as described in claim 1, 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 not present in the solid electrolyte layer.

6. The solid-state battery as claimed in claim 1, wherein, The sulfide-containing material includes lithium phosphorus sulfide chlorine (LPSCl).

7. The solid-state battery as claimed in claim 1, wherein, The additive material is selected from the group consisting of the following substances: (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); (Chemical Formula 26); (Chemical Formula 27); (Chemical Formula 28); (Chemical Formula 29); (Chemical Formula 30); (Chemical Formula 31); (Chemical Formula 32); (Chemical Formula 33); (Chemical Formula 34); (Chemical Formula 35); (Chemical Formula 36); (Chemical Formula 37); and its combinations.

8. The solid-state battery as claimed in claim 1, wherein, The sulfide-containing material has a first hardness of 0.1 to 1 GPa obtained by nanoindentation testing, and the additive material has a second hardness of 0.001 to 0.01 GPa obtained by nanoindentation testing.

9. The solid-state battery as claimed in claim 1, 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. The solid-state battery of claim 1, wherein, The solid-state battery is configured to operate at a pressure of less than 5 MPa.

11. The solid-state battery of claim 1, wherein, The specific capacity of the solid-state battery is greater than 100 mAh / g.

12. The solid-state battery of claim 1, wherein, The additive material is in powder form.

13. The solid-state battery as claimed in claim 1, wherein, The porosity of the solid electrolyte layer is 5% to 15%.

14. The solid-state battery as claimed in claim 1, wherein, The density of the solid electrolyte layer is increased by more than 10% compared to the density without the additive material.

15. A method for manufacturing the solid-state battery of claim 1, the method comprising: Providing the solid electrolyte layer includes ball milling the particles together with the additive material.

16. The method of claim 15, wherein, The ball milling causes A to interact with the sulfur in the sulfide-containing material of the particles, such that at least a portion of the additive material adheres to the surface of the particles.

17. A solid-state battery, comprising: positive electrode; negative electrode; A solid electrolyte layer is disposed between the positive electrode and the negative electrode, and is configured to enable lithium ion transport between the positive electrode and the negative electrode. in, The solid electrolyte layer comprises: Particles containing sulfide-containing materials; and Additive materials selected from the group consisting of the following substances: (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); (Chemical Formula 26); (Chemical Formula 27); (Chemical Formula 28); (Chemical Formula 29); (Chemical Formula 30); (Chemical Formula 31); (Chemical Formula 32); (Chemical Formula 33); (Chemical Formula 34); (Chemical Formula 35); (Chemical Formula 36); (Chemical Formula 37); and its combinations.

18. The solid-state battery of claim 17, wherein, The additive material is configured to interact with sulfur in the sulfide-containing material in the particles, and at least a portion of the additive material is sandwiched between two directly adjacent particles in the particles and contacts the surface of either of the two adjacent particles by covalent bonding and / or non-covalent attachment.

19. An electric vehicle comprising the solid-state battery of claim 1.

20. An electric vehicle comprising the solid-state battery of claim 17.

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