Solid-state battery device

Abstract

A solid-state battery device is provided. The present disclosure relates to a solid-state battery comprising a cell including: a positive electrode, a negative electrode, and a solid electrolyte disposed between the positive electrode and the negative electrode. The negative electrode includes first particles containing silicon and second particles containing a material configured to form an alloy with lithium. The second particles are softer than the first particles and are configured to compensate for changes in size of the first particles during charge and discharge cycles of the solid-state battery, so that when the first particles expand in size, the size of the second particles is compressed at a given pressure applied to the solid-state battery, and when the first particles shrink in size, the size of the second particles is expanded at a given pressure applied to the solid-state battery.

Description

solid-state battery devices

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to U.S. patent application Ser. No. 63 / 555,990, filed Feb. 21, 2024, and U.S. patent application Ser. No. 19 / 009,844, filed Jan. 3, 2025, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present disclosure relates to a solid-state battery device.

[0005] secondary battery

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

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

[0008] One challenge in solid-state battery design is achieving and maintaining sufficient lithium ion diffusion within the solid electrolyte material. Furthermore, volume changes (e.g., expansion and contraction) of certain battery components (e.g., electrodes) can occur during battery discharge and charging. These volume changes can result in mechanical stress or loss of contact between various components within the battery structure. Loss of contact between battery components can lead to degraded charge and discharge characteristics and a reduction in overall battery capacity. Researchers and engineers in the energy storage field are actively working to address these challenges. Efforts are focused on developing new materials and battery designs that can accommodate the mechanical stresses associated with battery cycling while achieving desirable lithium ion diffusion. Improving the stability of interfaces within solid-state batteries remains an area of ​​research. Overcoming the current limitations of solid-state battery systems could lead to significant advancements in energy storage capabilities across a wide range of applications.

[0009] Non-recognition of prior art

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

[0011] Beneficial effects of various types of metal-active materials

[0012] By applying various types of metallic active materials with different strengths, the weaker metallic material can act as both the active material and a buffer against size changes. By applying various metallic active materials with different strengths and mechanical properties, an all-solid-state battery capable of operating at low pressure may be desirable.

[0013] Various aspects of the present disclosure

[0014] The present disclosure relates to a solid-state battery comprising a cell comprising a cathode, an anode, and a solid electrolyte positioned between the cathode and the anode. The cathode comprises first particles comprising silicon and second particles comprising a material configured to form an alloy with lithium. The cathode does not comprise carbon-based particles, sulfide-based particles, or oxide-based particles. The solid electrolyte is configured to enable the movement of lithium ions between the cathode and the anode. The first and second particles do not form a combined domain comprising silicon and the material, but rather individually form discrete domains in the cathode. The second particles are softer than the first particles and are configured to compensate for changes in size of the first particles during charge and discharge cycles of the solid-state battery, such that when the first particles expand in size, the second particles compress in size at a given pressure applied to the solid-state battery, and when the first particles contract in size, the second particles expand in size at a given pressure applied to the solid-state battery, such that the second particles maintain direct or indirect contact with the first particles as well as with each other, thereby allowing the solid-state battery to operate at a lower pressure than would be required in the absence of the second particles in the negative electrode. The solid-state battery is subjected to a pressure of less than 10 MPa.

[0015] In general, the lithium ion diffusion coefficient of the negative electrode is 1 x 10 -14 cm 2 1 x 10 in / s -7 cm 2 / s is the range.

[0016] In general, the first particles have a first hardness in the range of 6 to 8 Mohs hardness, and the second particles have a second hardness in the range of 1 to 4 Mohs hardness.

[0017] In general, the first particles have a first hardness and the second particles have a second hardness, the second hardness being at least two Mohs hardness values ​​lower than the first hardness.

[0018] In general, the cathode electrode has a thickness that changes by less than 10% during charge and discharge cycles at a given pressure applied to the solid-state battery.

[0019] In general, the thickness of the cathode electrode ranges from 10 μm to 100 μm.

[0020] In general, the material of the second particles comprises a metal or a metal alloy.

[0021] In one general aspect, the material of the second particles comprises tin, a tin alloy, copper, a copper alloy, aluminum, an aluminum alloy, magnesium, a magnesium alloy, zinc, a zinc alloy, silver, a silver alloy, gold, a gold alloy, lead, a lead alloy, indium, an indium alloy or a combination thereof.

[0022] In general, the material of the second particles comprises tin or a tin alloy.

[0023] In general, the secondary particles do not contain lithium at the time of assembly prior to the initial charge and discharge of the battery.

[0024] In one general aspect, the present disclosure relates to a solid-state battery wherein the negative electrode comprises more first particles than second particles based on the total weight of the negative electrode active material.

[0025] In general, the cathode active material is essentially composed of first particles and second particles.

[0026] In one general aspect, the negative electrode active material comprises first particles in an amount of 10% to 90% by weight based on the total weight of the negative electrode active material, and second particles in an amount of 10% to 90% by weight based on the total weight of the negative electrode active material.

[0027] In one general aspect, the negative electrode active material comprises first particles in an amount of 40% to 60% by weight based on the total weight of the negative electrode active material, and second particles in an amount of 40% to 60% by weight based on the total weight of the negative electrode active material.

[0028] In general terms, the cathode electrode comprises at least 90% by weight of the first particles and the second particles based on the total weight of the cathode.

[0029] In one overall aspect, the second particles and the first particles form a bimodal distribution in the negative electrode, which is configured to reduce the porosity of the negative electrode by having the second particles positioned in the void spaces within the lattice of the first particles. The bimodal distribution increases surface contact during the charge and discharge cycles of the solid-state battery, allowing the second particles to maintain direct or indirect contact with the first particles as well as with each other, thereby enabling the solid-state battery to operate at a lower pressure than would be required in the absence of the bimodal distribution in the negative electrode.

[0030] In an overall aspect, the first particles have a first average particle size in the range of 10 μm to 1,000 μm, and the second particles have a second particle size in the range of 10 nm to 1,000 nm.

[0031] In general, the first particles have a first average particle size, the second particles have a second average particle size, and the second average particle size is less than half the first average particle size.

[0032] In general, the cathode electrode has a porosity of less than 30% based on the total volume of the cathode.

[0033] In general, solid-state batteries have a C-rate greater than 0.33.

[0034] In general, the cathode electrode additionally includes a binder.

[0035] In general, the cathode electrode has a porosity of at least 10% based on the total volume of the cathode.

[0036] In general, the cathode electrode is under a pressure in the range of 1 MPa to 5 MPa.

[0037] In general, solid-state batteries have specific capacities greater than 100 mAh / g.

[0038] In general, the cell thickness is less than 1 mm.

[0039] In general terms, the present disclosure relates to a method. The method comprises repeatedly charging and discharging a solid-state battery. The negative electrode is in direct contact with the solid electrolyte, and this direct contact is maintained after charging and discharging by compensating for changes in the size of the first particles using second particles.

[0040] The present disclosure also relates to a method for manufacturing a cell of a solid-state battery. The method comprises depositing a positive electrode layer and depositing a solid electrolyte layer. The method comprises forming a mixture by mixing first particles comprising silicon and second particles comprising a material configured to form an alloy with lithium. The negative electrode does not comprise carbon-based particles, sulfide-based particles, or oxide-based particles. The second particles are softer than the first particles. The method comprises depositing the mixture in a negative electrode layer in such a way that the second particles are configured to compensate for changes in size of the first particles during charge and discharge cycles of the solid-state battery, such that when the first particles expand in size, the second particles compress in size at a given pressure applied to the solid-state battery, and when the first particles contract in size, the second particles expand in size at a given pressure applied to the solid-state battery, such that the second particles generally maintain direct or indirect contact with the first particles as well as with each other, thereby allowing the solid-state battery to operate at a lower pressure than would be required in the absence of the second particles in the negative electrode layer. The present method comprises configuring a solid-state battery such that a solid electrolyte layer is positioned between the positive electrode layer and the negative electrode layer to enable the movement of lithium ions between the positive electrode layer and the negative electrode layer. The first particles and the second particles do not form a combined domain comprising silicon and the material, but rather individually form discrete domains in the negative electrode layer.

[0041] In general terms, the mixture additionally comprises a solvent and a binder.

[0042] In general, the material of the second particles comprises a metal or a metal alloy.

[0043] In one general aspect, the material of the second particles comprises tin, a tin alloy, copper, a copper alloy, aluminum, an aluminum alloy, magnesium, a magnesium alloy, zinc, a zinc alloy, silver, a silver alloy, gold, a gold alloy, lead, a lead alloy, indium, an indium alloy, or a combination thereof.

[0044] In one general aspect, the cathode layer comprises first particles in an amount of 10% to 90% by weight based on the total weight of the cathode layer, and second particles in an amount of 10% to 90% by weight based on the total weight of the cathode layer.

[0045] In general, the cathode layer comprises first particles in an amount of 40% to 60% by weight based on the total weight of the cathode layer, and second particles in an amount of 40% to 60% by weight based on the total weight of the cathode layer.

[0046] In one general aspect, a solid-state battery is manufactured by the above-mentioned method of manufacturing a battery.

[0047] Not limited to summary

[0048] It is to be understood that this summary is not exhaustive. Various other aspects are described and illustrated herein.

[0049] Beneficial effects of different particle sizes

[0050] In all-solid-state batteries utilizing lithium diffusion, good contact between active materials may be desirable. Lithium diffusion can be promoted by improving contact using bimodal mixed particles rather than single-size particles. This can minimize lithium dendrite formation at low pressures and high C-rates.

[0051] Figure 1 is an embodiment of a solid-state battery according to the present disclosure.

[0052] FIG. 2 is a graph of embodiments of a solid-state battery device according to the present disclosure.

[0053] FIG. 3 is a graph of embodiments of a solid-state battery device according to the present disclosure.

[0054] Not limited to examples

[0055] The examples presented herein illustrate specific non-limiting embodiments of the invention and should not be construed as limiting the scope of the claims in any way.

[0056] Examples and Examples

[0057] The subject matter of the present disclosure will now be described and discussed in more detail with reference to the accompanying drawings, wherein like reference numerals designate like elements or parts throughout, unless otherwise specified. The subject matter of the present disclosure should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to satisfy applicable legal requirements. Indeed, numerous modifications and other embodiments of the subject matter of the present disclosure will occur to those skilled in the art to which the subject matter of the present disclosure pertains. Therefore, it should be understood that the subject matter of the present disclosure is not limited to the specific embodiments set forth herein, and that modifications and other embodiments are intended to fall within the scope of the appended claims.

[0058] "a", "an", and "the"

[0059] As used herein, singular terms include plurals unless the context clearly dictates otherwise. The plural includes the singular, and vice versa. Thus, references to "a," "an," and "the" generally include the plural of each term. For example, although the present disclosure has been described in terms of "layers," "substrates," "cells," and the like, one or more of these elements, including combinations of these elements and other elements, may be used.

[0060] "approximately"

[0061] The term "about" refers to and includes the indicated value and the upper and lower ranges of that value.

[0062] "include", "consist essentially of" and "consist of"

[0063] The words "include," "including," and "comprising" are to be construed inclusively, not exclusively. Similarly, the terms "include," "comprising," and "or" are to be construed inclusively, unless the context clearly prohibits such interpretation. Disclosure of an embodiment defined using the term "comprising" also discloses an embodiment "consisting essentially of" and "consisting of" the disclosed components. The phrase "consisting of" excludes any unspecified element, step, or component.

[0064] "and / or"

[0065] The term "and / or" used in the context of "X and / or Y" should be interpreted as "X", "Y" or "X and Y".

[0066] "Above" and "Beyond"

[0067] As used herein, the terms "on," "applied on," "formed on," "deposited on," "provided on," and similar terms mean applied, formed, superimposed, deposited, or provided in contact with an underlying or upper surface. Conversely, the terms "over," "applied over," "formed over," "deposited over," "overlay," "provided over," and similar terms mean applied, formed, superimposed, deposited, or provided on or over a surface, but not necessarily in contact with the surface. For example, a cambium layer "applied over" a substrate layer may be in contact with the substrate without an intermediate material; however, the same phrase does not exclude the presence of one or more other layers of the same or different composition located between the cambium layer and the substrate layer.

[0068] Markush Group

[0069] The term "combination thereof" as used herein is included in the Makushi-type expression and refers to a combination or mixture of one or more elements selected from a group of elements disclosed in the Makushi-type expression, and refers to the presence of one or more elements selected from that group of elements. The term "combination thereof" includes all possible combinations of all elements referred to by the term.

[0070] "between"

[0071] The term "between" as used herein includes both endpoints.

[0072] Numerical range

[0073] Moreover, all numerical ranges disclosed herein should be understood to include all integers, whole numbers, or fractions within that range. Furthermore, all numerical ranges disclosed herein are intended to include all subranges subsumed therein, and such numerical ranges should be construed to support claims to any number or subset of numbers within that range. For example, a disclosure of a range from 1 to 10 should be construed to support ranges from 1 to 8, from 3 to 7, from 1 to 9, from 3.6 to 4.6, from 3.5 to 9.9, etc. When a range is given, all endpoints of that range and / or numbers within that range can be combined within the scope of the present disclosure.

[0074] "include", "etc." and "for example"

[0075] As used herein, the terms “include,” “including,” “such as,” “for example,” and similar terms mean “including but not limited to.”

[0076] Combination of examples

[0077] The term "example" as used herein, especially when followed by a list of terms, is merely exemplary and should not be construed as exclusive or comprehensive. Any embodiment disclosed herein may be combined with any other embodiment disclosed herein, unless expressly indicated otherwise.

[0078] particle size

[0079] Particle size as used herein refers to the average particle diameter (D50) 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). The size may be the diameter of a spherical particle or the length measured along the longest dimension for particles of ellipsoidal or other irregular shapes. As used herein, the "D 50 " refers to the diameter at which 50% of the particles have a smaller diameter.

[0080] solid-state lithium-ion batteries

[0081] Solid-state batteries can accept charge and discharge an electrical load multiple times. Solid-state batteries contain electrodes—an anode and a cathode—and an electrolyte that allows lithium ions to move between the electrodes. Unlike conventional liquid electrolyte batteries, solid-state batteries do not contain any liquid. Electricity flows between the electrodes when a circuit is formed between them. During charging of a lithium-ion rechargeable battery, lithium ions are released from the anode and inserted into the active material of the cathode. During discharging of a lithium-ion rechargeable battery, lithium ions are released from the cathode and inserted into the active material of the anode. As the lithium ions shuttle between the electrodes, they transfer energy.

[0082] Composition of solid-state batteries

[0083] The present disclosure provides a solid-state battery (100) comprising a positive electrode (102), a negative electrode (104), and a solid electrolyte layer (106) positioned between the positive electrode (102) and the negative electrode (104). Although listed as examples, the solid-state battery (100) does not require all of these components. For example, in some configurations, the negative electrode (104) may be omitted, such as in an anodeless system.

[0084] Optional additional layers

[0085] The solid-state battery (100) may optionally include one or more additional layers, such as a separator layer, a protective layer, a suppression layer, a solid electrolyte interfacial layer, or a combination thereof.

[0086] protective layer

[0087] For example, a protective layer may be included between the electrode (102) and the electrode (104) and the solid electrolyte layer (106), and / or a protective layer may be included between the electrode (102) and the current collector (110) in a non-cathode system. The protective layer may also help improve the overall life and safety of the battery by mitigating dendrite formation, particularly on the cathode side. In some cases, the protective layer may help reduce undesirable side reactions by improving the interfacial stability between the electrode and the electrolyte. Additionally, the protective layer may enhance the mechanical properties of the electrode-electrolyte interface, which may be beneficial in maintaining good contact during cycling.

[0088] protective layer material

[0089] This protective layer may include materials such as lithium phosphate, lithium titanate, and lithium lanthanum zirconium oxide (LLZO), which may help prevent undesirable side reactions at the electrode-electrolyte interface. Other options for the protective layer material include, but are not limited to, lithium niobium oxide (LiNbO3), lithium tantalum oxide (LiTaO3), lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium silicate, and lithium boron oxide.

[0090] membrane layer

[0091] A separator layer may also be included in some configurations of the solid-state battery (100). Such a separator layer can provide additional mechanical support to the battery structure while enabling efficient ion transport. The separator layer may also be designed to have a gradient structure with properties optimized for contact with both the positive and negative electrode materials. This gradient structure may, for example, include varying porosity, composition, or surface properties across the thickness of the separator. In some aspects, the separator surface may be functionalized with ion-conducting groups or coatings to enhance lithium ion transport at the electrode-separator interface. The separator layer may further be designed as a multilayer by incorporating different materials optimized for specific functions, for example, a mechanically strong core layer sandwiched between ion-conducting outer layers. The separator layer may additionally be designed to be self-healing, for example, to reform bonds after mechanical stress to help prevent short circuits due to dendrite growth.

[0092] Material of the membrane layer

[0093] While traditional liquid electrolyte batteries often use porous polymer separators, solid-state batteries may use thin ceramic or glass-ceramic layers as separators. Materials such as LLZO, LATP (lithium aluminum titanium phosphate), or LAGP (lithium aluminum germanium phosphate) can be used for this purpose. Other separator layer materials suitable for solid-state batteries include lithium phosphate oxynitride (LiPON), lithium lanthanum titanate (LLTO), and Li6BaLa2Ta2O. 12 Lithium garnet-type materials such as Li 10 GeP2S 12 There are sulfide-based materials such as , and polymer-ceramic composites combining polyethylene oxide (PEO) and ceramic fillers.

[0094] solid-state battery cells

[0095] Figure 1 illustrates a cell (101) of a solid-state battery (100) according to one embodiment. The cell (101) includes a positive electrode (102), a negative electrode (104), and a solid electrolyte layer (106) positioned between the positive electrode (102) and the negative electrode (104). The cell (101) may optionally include one or more additional layers, such as a separator layer, a protective layer, a suppression layer, a solid electrolyte interfacial layer, or a combination thereof.

[0096] Cell composition

[0097] As illustrated in FIG. 1, the solid-state battery (100) may include a single cell (101). In other embodiments, the solid-state battery (100) may include a plurality of cells, for example, at least two cells, at least three cells, or at least four cells. Connecting the cells in series increases the voltage of the solid-state battery (100), and connecting the cells in parallel increases the ampere-hour capacity of the solid-state battery (100).

[0098] Cell dimensions

[0099] A cell (101) may have a width (w1), a length (l1), and a thickness (t1).

[0100] Cell thickness

[0101] The thickness (t1) of the cell (101) can have any value or approximately a value in the range of exactly or approximately 100 μm to approximately 5000 μm, for example, about 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, It can be 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 selecting any two values ​​within a range from about 100 μm to about 5000 μm (e.g., between about 100 μm and about 5,000 μm or between about 100 μm and about 1,000 μm).

[0102] Aspect ratio of width

[0103] The width (w1) of the cell (101) may be greater than the thickness (t1) of the cell (101). In some embodiments, the aspect ratio of the width (w1) to the thickness (t1) is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, at least 260, at least 270, at least 280, at least 290, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550, at least 600, at least 650, at least 700, at least 750, It can be 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.

[0104] Aspect ratio of length

[0105] The length (l1) of the cell (101) may be greater than the thickness (t1) of the cell (101). In some embodiments, the aspect ratio of the length (l1) to the thickness (t1) is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, at least 260, at least 270, at least 280, at least 290, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550, at least 600, at least 650, at least 700, at least 750, It can be 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.

[0106] anode electrode

[0107] The positive electrode (102) is associated with one polarity (e.g., the positive electrode) of the solid-state battery (100). The positive electrode (102) is configured as the positive electrode during discharge of the solid-state battery (100). The positive electrode (102) is suitably configured to allow lithium ion diffusion between the current collector (108) and the solid electrolyte layer (106). The positive electrode (102) is in electrical communication with the current collector (108).

[0108] Location of the anode electrode

[0109] In embodiments, the positive electrode (102) is formed on and in direct contact with the current collector (108). In other embodiments, another functional layer may be interposed between the positive electrode (102) and the current collector (108).

[0110] Materials for anode electrodes

[0111] The positive electrode (102) may be capable of reversible intercalation and deintercalation of lithium ions. For example, the positive electrode (102) may include only a positive electrode active material. In another embodiment, the positive electrode (102) may optionally include one or more of conductive carbon, a solid electrolyte material, and a binder. Optionally, the positive electrode (102) may further include additives such as oxidation stabilizers, reduction stabilizers, flame retardants, heat stabilizers, antifogging agents, thickeners, plasticizers, ionic conductivity enhancers, binders (described in more detail below), dispersants, wetting agents, adhesion promoters, crosslinkers, colorants, and the like, or combinations thereof.

[0112] Examples of additives

[0113] Examples of such additives may include butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT) as oxidation stabilizers, ascorbic acid or sodium sulfite as reduction stabilizers, aluminum hydroxide or magnesium hydroxide as flame retardants, phenolic compounds or phosphites as heat stabilizers, polyethylene glycol or silica nanoparticles as antifogging agents, carboxymethyl cellulose (CMC) or xanthan gum as thickeners, dibutyl phthalate or triethyl citrate as plasticizers, ceramic fillers or ionic liquids as ionic conductivity enhancers, polyvinylpyrrolidone or sodium dodecyl sulfate as dispersants, polysorbates or poloxamers as wetting agents, silanes or titanates as adhesion promoters, peroxides or aziridines as crosslinkers, and carbon black or metal oxides as colorants.

[0114] positive electrode active material

[0115] The cathode active material is lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), Li[Ni a Co b Mn cM 1 d ]O2(where M 1 is any one element or a combination thereof selected from the group consisting of Al, Ga, and In, and 0.3≤a<1.0, 0≤b≤0.5, 0≤c≤0.5, 0≤d≤0.1, and a+b+c+d=1), Li(Li e M 2 f-e-f M 3 f′ )O 2-g A g (Here 0≤e≤0.2, 0.6≤f≤1, 0≤f′≤0.2, 0≤g≤0.2, M 2 contains at least one element selected from the group consisting of Mn and Ni, Co, Fe, Cr, V, Cu, Zn and Ti, and M 3 is at least one element selected from the group consisting of Al, Mg and B, and A is at least one element selected from the group consisting of P, F, S and N), or may include one or more transition metals substituted in these compounds. Also, Li 1+h Mn 2-h O4 (where 0≤h≤0.33), LiMnO3, LiMn2O3, LiMnO2 may also be included. In addition, lithium copper oxide (Li2CuO2), LiV3O8, V2O 5　 or vanadium oxides such as Cu2V2O7, LiNi 1-i M 4 i Ni-site type lithium nickel oxide, LiMn, expressed as O2 (where M4 = Co, Mn, Al, Cu, Fe, Mg, B or Ga, and 0.01≤y≤0.3) 2-j M 5 j O2 (where M5 = Co, Ni, Fe, Cr, Zn, or Ta, and 0.01≤y≤0.1) or Li2Mn3M 6 ​​​​​It may include a lithium manganese complex oxide represented by O8 (wherein M6 = Fe, Co, Ni, Cu, or Zn), LiMn2O4 in which Li is partially substituted with an alkaline earth metal ion, a disulfide compound, LiFe3O4, Fe2(MoO4)3, the like, or a combination thereof.

[0116] Phosphate-based materials

[0117] In addition to the positive electrode active materials mentioned above, the positive electrode may include other types of materials. For example, lithium iron phosphate (LiFePO4) can be used as the positive electrode active material due to its excellent thermal stability and long lifespan. Lithium manganese iron phosphate (LiMn x Fe 1-x Other phosphate-based materials may also be suitable, such as lithium vanadium phosphate (LiVOPO4), lithium titanium phosphate (LiTi2(PO4)3), lithium nickel phosphate (LiNiPO4), fluorophosphates such as LiVPO4F or LiFeSO4F, or lithium cobalt phosphate (LiCoPO4).

[0118] layered oxide materials

[0119] The cathode active material is also Li(Ni 1-x-y Co x Mn y )O2(NCM) or Li(Ni 1-x-y Co x Al y )O2(NCA) can contain layered oxide materials of various compositions, where the ratios of Ni, Co, Mn and Al can be adjusted to optimize performance characteristics. For example, NCM811(LiNi 0.8 Co 0.1 Mn 0.1 High nickel content NCM materials such as O2) can be used to achieve higher energy density. In some cases, the cathode active material is LiNi0.5Mn 1.5It may contain a spinel structure such as O4, which can provide high-voltage operation. Alternatively, materials with a tabolite structure, such as LiFeSO4F or LiVPO4F, can be used for their potential high energy density and excellent thermal stability.

[0120] Composite or mixed cathode materials

[0121] Composite or hybrid cathode materials combining two or more active materials may also be used. For example, a mixture of layered oxides and spinel materials may be used to balance energy density and power output. In another example, lithium iron phosphate may be mixed with one or more of the cathode active materials described above. In some embodiments, the cathode active material may include surface-modified versions of the aforementioned compounds, wherein the surface modification is intended to improve stability, conductivity, or other performance indicators.

[0122] A new kind of material

[0123] Cathode active materials may also include novel classes of materials, such as disordered rock salt structures (e.g., Li3NbO4-based materials), lithium-rich semi-perovskites (e.g., Li3OCl), cation-disordered oxides (e.g., Li-Mn-VO system), or high-entropy oxides, which may offer a desirable combination of high capacity and structural stability. In some cases, the cathode active materials may include dopants or substitutional elements to further tailor their electrochemical properties.

[0124] Particle characteristics of positive electrode active materials

[0125] The positive electrode active material may have a particle shape. The cathode active material may have a particle size ranging from about 1 nm to about 1000 μm, for example, about 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, 480 nm, 490 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 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 μm, 430 μm, 440 μm, 450 μm, 460 μm, 470 μm, 480 μm, 490 μm,The particle size of the positive electrode active material may be 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 embodiments, the particle size of the positive electrode active material may be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within a range from about 1 nm to about 1,000 μm (e.g., between about 10 nm and about 1,000 μm). The gap between the positive electrode active material particles of the positive electrode (102) may be filled with a solid electrolyte material.

[0126] Amount of positive active material in the positive electrode

[0127] The amount of the positive electrode active material in the solid-state battery (100) affects the charge and discharge capacity of the solid-state battery (100). To manufacture a high-capacity positive electrode (102), the positive electrode (102) may include a high level of the positive electrode active material. For example, the positive electrode (102) includes equal to, about, or more than 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99 wt % of the positive electrode active material, based on the total weight of the positive electrode (102). In embodiments, the amount of the positive electrode active material of the positive electrode (102) can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within a range from a value greater than 0 to about 100 wt% (e.g., between about 40 wt% and about 98 wt%).

[0128] Conductive material of the anode electrode

[0129] The conductive material of the positive electrode (102) is not particularly limited as long as it has conductivity without causing any chemical change in the solid-state battery (100). For example, the conductive material may be graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black or thermal black; conductive fibers such as carbon fibers or metal fibers; carbon nanotubes (CNTs) including both single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs); metal powders such as fluorocarbon, aluminum or nickel powders; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; conductive polymers such as polyphenylene derivatives; It may include graphene, metallic 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, the like, or combinations thereof.

[0130] Amount of conductive material within the anode electrode

[0131] The anode electrode (102) comprises exactly or approximately 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt % of the conductive material, based on the total weight of the anode electrode (102). In embodiments, the amount of the conductive material of the anode electrode (102) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 1 wt % and about 30 wt %).

[0132] Materials for binders

[0133] Binders include, for example, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), poly(ethylene-co-vinyl acetate) (PEVA), poly(vinyl acetate) (PVA), chitosan, guar gum (GG), xanthan gum, carrageenan, pectin, water-soluble polymers, It may include various types of binder polymers such as lignin, polymers thereof in which hydrogen atoms are substituted with Li, Na or Ca, various copolymers thereof, the like, or combinations thereof.

[0134] Other binder materials

[0135] In addition to the binder materials mentioned above, other types of binder materials can be used to improve the performance and stability of the positive electrode. For example, water-soluble binders such as sodium alginate, gelatin, or polyacrylamide can be used to improve the environmental friendliness of the electrode manufacturing process. These binders can also provide advantages in terms of electrode flexibility and adhesive strength. In some cases, conductive binders such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) or polyaniline (PANI) can be used to simultaneously improve the mechanical integrity and electrical conductivity of the electrode.

[0136] New binder system

[0137] Novel binder systems, such as self-healing polymers or supramolecular assemblies, may be incorporated to enhance the long-term stability and lifespan of batteries. Additionally, composite binders combining multiple polymers or incorporating inorganic nanoparticles may be used to tailor the mechanical, thermal, and electrochemical properties of the electrode. In some embodiments, bio-derived or biodegradable binders, such as cellulose derivatives or chitosan, may be used to reduce the environmental impact of battery production and disposal.

[0138] Binder content in the positive electrode

[0139] The anode electrode (102) can include exactly or approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt % of the binder, based on the total weight of the anode electrode (102). In embodiments, the amount of binder in the anode electrode (102) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 1 wt % and about 30 wt %).

[0140] solid electrolyte material

[0141] The solid electrolyte material of the positive electrode (102) may be composed identically to the material of the solid electrolyte layer (106) discussed below. The solid electrolyte material of the positive electrode (102) may be identical to or different from the material of the solid electrolyte layer (106).

[0142] Amount of solid electrolyte material in the positive electrode

[0143] The anode electrode (102) can include about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt % of the solid electrolyte material, based on the total weight of the anode electrode (102). In embodiments, the amount of the solid electrolyte material of the anode electrode (102) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 1 wt % and about 30 wt %).

[0144] Thickness of the anode electrode

[0145] The thickness (t2) of the anode electrode (102) can be any value in the range from 0 to 1000 μm or approximately thereto, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400,410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, It can be 920, 930, 940, 950, 960, 970, 980, 990, 1,000 μm. In embodiments, the thickness (t2) of the positive electrode (102) can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within a range from a value greater than 0 to about 1,000 μm (e.g., between about 10 μm and about 1,000 μm).

[0146] Porosity of the anode electrode

[0147] The porosity of the anode electrode (102) can be any value in the range of 0 to 20 volume % or approximately thereabout, based on the total volume of the anode electrode (102), for example, 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 embodiments, the porosity of the anode 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 % (e.g., between 0 volume % and about 18 volume %).

[0148] Lithium ion diffusion in the positive electrode

[0149] The anode electrode (102) has a value greater than 0 and a value of 1 x 10 -7 cm 2 / s or approximately the lithium ion diffusion rate, for example 1 x 10 -14 cm 2 / s, 1 x 10 -13 cm 2 / s, 1 x 10 -12 cm 2 / s, 1 x 10 -11 cm 2 / s, 1 x 10 -10 cm 2 / s, 1 x 10 -9 cm 2 / s, 1 x 10 -8 cm 2 / s, or 1 x 10 -7 cm 2 / s may be. In embodiments, the lithium ion diffusion coefficient of the positive electrode (102) may be selected from any two values ​​listed above or from a value greater than 0 to 1 x 10 -7 cm 2 / s can be a range formed by selecting any two numbers within the range (e.g. 1 x 10 -14 cm 2 / s and about 1 x 10-7 cm 2 / s between).

[0150] Current collector of positive electrode

[0151] The collector (108) collects the electric energy generated from the positive electrode (102) and supports the positive electrode (102).

[0152] Materials for current collectors of positive electrodes

[0153] The material of the current collector (108) is not particularly limited as long as it allows adhesion of the positive electrode (102), has appropriate electrical conductivity, and does not cause significant chemical changes in the solid-state battery (100) over the voltage range of the solid-state battery (100). For example, the current collector (108) is made of or includes, but is not limited to, a metal, conductive carbon, or conductive ceramic. The metal of the current collector (108) may include, but is not limited to, one or more of aluminum, an aluminum alloy, copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, iron, an iron alloy (e.g., steel, stainless steel), silver, a silver alloy, gold, platinum, palladium, chromium, molybdenum, tungsten, tantalum, niobium, zirconium, vanadium, manganese, cobalt, indium, tin, lead, bismuth, or combinations thereof.

[0154] The geometric structure of the entire house

[0155] The current collector (108) may also be configured in a variety of other geometries to optimize performance and integration with the positive electrode (102), and may be sized to fit specific form factors such as pouch-shaped, cylindrical, and / or prismatic.

[0156] Current collector shape of the positive electrode

[0157] It is possible to increase the adhesion of the positive electrode (102) to the current collector (108) by forming fine surface irregularities on the surface of the current collector (108). The current collector (108) may have various shapes, such as a film, a sheet, a foil, a mesh, a porous body, a foam, a non-woven fabric, the like, or a combination thereof.

[0158] Examples of the shape and size of the entire house

[0159] For example, the current collector (108) may be configured with a mesh or grid structure that can provide enhanced mechanical support while maintaining a high surface area for electrode adhesion. In some embodiments, the current collector (108) may be designed with a corrugated or wavy pattern, which can increase the contact area with the positive electrode material and improve overall conductivity. The current collector (108) may also be fabricated as a perforated sheet to enable better electrolyte penetration and ion transport. In certain cases, the current collector (108) may be formed into a three-dimensional structure, such as an interconnected fiber network or a honeycomb configuration, which can facilitate efficient current collection while improving the structural integrity of the electrode assembly.

[0160] Current collector thickness of the positive electrode

[0161] The thickness (t3) of the current collector (108) can be any value in the range from 0 to 500 μm or approximately thereto, for example, 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, It can be 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or 500 μm. In embodiments, the thickness (t3) of the current collector (108) can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within a range of 500 μm from a value greater than 0 (e.g., between about 5 μm and about 500 μm).

[0162] Method for manufacturing anode electrode

[0163] The anode electrode (102) can be obtained by various methods.

[0164] Dry powder coating process

[0165] For example, a dry powder coating process may be used, which can reduce the environmental impact by reducing the use of solvents, in which the positive active material, conductive additive, and binder are mixed in a dry state and then applied directly to the current collector (108) using electrostatic deposition or mechanical compression.

[0166] 3D printing

[0167] In some cases, the anode electrode (102) may be fabricated using additive manufacturing techniques, such as 3D printing. This approach allows for precise control over the electrode structure and porosity, potentially improving electrode performance and energy density. Various 3D printing methods, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW), may be utilized, depending on the specific material and desired electrode properties.

[0168] electrospinning

[0169] Another method for manufacturing a positive electrode (102) may involve electrospinning. In this process, a solution containing a positive electrode active material, a conductive additive, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be collected directly onto a current collector (108) to form a porous electrode structure with a high surface area.

[0170] Tape casting

[0171] In some embodiments, the positive electrode (102) may be manufactured using a tape casting method. This technique involves applying a slurry of electrode material onto a moving carrier film using a doctor blade, followed by drying and calendering. The resulting electrode tape may then be laminated to a current collector (108).

[0172] spray coating

[0173] Alternatively, the positive electrode (102) can be fabricated using a spray coating technique. In this method, a fine mist of electrode slurry is sprayed onto a current collector (108) using compressed air or ultrasonic atomization. This approach can enable the production of a thin, uniform electrode layer and may be particularly useful for large-scale production.

[0174] Freeze casting

[0175] In some cases, the positive electrode (102) may be manufactured using a freeze-casting process. This process involves freezing a slurry of electrode material, followed by sublimation of the ice to create a porous structure. The resulting porous electrode may then be sintered and attached to a current collector (108).

[0176] sol-gel process

[0177] In some applications, the positive electrode (102) may be manufactured using a sol-gel process. This process involves forming a colloidal suspension (sol) containing the positive electrode active material and other components, and then converting it into a gel-like network. This gel may be applied to a current collector (108) and then heat-treated to form the final electrode structure.

[0178] slurry-based process

[0179] For example, the positive electrode active material can be mixed with a solvent and stirred, optionally forming a slurry together with a binder, a conductive material, and a dispersant. This slurry can then be applied (e.g., coated) to a current collector (108), followed by pressurization and drying to obtain a positive electrode (102).

[0180] Method for applying slurry for anode electrode

[0181] Application of the slurry to the anode electrode (102) may include a technique selected from the group consisting of slot die coating, gravure coating, spin coating, spray coating, roll coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, plate printing, intaglio printing, offset printing, the like, and combinations thereof.

[0182] Double-layer slot die coating

[0183] In some embodiments, the positive electrode (102) may be fabricated using a double-layer slot-die coating (DLD) technique. This method involves simultaneously depositing two different electrode material layers onto a current collector (108) in a single pass. The DLD process enables the creation of a gradient structure within the electrode, which can optimize both electrochemical performance and mechanical properties. Additionally, this technique allows for the integration of functional interlayers or protective coatings as part of the electrode fabrication process, potentially improving overall battery performance and cycle life.

[0184] Solvent for slurry for positive electrode

[0185] The solvent for forming the positive electrode (102) may include water and / or an organic solvent such as N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), acetone, dimethyl acetamide, dimethyl sulfoxide (DMSO), isopropyl alcohol, the like, or a combination thereof. The solvent may be used in an amount sufficient to dissolve and disperse the electrode components, i.e., the positive electrode active material, the binder, and the conductive material, and may be determined in consideration of the slurry coating thickness, the production yield, the like, or a combination thereof. Additional solvents may include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0186] Method without using solvents

[0187] In some aspects of the present disclosure, the positive electrode (102) can be manufactured using solvent-free methods such as dry powder processing or melt extrusion, which can provide environmental and cost advantages by reducing the use of liquid solvents.

[0188] Dispersant for slurry for positive electrode

[0189] The dispersant for forming the positive electrode (102) may include an aqueous dispersant and / or an organic dispersant, and may include, for example, N-methyl-2-pyrrolidone. Other possible dispersants may include polyvinylpyrrolidone (PVP), carboxymethyl cellulose (CMC), sodium dodecyl sulfate (SDS), Triton X-100, polyethylene glycol (PEG), polyacrylic acid (PAA), and various surfactants such as polysorbates or poloxamers.

[0190] Drying technology for slurry for anode electrodes

[0191] The slurry for the anode electrode (102) can be dried by irradiating it with heat, electron beams (E-beams), gamma rays, ultraviolet rays (G, H, I-rays), the like, or a combination thereof to evaporate the solvent. For example, the slurry can be vacuum-dried at room temperature. During the drying step, the solvent is removed by evaporation, but other components remain without evaporation to form the anode electrode (102).

[0192] Additional drying technology

[0193] In addition to the drying techniques mentioned, the positive electrode (102) may be dried using other methods such as infrared (IR) drying, microwave drying, or freeze drying.

[0194] Combination of drying technologies

[0195] In some embodiments, 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.

[0196] Cathode electrode general

[0197] The negative electrode (104) is associated with one polarity (e.g., the negative electrode) of the solid battery (100), which is different from the polarity of the positive electrode (102). The negative electrode (104) is configured as the negative electrode during discharge of the solid battery (100). The negative electrode (104) is suitably configured to allow lithium ion diffusion between the current collector (110) and the solid electrolyte layer (106).

[0198] Location of the cathode electrode

[0199] The negative electrode (104) is in electrical communication with the current collector (110). In embodiments, the negative electrode (104) is formed on and in direct contact with the current collector (110). In other embodiments, another functional layer may be interposed between the negative electrode (104) and the current collector (110).

[0200] Non-cathode electrode system

[0201] In some embodiments, as previously described, the solid-state battery (100) may utilize a non-anode electrode system. In such a configuration, the anode electrode (104) may be omitted, and lithium metal may be deposited directly onto the current collector (110) during charging. This approach could potentially increase the energy density of the battery and eliminate the need for a separate cathode material, while potentially reducing the overall thickness of the battery structure.

[0202] Materials for cathode electrodes

[0203] The negative electrode (104) may be capable of reversible insertion and de-insertion of lithium ions. For example, the negative electrode (104) may include only the negative electrode active material. In other embodiments, the negative electrode (104) may include conductive particles, a binder, the like, or a combination thereof.

[0204] Additives for cathode electrodes

[0205] Optionally, the cathode electrode (104) may further comprise additives such as oxidation stabilizers (e.g., butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tert-butylhydroquinone), reduction stabilizers (e.g., ascorbic acid, sodium sulfite, erythorbic acid, sodium metabisulfite), flame retardants (e.g., aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine cyanurate), heat or light stabilizers (e.g., phenolic compounds, phosphites, hindered amine light stabilizers, UV absorbers such as benzophenone or benzotriazole), antifogging agents (e.g., polyethylene glycol, silica nanoparticles, glycerol, sorbitol), thickeners (e.g., carboxymethyl cellulose, xanthan gum), the like, or combinations thereof.

[0206] Other additives for cathode electrodes

[0207] Additionally, conductive additives such as carbon black, graphene, or carbon nanotubes may be included to enhance electrical conductivity, and binder modifiers such as styrene-butadiene rubber or polyacrylic acid may be included to improve adhesion and mechanical stability. Furthermore, functional additives such as fluoroethylene carbonate or vinylene carbonate may be included to promote the formation of a stable solid electrolyte interfacial layer on the cathode surface.

[0208] Materials for negative electrode active materials

[0209] The negative electrode active material may be made of or include various materials such as, but not limited to, alkali metals, alkaline earth metals, Group 3B metals, transition metals, metalloids, alloys thereof, conductive carbon, the like, or combinations thereof. In embodiments, the negative electrode active material may include, but is not limited to, silicon, a silicon alloy, lithium, a lithium alloy, conductive carbon, or combinations thereof. In embodiments, the lithium alloy is made of or includes a lithium alloy that includes silicon, chlorine, or combinations thereof. A lithium metal thin film may be used as the negative electrode active material.

[0210] Other negative electrode active materials

[0211] The negative active material is a carbon-based material such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, or a metal compound that can form an alloy with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, Al alloy, or SiO x (0 <x<2), SnO2, 바나듐 산화물이나 리튬 바나듐 산화물과 같은 리튬 이온을 도핑 및 탈도핑할 수 있는 금속 산화물, 그리고 Si-C 복합체나 Sn-C 복합체와 같은 금속 화합물과 탄소계 재료의 복합체를 포함할 수 있다.

[0212] carbon-based materials

[0213] The carbonaceous material may include low-crystalline carbon, high-crystalline carbon, the like, or a combination thereof. Representative examples of low-crystalline carbon include soft carbon or hard carbon, and representative examples of high-crystalline carbon include high-temperature calcined carbon such as amorphous, plate-like, flake-like, spherical, or fibrous natural or artificial graphite, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesocarbon microbeads, mesophase pitch, coke derived from petroleum or coal tar pitch, the like, or a combination thereof.

[0214] metal carbon composite materials

[0215] Alternatively, according to an aspect of the present disclosure, the cathode electrode (104) may comprise a metal carbon composite, such as a silver-carbon blend or composite, as the cathode material, wherein silver particles are composited between amorphous and / or crystalline carbon particles. Silver is used herein as an example, but other metals, including tin and / or zinc, may be used. Silicon may be used in place of silver.

[0216] Additional materials for negative electrode active materials

[0217] In addition to the materials mentioned above, the negative electrode active material is lithium titanate (Li4Ti5O 12 ) or titanium-based compounds such as titanium dioxide (TiO2), which can provide excellent cycling stability and high-rate charge-discharge capability. Other potential materials include molybdenum oxide (MoO2), which can provide high theoretical capacity. x ), iron oxide (FeO x ), or nickel oxide (NiO x ) may include transition metal oxides such as silicon-graphite composites or tin-carbon composites. In some cases, composite materials combining different active materials, such as silicon-graphite composites or tin-carbon composites, may be used to utilize the strengths of each material while alleviating the limitations of the individual materials.

[0218] Dendrite formation

[0219] When the negative electrode (104) is made of or includes lithium or a lithium alloy, dendrites may form on the negative electrode (104). Dendrites are metallic lithium structures that form when excess lithium ions accumulate on the surface of the negative electrode (104). The formed dendrites may damage the solid electrolyte layer (106), reduce the battery capacity of the solid-state battery (100), and / or cause undesirable performance of the solid-state battery (100). Dendrite formation is a significant challenge in lithium-based batteries, as these structures can grow through the electrolyte, potentially causing short circuits and safety hazards. The growth rate and morphology of the dendrites may be affected by factors such as current density, temperature, and the characteristics of the electrolyte-electrode interface.

[0220] Advantages of Solid Electrolytes for Mitigating Dendrite Formation

[0221] Solid electrolytes offer several advantages over liquid electrolytes in mitigating dendrite formation. The mechanical strength of solid electrolytes can help inhibit dendrite growth by providing a physical barrier to lithium metal penetration. Furthermore, the uniform ion distribution of solid electrolytes can promote more uniform lithium deposition, reducing the likelihood of localized dendrite nucleation. Some solid electrolytes can also form a stable interface with the lithium metal anode, further inhibiting dendrite formation. However, while solid electrolytes can significantly reduce the risk of dendrite growth, they may not completely eliminate it, and ongoing research aims to develop advanced solid electrolyte materials with enhanced dendrite inhibition capabilities.

[0222] Shape of negative active material

[0223] The negative active material may have a particle shape or may be in a continuous, single form (e.g., a thin film or sheet).

[0224] particle size

[0225] In embodiments where the negative active material is in particle form, the negative active material may have a particle size ranging from exactly or approximately 10 nm to exactly or approximately 1000 μm, for example, about 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, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm, 600 nm, 610 nm, 620 nm, 630 nm, 640 nm, 650 nm, 660 nm, 670 nm, 680 nm, 690 nm, 700 nm, 710 nm, 720 nm, 730 nm, 740 nm, 750 nm, 760 nm, 770 nm, 780 nm, 790 nm, 800 nm, 810 nm, 820 nm, 830 nm, 840 nm, 850 nm, 860 nm, 870 nm, 880 nm, 890 nm, 900 nm, 910 nm, 920 nm, 930 nm, 940nm, 950 nm, 960 nm, 970 nm, 980 nm, 990 nm, 1000 nm, 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, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm 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, 980 μm, 990 μm, or 1,000 μm. In embodiments, the particle size of the negative active material may be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within a range from exactly or approximately 10 nm to exactly or approximately 1,000 μm (e.g., about 10 nm and about 1,000 μm between).

[0226] Amount of negative active material

[0227] The amount of the negative active material in the solid-state battery (100) affects the charge and discharge capacity of the solid-state battery (100). To manufacture a high-capacity negative electrode (104), the negative electrode (104) may include a high level of the negative active material. For example, the negative electrode (104) includes exactly, approximately, or greater than 70, 80, 90, 95, 98, 99, or 100 wt % of the negative active material based on the total weight of the negative electrode (104). In embodiments, the amount of the negative active material in the negative electrode (104) may be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 70 wt % and about 100 wt %).

[0228] Binder material for cathode electrode

[0229] The binder may include various types of binder polymers, such as, for example, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, EPDM, sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, polymers thereof in which hydrogen atoms are substituted with lithium, sodium or calcium, various copolymers thereof, the like, or combinations thereof.

[0230] Examples of binder materials for cathode electrodes

[0231] In addition to the binders mentioned above, other binders suitable for use in the negative electrode may include polyimides, polyamide-imides, polyurethanes, polyethylene oxide (PEO), poly(ethylene-co-vinyl acetate) (PEVA), poly(vinyl acetate) (PVA), alginates, chitosan, guar gum, xanthan gum, carrageenan, pectin, gelatin, lignin, and various water-soluble polymers or derivatives thereof. In some cases, conductive polymers such as polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene) (PEDOT) may also be used as binders to simultaneously improve adhesion and electrical conductivity.

[0232] Binder content of the negative electrode

[0233] The cathode electrode (104) can include exactly or approximately 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt % of the binder, or any other wt % within the range of 0 to 30 wt %, based on the total weight of the cathode electrode (104). In embodiments, the amount of binder in the cathode 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 30 wt % (e.g., between about 0 wt % and about 30 wt %).

[0234] Thickness of the cathode electrode

[0235] The cathode electrode (104) can have a thickness of exactly or approximately 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 μm. In embodiments, the thickness (t4) of the cathode electrode (104) can be within a range formed by selecting any two values ​​listed above or selecting any two values ​​within a range from 10 μm to about 100 μm (e.g., between about 10 μm and about 100 μm or between about 10 μm and about 20 μm).

[0236] Porosity of the cathode electrode

[0237] The porosity of the cathode electrode (104) can be approximately 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 %, based on the total volume of the cathode electrode (104). In embodiments, the porosity of the cathode 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 about 18 volume %.

[0238] Lithium ion diffusion in the negative electrode

[0239] The cathode electrode (104) is exactly or approximately 1 x 10 -14 cm 2 / s, 1 x 10 -13 cm 2 / s, 1 x 10 -12 cm 2 / s, 1 x 10 -11 cm 2 / s, 1 x 10 -10 cm 2 / s, 1 x 10 -9 cm 2 / s, 1 x 10 -8 cm 2 / s, or 1 x 10 -7 cm 2 / s may have a lithium ion diffusivity of 104. In embodiments, the lithium ion diffusivity of the negative electrode (104) may be selected from any two values ​​listed above or may be exactly or approximately 1 x 10 -14 cm 2 Exactly or approximately 1 x 10 in / s -7 cm 2 / s can be formed by selecting any two numbers within the range.

[0240] Current collector of the negative electrode

[0241] The current collector (110) collects the electric energy generated from the cathode electrode (104) and supports the cathode electrode (104).

[0242] Material for current collector of negative electrode

[0243] The material of the current collector (110) is not particularly limited as long as it allows adhesion of the negative electrode (104), has appropriate electrical conductivity, and does not cause significant chemical changes in the solid-state battery (100) within the voltage range of the solid-state battery (100). For example, the current collector (110) may be made of or include, but is not limited to, a metal or conductive carbon.

[0244] Metal for current collector

[0245] The metal of the current collector (110) may include, but is not limited to, one or more 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 a combination thereof.

[0246] Current collector shape of the negative electrode

[0247] It is possible to increase the adhesion of the negative electrode (104) to the current collector (110) by forming fine surface irregularities on the surface of the current collector (110). The current collector (110) may have various shapes, such as a film, a sheet, a foil, a mesh, a porous body, a foam, a non-woven fabric, the like, or a combination thereof. In addition to the shapes mentioned above, the current collector (110) may be configured as a honeycomb structure, a perforated sheet, a woven or non-woven mesh, a sintered porous body, or a three-dimensional interconnected network. These various shapes can be adjusted to optimize the surface area, mechanical strength, and current collection efficiency of the current collector (110).

[0248] Current collector design of the negative electrode

[0249] Additionally, the current collector (110) can be designed to fit various solid-state battery shapes, 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.

[0250] Current collector thickness of the negative electrode

[0251] The thickness (t5) of the current collector (110) is exactly or approximately 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, It may be 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 embodiments, the thickness (t5) of the collector (110) may be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within a range from exactly or approximately 1 μm to exactly or approximately 500 μm (e.g., between about 5 μm and about 500 μm).

[0252] Method for manufacturing a cathode electrode

[0253] The cathode electrode (104) can be obtained by various methods, such as atomic deposition, extrusion, rolling, slurry methods, or a combination thereof. In addition to the methods mentioned, the cathode electrode (104) can be manufactured using various other techniques, including a dry electrode process. These alternative methods may offer advantages in terms of environmental impact, cost-effectiveness, and scalability.

[0254] dry powder coating

[0255] As an alternative to the slurry method, dry powder coating can be used. In this process, the negative active material, conductive additive, and binder are mixed in a dry state and then applied directly to the current collector (110) using electrostatic deposition or mechanical compression. This method can potentially reduce environmental impact and process time by reducing the use of solvents.

[0256] 3D printing

[0257] 3D printing, an additive manufacturing technology, can be used to fabricate the cathode electrode (104). Various 3D printing methods, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW), can be utilized depending on the specific material and desired electrode properties. This approach allows for precise control over the electrode structure and porosity.

[0258] electrospinning

[0259] Electrospinning is another potential method for fabricating negative electrodes (104). In this process, a solution containing the negative active material, a conductive additive, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be directly collected on a current collector (110) to form a highly porous electrode structure with a high surface area.

[0260] Tape casting

[0261] A negative electrode (104) can be manufactured using tape casting. This technique involves applying a slurry of electrode material onto a moving carrier film using a doctor blade, followed by drying and calendering. The resulting electrode tape can then be laminated to a current collector (110).

[0262] spray coating

[0263] Spray coating technology can be used to fabricate the cathode electrode (104). In this method, a fine mist of electrode slurry is sprayed onto a current collector (110) using compressed air or ultrasonic atomization. This approach can enable the production of a thin, uniform electrode layer and may be particularly useful for large-scale production.

[0264] Freeze casting

[0265] Freeze-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 create a porous structure. The resulting porous electrode can then be sintered and attached to a current collector (110).

[0266] sol-gel process

[0267] In some cases, a sol-gel process may be used to fabricate the negative electrode (104). This method involves forming a colloidal suspension (sol) containing the negative electrode active material and other components, and then converting it into a gel-like network. This gel may be applied to a current collector (110) and then heat-treated to form the final electrode structure.

[0268] gas deposition

[0269] In certain applications, physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques can be used to form a thin-film anode directly on a current collector (110). These methods can produce very uniform and dense electrode layers, which can be particularly useful for certain types of solid-state batteries.

[0270] Alloying and ball milling

[0271] Mechanical alloying and high-energy ball milling can be used to prepare composite anode materials, which can then be pressed into an electrode or applied to a current collector (110) using one of the methods described above. This technique may be particularly useful for producing nanostructured or amorphous anode materials with enhanced electrochemical properties.

[0272] Slurry method

[0273] For example, a negative electrode active material can be mixed with a solvent and stirred, optionally including a binder and a dispersant, to form a slurry. Then, this slurry can be applied (e.g., coated) to a current collector (110), followed by pressurization and drying to obtain a negative electrode (104).

[0274] Method for applying slurry for cathode electrode

[0275] Application of the slurry for the negative electrode (104) may include a technique selected from the group consisting of slot die coating, gravure coating, spin coating, spray coating, roll coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, plate printing, intaglio printing, offset printing, the like, and combinations thereof. In addition to the aforementioned techniques, other methods of applying the negative electrode slurry to the current collector may include doctor blade coating, dip coating, and meniscus coating.

[0276] Double-layer slot die coating

[0277] Double-layer slot-die coating can also be used, allowing for the simultaneous application of two different electrode material layers to the current collector in a single pass. This method can create a gradient structure within the electrode, optimizing both electrochemical performance and mechanical properties.

[0278] Solvent for slurry for cathode electrode

[0279] The solvent for forming the negative electrode (104) may include water and / or an organic solvent such as N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), acetone, dimethyl acetamide, dimethyl sulfoxide (DMSO), isopropyl alcohol, the like, or a combination thereof. The solvent may be used in an amount sufficient to dissolve and disperse the electrode components, i.e., the negative electrode active material and the binder, and may be determined in consideration of the slurry coating thickness, production yield, the like, or a combination thereof. Additional solvents such as ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene may be included.

[0280] Method without using solvents

[0281] In some embodiments, the cathode electrode (104) may be manufactured using solvent-free methods, such as dry powder processing or melt extrusion, which may provide environmental and cost advantages by eliminating the use of liquid solvents.

[0282] Dispersant for slurry for cathode electrode

[0283] The dispersant for forming the cathode electrode (104) may include an aqueous dispersant and / or an organic dispersant, and may include, for example, N-methyl-2-pyrrolidone. Other examples of aqueous dispersants may include sodium dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP), and carboxymethyl cellulose (CMC), and additional organic dispersants may include Triton X-100, polyethylene glycol (PEG), and various surfactants such as polysorbates or poloxamers.

[0284] How to avoid using dispersants

[0285] In some embodiments, the cathode electrode (104) may be manufactured using methods that do not require a dispersant, such as dry powder processing or certain additive manufacturing techniques.

[0286] Drying technology for slurry for cathode electrode

[0287] The slurry for the cathode electrode (104) can be dried by irradiating it with heat, electron beams (E-beams), gamma rays, ultraviolet rays (G, H, I-rays), the like, or a combination thereof to evaporate the solvent. For example, the slurry can be vacuum-dried at room temperature. During the drying step, the solvent is removed by evaporation, but other components remain without evaporation to form the cathode electrode (104).

[0288] Other drying techniques

[0289] In addition to the drying techniques mentioned, several other methods for drying the cathode electrode (104) may be used. These additional techniques may offer various advantages depending on the specific material, production requirements, and desired electrode properties.

[0290] Infrared (IR) drying

[0291] Infrared (IR) drying can be used to rapidly heat the electrode surface to promote solvent evaporation. This method can be particularly effective for thin electrode coatings and allows for precise control of the drying process.

[0292] Microwave drying

[0293] Microwave drying is another option that can provide volumetric heating of the electrode material, allowing for more uniform drying across the electrode thickness. In some cases, a combination of convection and microwave drying may be used to optimize drying speed and uniformity.

[0294] Freeze drying

[0295] Freeze-drying, or lyophilization, can be utilized for certain electrode formulations. This process involves freezing the slurry and then sublimating the solvent under vacuum conditions. Freeze-drying can help maintain the porous structure of the electrode, which can be beneficial for electrolyte penetration and ion transport.

[0296] Supercritical CO2 drying

[0297] Supercritical CO2 drying is an advanced technique for specialized electrode materials. This method involves replacing the solvent with liquid CO2, then evacuating it to a supercritical state. This approach can help preserve the fine nanostructures within the electrode and is particularly useful for aerogel-based electrodes.

[0298] Two-stage drying

[0299] In some cases, a two-step drying process may be used. For example, an initial drying step may be performed at a low temperature to remove the bulk solvent, followed by a higher temperature step to remove residual solvent and potentially initiate desired chemical reactions within the electrode material.

[0300] Ultrasonic drying

[0301] Ultrasonic drying may also be considered for certain electrode formulations. This technique uses high-frequency sound waves to agitate solvent molecules, potentially accelerating the drying process and improving solvent removal from the porous structure within the electrode.

[0302] General solid electrolyte layer

[0303] The solid electrolyte layer (106) is suitably configured to enable lithium ion diffusion between the positive electrode (102) and the negative electrode (104). The solid electrolyte layer (106) provides an electrically conductive path for the movement of charge carriers between the positive electrode (102) and the negative electrode (104). The solid electrolyte layer (106) is in electrical communication with the positive electrode (102) and the negative electrode (104).

[0304] Location of solid electrolyte

[0305] In embodiments, the solid electrolyte layer (106) is formed on and in direct contact with the anode electrode (102) or the cathode electrode (104). In embodiments, the solid electrolyte layer (106) is in direct contact with the anode electrode (102) and the cathode electrode (104). In other embodiments, another functional layer may be interposed between the solid electrolyte layer (106) and the anode electrode (102) and / or the cathode electrode (104).

[0306] Materials for solid electrolyte layers

[0307] The solid electrolyte layer (106) may be capable of transporting lithium ions. The material of the solid electrolyte layer (106) is not particularly limited as long as it allows adhesion to adjacent layers, has appropriate electrical conductivity, and does not cause significant chemical changes to the solid battery (100) within the voltage range of the solid battery (100). For example, the solid electrolyte layer (106) may include, but is not limited to, various inorganic solid electrolytes, polymer solid electrolytes, and / or polymer gel electrolytes. Additionally or alternatively, the solid electrolyte layer (106) may include, but is not limited to, ceramic electrolytes, glass electrolytes, hybrid organic-inorganic electrolytes, and nanostructured electrolytes.

[0308] Inorganic solid electrolyte

[0309] Inorganic solid electrolytes may include, but are not limited to, crystalline solid electrolytes, amorphous solid electrolytes, glass ceramic solid electrolytes, the like, or combinations thereof. The inorganic solid electrolytes may be sulfide-based, oxide-based, the like, or combinations thereof. In addition to sulfide-based and oxide-based inorganic solid electrolytes, other types of inorganic solid electrolytes may include halide-based electrolytes, nitride-based electrolytes, and borate-based electrolytes. For example, lithium-rich semi-perovskites (LiRAPs) such as Li3OCl and Li3OBr, lithium nitride (Li3N), and lithium borohydride (LiBH4) have been studied as potential solid electrolyte materials for lithium-ion batteries.

[0310] Sulfide-based solid electrolyte

[0311] The sulfide-based solid electrolyte contains sulfur (S) and has the ionic conductivity of a metal belonging to group I or group II of the periodic table, and may include Li-PS-based glass or Li-PS-based glass ceramic.

[0312] Examples of sulfide-based solid electrolytes

[0313] For example, sulfide-based solid electrolytes may include lithium sulfide, silicon sulfide, germanium sulfide, and boron sulfide. Specific examples of inorganic solid electrolytes include Li 3.833 Sn 0.833 As 0.166 S4, Li4SnS4, Li 3.25 Ge 0.25 P 0.75 S4, Li2S—P2S0, B2S3—Li2S, XLi2S-(100x)P2S 5　 (x=7080), Li2S—SiS2—Li3N, Li2S—P2S5—LiI, Li2S—SiS2—LiI, Li2S—B2S3—LiI, Li3N, LISICON, LIPON (Li 3+y PO 4-x N x ), thio-LISICON (Li 3.25 Ge 0.25 P0.75 S4), Li2O—Al2O3—TiO2—P2O 5　 (LATP), Li2S—P2S5, Li2S—LiI—P2S5, Li2S—LiI—Li2O—P2S5, Li2S—LiBr—P2S5, Li2S—Li2O—P2S5, Li2S—Li3PO4—P2S5, Li2S—P2S5—P2O5, Li2S—P2S5—SiS2, Li2S―P2S5―SnS, Li2S―P2S5―Al2S3, Li2S―GeS2, Li2S―GeS2―ZnS, Li10GeP2S 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 , similar thereto, or combinations thereof.

[0314] doped variants

[0315] In some cases, Al-doped Li 10 GeP2S 12 Doped variants of these materials, such as Sb-doped Li6PS5Cl, can also be used to further improve ionic conductivity or stability.

[0316] Oxide-based solid electrolyte

[0317] Oxide-based solid electrolyte materials contain oxygen (O) and have the ionic conductivity of metals belonging to group I or II of the periodic table.

[0318] Examples of oxide-based solid electrolyte materials

[0319] Oxide-based solid electrolyte materials include LLTO-based compounds, Li6La2CaTa2O 12 , Li6La2ANb2O 12 (A is Ca or Sr), Li2Nd3TeSbO 12 , Li3BO 2.5 N 0.5, Li9SiA1O8, LAGP compounds, LATP compounds, Li 1+x Ti 2x Al x Si y (PO4) 3y　 (0≤x≤1, 0≤y≤1), LiAl x Zr 2x　 (PO4) 3　 (0≤x≤1, 0≤y≤1), LiTi x Zr 2x (PO4) 3　 (0≤x≤1, 0≤y≤1), LISICON compounds, LIPON compounds, perovskite compounds, NASICON compounds and LLZO compounds or compounds derived therefrom (e.g., Al-doped Li7La3Zr2O 12 and Ta-doped Li7La3Zr2O 12 ) may include at least one selected from the group consisting of Li3OCl and Li3OBr. Lithium-rich semi-perovskites such as Li3OCl and Li3OBr have also been studied as potential oxide-based solid electrolytes.

[0320] composite oxide electrolyte

[0321] In some cases, composite oxide electrolytes combining multiple oxide materials, such as LLZO-LATP composites, may be used to take advantage of the advantages of different oxide systems.

[0322] polymer solid electrolyte

[0323] The polymer solid electrolyte is a composite of an electrolyte salt and a polymer resin and has lithium ion conductivity. The polymer solid electrolyte may include a polyether polymer, a polycarbonate polymer, an acrylate polymer, a polysiloxane polymer, a phosphazene polymer, a polyethylene derivative, an alkylene oxide derivative, a phosphate polymer, polyazitated lysine, a polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, a polymer containing an ionically dissociable group, a biopolymer such as poly(ethylene imine) (PEI), poly(methyl methacrylate) (PMMA), poly(acrylonitrile) (PAN), poly(ethylene succinate) (PES), chitosan, and a cellulose derivative, the like, or a combination thereof.

[0324] Polymer resin for solid polymer electrolyte

[0325] The solid polymer electrolyte may comprise a polymer resin, such as a branched copolymer comprising a polyethylene oxide (PEO) backbone copolymerized with a monomer comprising an amorphous polymer such as, for example, PMMA, polycarbonate, polydiloxane (PDMS), and / or phosphazene, a comb polymer, a cross-linked polymer resin, polyethylene glycol (PEG), polypropylene oxide (PPO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(ethylene oxide-co-propylene oxide) (PEO-PPO), poly(ethylene imine) (PEI), poly(vinyl pyrrolidone) (PVP), poly(vinyl alcohol) (PVA), various block copolymers or graft copolymers comprising these materials, the like, or combinations thereof.

[0326] polymer gel electrolyte

[0327] The polymer gel electrolyte can be formed by incorporating an organic electrolyte, an ionic liquid, a monomer, or an oligomer including an organic solvent and an electrolyte salt into a polymer resin, and may include similar ones, or combinations thereof. The polymer resin for the polymer gel can include a polyether polymer, a PVC polymer, a PMMA polymer, polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene: PVDF-co-HFP), similar ones, or combinations thereof.

[0328] Examples of polymer gel electrolytes

[0329] Examples of polymer gel electrolytes that may be suitable for solid-state batteries include poly(ethylene oxide) (PEO), poly(methyl methacrylate-co-ethyl acrylate) (PMMA-EA), poly(acrylonitrile-co-methyl methacrylate) (PAN-MMA), poly(vinyl acetate) (PVAc), poly(ethylene glycol diacrylate) (PEGDA), poly(vinyl pyrrolidone) (PVP), poly(ethylene glycol methyl ether acrylate) (PEGMEA), poly(ethylene glycol methyl ether methacrylate) (PEGMEMA), poly(ionic liquid) (PIL), poly(ethylene glycol-co-propylene glycol) (PEG-PPG), poly(vinyl alcohol-co-ethylene) (PVA-PE), poly(acrylamide) (PAM), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(ethylene It includes a gel electrolyte based on poly(glycol-co-polyethylene oxide) (PEG-PEO) and poly(methacrylic acid) (PMAA).

[0330] electrolyte salt

[0331] The electrolyte salt is an ionizable lithium salt and can be represented as Li+X-. X- may comprise an anion selected from the group consisting of 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 and the like.

[0332] Examples of lithium salts

[0333] For example, lithium salts include LiTFSI, LiCl, LiBr, LiI, LiClO4, lithium tetrafluoroborate (LiBF4), LiB 10 Cl 10 , lithium hexafluorophosphate (LiPF6), LiAsF6, LiSbF6, LiAlCl4, LiSCN, LiCF3CO2, LiCH3SO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC4F9SO3, LiC(CF3SO2)3, (CF3SO2)2NLi, lithium chloroborate, lithium lower aliphatic carboxylate, lithium 4-phenylborate imide, lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 4,5-dicyano-2-(trifluoromethyl)imidazolidide (LiTDI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and Any one selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), the like, and combinations thereof. The electrolyte salt may comprise any combination of the salts described herein.

[0334] Amount of electrolyte salt

[0335] The solid electrolyte layer (106) may comprise exactly or approximately 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 by weight based on the total weight of the solid electrolyte layer (106). In embodiments, the amount of the electrolyte salt in the solid electrolyte layer (106) may be within a range formed by selecting any two values ​​listed above or by selecting any two values ​​within a range between about 0 parts by weight and about 400 parts by weight or between about 60 parts by weight and about 400 parts by weight, based on the total weight of the solid electrolyte layer (106).

[0336] Ionic conductivity of the solid electrolyte layer

[0337] The solid electrolyte layer (106) may have appropriate reduction stability and / or ionic conductivity. Since the solid electrolyte layer (106) primarily functions to transport lithium ions between the electrodes, the solid electrolyte layer (106) may have, for example, exactly, approximately, or 10 -7 S / cm, 10 -6 S / cm, 10 -5 S / cm, or 10 -4 It may include a desirable ionic conductivity greater than S / cm.

[0338] Thickness of the solid electrolyte layer

[0339] The thickness (t6) of the solid electrolyte layer (106) is exactly or approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, or 1,000 μm. In embodiments, the thickness (t6) of the solid electrolyte layer (106) can be within a range formed by selecting any two numbers listed above or selecting any two numbers within a range between 0 and exactly or approximately 1,000 μm (e.g., between about 5 μm and about 1,000 μm, between about 30 μm and about 100 μm, or between about 30 μm and about 50 μm).

[0340] semi-finished products

[0341] The cell (101) illustrated in FIG. 1 may be provided as a semi-finished product. In embodiments, the cell (101) may be stored, transported, and / or delivered to a reseller, customer, or similar person who completes the manufacture of a battery assembly or product including the cell (101). In other embodiments, the cell (101) is a finished battery assembly or product.

[0342] Battery sealing

[0343] The housing (112) of the solid-state battery may be sealed to complete the fabrication of the solid-state battery (100) so that it can function as a battery. The sealing process may include various techniques to protect the internal components from external environmental factors and maintain the integrity of the battery structure. For example, the housing (112) may be hermetically sealed using laser welding, ultrasonic welding, or adhesive bonding. In some cases, the sealing process may also include the introduction of a protective atmosphere or the removal of air to create a vacuum. This sealing step may help prevent moisture ingress, which could potentially degrade the performance of the sulfide-based solid electrolyte. Additionally, the sealing process may include safety features, such as a pressure relief mechanism, to manage gas buildup that may occur during battery operation.

[0344] After sealing the battery

[0345] Once properly sealed, the solid-state battery (100) is ready for final quality control testing, including electrical testing, leak detection, and visual inspection. After passing these tests, the solid-state battery (100) can be packaged and sold as a finished product ready for integration into various electronic devices, electric vehicles, energy storage systems (e.g., energy storage systems for storing power generated by wind turbines and / or solar power generators), and the like.

[0346] Battery configuration

[0347] The solid-state battery (100) can be provided in various configurations to suit various applications and device requirements. In some aspects, the battery may be manufactured in a cylindrical shape, which may be advantageous for certain types of portable electronic devices or automotive applications. Alternatively, the solid-state battery (100) may be manufactured in a prismatic shape, which allows for more efficient space utilization in rectangular devices. In other cases, a pouch shape may be used, which provides flexibility in shape and potentially reduces overall battery weight. The pouch shape may also be particularly suitable because it may facilitate the application and control of uniform pressure within the solid-state battery.

[0348] Selection of configuration

[0349] The choice of configuration may vary depending on factors such as the intended use, space constraints, thermal management requirements, and manufacturing considerations. In some embodiments, hybrid or customized configurations combining different form factors may be utilized as needed. The diversity of battery form factors allows for the integration of solid-state batteries into a wide range of products, from small wearable devices to large-scale energy storage systems.

[0350] voltage

[0351] The solid state battery (100) is exactly or approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, The solid state battery (100) may be configured to output a voltage of 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 embodiments, the output voltage of the solid state battery (100) may be within a range formed by selecting any two numbers listed above or selecting any two numbers within a range between 0 and exactly or approximately 500 V (e.g., between about 1 V DC and about 500 V DC).

[0352] volume

[0353] The solid-state battery (100) can be configured to have a capacity of exactly, approximately, or greater than 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, or 300 mAh / g. In embodiments, the capacity of the solid-state battery (100) can be within a range formed by selecting any two numbers listed above or selecting any two numbers within a range between 0 and 300 mAh / g or between 0 and about 300 mAh / g (e.g., between about 100 mAh / g and about 300 mAh / g).

[0354] Calculating volume expansion ratio

[0355] The solid-state battery (100) can be configured to have a desirable volume expansion ratio. The volume expansion ratio can be calculated by comparing the thickness change after the first charge and discharge cycle with the initial thickness. The volume expansion ratio can be a ratio of the thickness change to the initial thickness. The first charge and discharge cycle is performed by performing a CC-CV charge at 0.1 C and cutting at 4.25 to 4.4 V and at 0.02 C, and performing a CC discharge at 0.1 C and cutting at 3 V. The volume expansion ratio can be calculated by Equation 1 below, where A represents the thickness before charge and discharge and B represents the thickness after charge and discharge. The thickness can be measured using a Mouser micrometer or a scanning electron microscope (SEM).

[0356]

[0357] Mathematical formula 1

[0358] Volume expansion ratio = [(BA) / A] × 100

[0359]

[0360] C-rate

[0361] The C-rate used here refers to the discharge rate relative to the battery's maximum capacity. For example, a 1C rate means that the discharge current will discharge the entire battery in 1 hour. For example, for a battery with a capacity of 20 ampere-hours, the discharge current at 1C would be 20 amperes.

[0362] C-rate of the battery

[0363] The solid state battery (100) can have a C-rate that is exactly, approximately, or greater than 0.33, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5. In embodiments, the C-rate of the solid state battery (100) can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 0.33 and about 5).

[0364] Other examples of volume expansion

[0365] Other methods for measuring and calculating the volume expansion of solid-state batteries may include using volume expansion measurements (e.g., gas pycnometers), in-situ dilatometry, X-ray tomography, strain gauge measurements, optical methods (e.g., digital image correlation or laser interferometry), pressure-based methods, and electrochemical strain microscopy.

[0366] contradiction

[0367] The additional features, embodiments, and examples discussed below may be applied to various aspects of the invention discussed above. However, if there is a conflict between the information discussed in the preceding section and the information discussed in the following section, the information in the preceding section shall apply.

[0368] Absence of carbon particles, sulfide particles, and oxide particles

[0369] The negative active material does not include carbon-based particles, sulfide-based particles, or oxide-based particles. For example, the negative electrode (104) may not include carbon-based particles, sulfide-based particles, or oxide-based particles. Carbon-based particles, sulfide-based particles, or oxide-based particles may occupy space within the negative electrode while contributing little or no to the capacity of the battery, thereby reducing energy capacity. Carbon-based particles, sulfide-based particles, or oxide-based particles may reduce contact between particles within the battery cell, which may require a higher pressure to be applied to the solid-state battery than would be required if the negative electrode did not contain carbon-based particles, sulfide-based particles, or oxide-based particles.

[0370] Characteristics of negative active materials

[0371] The negative electrode active material may have a particle shape. For example, the negative electrode active material may include, consist essentially of, or consist of first particles and second particles. The first particles and the second particles may not form a combined domain (e.g., a domain comprising silicon and a material, if the first particles comprise silicon and the second particles comprise a material), but may individually form discrete domains in the negative electrode (104). For example, referring to the detailed drawing of FIG. 1 , the first particles (114) form a discrete domain distinct from the second particles (116).

[0372] Amount of negative active material in the negative electrode

[0373] The amount of the negative active material of the solid-state battery (100) affects the charge and discharge capacity of the solid-state battery (100). To manufacture a high-capacity negative electrode (104), the negative electrode (104) may include a high level of the negative active material. For example, the negative electrode (104) includes exactly, approximately, or greater than 70, 80, 90, 95, 98, 99, or 100 wt % of the negative active material based on the total weight of the negative electrode (104). In embodiments, the amount of the negative active material of the negative electrode (104) may be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 70 wt % and about 100 wt %).

[0374] Total amount of first and second particles of negative active material

[0375] The negative active material can comprise greater than or equal to about 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the first particles and the second particles, based on the total weight of the negative active material. In embodiments, the amount of the first particles and the second particles in the negative active material can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 50% and about 99%, based on the total weight of the negative active material).

[0376] The amount of first particles

[0377] In embodiments, the negative active material can include about 10, 20, 30, 40, 50, 60, 70, 80, or 90 wt % of the first particles, based on the total weight of the negative active material. In embodiments, the amount of the first particles in the negative active material can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 10% and about 90%, between about 10% and about 20%, or between about 40% and about 60%, based on the total weight of the negative active material).

[0378] Amount of secondary particles

[0379] In embodiments, the negative active material can include about 10, 20, 30, 40, 50, 60, 70, 80, or 90 wt % of the second particles, based on the total weight of the negative active material. In embodiments, the amount of the second particles in the negative active material can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 10% and about 90%, between about 10% and about 20%, or between about 40% and about 60%, based on the total weight of the negative active material). In embodiments, the negative active material can include more of the first particles than of the second particles, based on the total weight of the negative active material.

[0380] Advantages of the materials of the first and second particles

[0381] The negative electrode active material can be made of or include various materials, such as, but not limited to, alkaline earth metals, alkaline earth metals, Group 3B metals, transition metals, metalloids, alloys thereof, or combinations thereof. The first particles and the second particles can include different materials. For example, the second particles can be softer than the first particles and configured to compensate for changes in size of the first particles during charge and discharge cycles of the solid-state battery. For example, when the first particles expand in size, the second particles can compress in size under a given pressure applied to the solid-state battery. When the first particles contract in size, the second particles can expand in size under a given pressure applied to the solid-state battery. The second particles can generally maintain direct or indirect contact with the first particles as well as with each other, which allows the solid-state battery to operate at a lower pressure than would be required in the absence of the second particles in the negative electrode.

[0382] Material of the first particles

[0383] The material of the first particles may be capable of reversible insertion and de-insertion of lithium ions. The first particles of the negative active material may comprise, consist essentially of, or consist of silicon.

[0384] Materials of secondary particles

[0385] The material of the second particles may be capable of reversible insertion and de-insertion of lithium ions. The second particles of the negative active material may include a first material compound capable of forming an alloy with lithium. The first material compound may include, consist essentially of, or consist of a metal or a metal alloy, such as, but not limited to, tin, a tin alloy, copper, a copper alloy, aluminum, an aluminum alloy, magnesium, a magnesium alloy, zinc, a zinc alloy, silver, a silver alloy, gold, a gold alloy, lead, a lead alloy, indium, an indium alloy, the like, or combinations thereof. In embodiments, the second particles may include, consist essentially of, or consist of tin or a tin alloy. The second particles may be free of lithium at the time of battery assembly prior to initial charge and discharge. For example, the second particles may include 0.1% or less of lithium based on the total weight of the second particles at the time of battery assembly prior to initial charge and discharge.

[0386] Example materials for secondary particles

[0387] The second particles of the negative active material may include a tin-lithium alloy. The weight concentration of tin in the tin-lithium alloy is greater than the weight concentration of lithium. For example, the weight concentration of tin in the tin-lithium alloy may be at least 1% greater than the weight concentration of lithium, for example, at least 2% greater, at least 5% greater, at least 10% greater, or at least 20% greater. In embodiments, the weight concentration of lithium in the tin-lithium alloy may be configured to vary depending on the state of charge of the solid-state battery.

[0388] Hardness of the first particles

[0389] The first particles may be harder than the first particles. For example, the first particles may have a first hardness of about 6, 6.5, 7, 7.5, or 8 on the Mohs scale. In embodiments, the first hardness of the first particles may be within a range formed by selecting any two values ​​listed in the immediately preceding sentence (e.g., between about 6 and about 8 on the Mohs scale).

[0390] Hardness of the second particles

[0391] The second particles may be softer than the first particles. For example, the second particles may have a second hardness of about 1, 1.25, 1.5, 1.75, 2, 3, or 4 on the Mohs scale. In embodiments, the second hardness of the second particles may be within a range formed by selecting any two values ​​listed in the immediately preceding sentence (e.g., between about 1 and about 4 on the Mohs scale).

[0392] Comparison of hardness

[0393] To compensate for size changes of the first particles during charge and discharge cycles of the solid-state battery, the second hardness can be at least, exactly, or about 2, 3, 4, 4.5, 5, or 5.5 Mohs hardness values ​​lower than the first hardness. In embodiments, the second hardness of the second particles can have a hardness value lower than the first hardness within a range formed by selecting any two values ​​listed in the immediately preceding sentence (e.g., lower by between about 2 and about 5.5 Mohs hardness values).

[0394] Particle size of negative active material

[0395] The negative active material can have a particle size of exactly or approximately 10 nm, 20 nm, 30 nm, 50 nm, 70 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 1,000 nm, 10 μm, 20 μm, 30 μm, 50 μm, 70 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500, or 1,000 μm. In embodiments, the particle size of the negative active material can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 10 nm and about 1,000 μm or between about 100 nm and about 500 μm). The particle size of the first particles in the negative active material can be the same as or different from the particle size of the second particles.

[0396] Advantages of different particle sizes

[0397] In embodiments where the first particles have different particle sizes than the second particles, the second particles and the first particles may form a bimodal distribution in the negative electrode (104). This bimodal distribution may be configured such that the second particles are positioned in the void spaces within the lattice of the first particles, thereby reducing the porosity of the negative electrode (104). The bimodal distribution may increase surface contact during charge and discharge cycles of the solid-state battery (100), such that the second particles generally maintain direct or indirect contact with the first particles as well as with each other. This may allow the solid-state battery (100) to operate at a lower pressure than would be required in the absence of the bimodal distribution in the negative electrode (104). In embodiments, the negative electrode (104) may have additional particles that form a larger distribution than the bimodal distribution.

[0398] Particle size of the first particles

[0399] The first particles can have a particle size of exactly or approximately 10 μm, 20 μm, 30 μm, 50 μm, 70 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500, or 1,000 μm. In embodiments, the particle size of the first particles can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 10 μm and about 1,000 μm or between about 10 μm and about 500 μm).

[0400] Particle size of secondary particles

[0401] The second particles can have a particle size of exactly or approximately 10 nm, 20 nm, 30 nm, 50 nm, 70 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, or 1,000 nm. In embodiments, the particle size of the second particles can be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between about 10 nm and about 1,000 nm). In embodiments, the particle size of the second particles can be less than half the particle size of the first particles, such as at least 10 times smaller, at least 100 times smaller, or at least 200 times smaller.

[0402] Improved thickness stability of the cathode electrode

[0403] In embodiments, the thickness (t4) of the negative electrode (104) may vary by less than 10%, 5%, 2%, 1%, or 0% during charge and discharge cycles at a given pressure applied to the solid-state battery (e.g., less than or equal to 10 MPa, less than or equal to 8 MPa, less than or equal to 5 MPa). In embodiments, the thickness (t4) of the negative electrode (104) may vary within a range formed by selecting any two values ​​listed in the immediately preceding sentence (e.g., between about 0% and about 10%).

[0404] Porosity of the cathode electrode

[0405] The porosity of the cathode electrode (104) may be about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 27, or 30 volume % based on the total volume of the cathode electrode (104). In embodiments, the porosity of the cathode electrode (104) may be within a range formed by selecting any two numbers listed in the immediately preceding sentence (e.g., between 0 volume % and about 30 volume % or between about 10 volume % and about 30 volume %).

[0406] Pressure applied to the battery

[0407] The layers of the solid state battery (100) can be under a pressure of exactly or approximately 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa. In embodiments, the layers of the solid state battery (100) can be within a range formed by selecting any two values ​​listed in the immediately preceding sentence (e.g., between about 1 MPa and about 10 MPa, or between 1 MPa and 5 MPa). For example, the negative electrode can be under a pressure in a range between about 1 MPa and about 10 MPa, or between 1 MPa and 5 MPa.

[0408] How to use solid-state batteries

[0409] A method of using a solid-state battery is provided. The method comprises repeatedly charging and discharging the solid-state battery. The negative electrode is in direct contact with the solid electrolyte, and this direct contact is maintained after charging and discharging by compensating for size changes in the first particles using second particles.

[0410] Method for manufacturing a solid-state battery

[0411] A method of manufacturing a cell of a solid-state battery is provided. The method comprises depositing a positive electrode layer and a solid electrolyte layer. The method comprises mixing first particles and second particles to form a mixture. The method comprises depositing the mixture on a negative electrode layer in such a way that the second particles are configured to compensate for changes in size of the first particles during charge and discharge cycles of the solid-state battery. When the first particles expand in size, the second particles compress in size at a given pressure applied to the solid-state battery, and when the first particles contract in size, the second particles expand in size at a given pressure applied to the solid-state battery, such that the second particles generally maintain direct or indirect contact with the first particles as well as with each other, thereby allowing the solid-state battery to operate at a lower pressure than would be required in the absence of the second particles in the negative electrode layer. The method comprises configuring the solid-state battery such that a solid electrolyte layer is positioned between the positive electrode layer and the negative electrode layer to allow movement of lithium ions between the positive electrode layer and the negative electrode layer.

[0412] Example

[0413] To facilitate understanding of the present disclosure, examples will be described in more detail below. However, the following examples are for illustrative purposes only and the scope of the present disclosure is not limited thereto.

[0414] Manufacturing process of the examples

[0415] The cathode composite was prepared by shear mixing the cathode active material, solid electrolyte, and electronic conductive material using a mortar and pestle. In a 10 mm die, the solid electrolyte powder was pressed at 300 MPa to form a separator layer. For the anode electrode, a slurry was formed by mixing cathode particles with N-methyl-2-pyrrolidone as a solvent and polyvinylidene as a binder in the desired ratio. The slurry was cast onto a copper current collector and vacuum-dried at 80 degrees Celsius. The cathode composite powder was then applied to the first side of the separator layer, and the anode electrode was placed on the second side of the separator layer. The three layers (anode-separator-cathode) were pressed at 500 MPa to assemble the cell.

[0416] Example 1

[0417] A first embodiment of a solid-state battery comprising a negative active material comprising 50 wt% of first particles comprising silicon and 50 wt% of second particles comprising tin was tested for specific capacity under an applied pressure of 75 MPa.

[0418] Second Example

[0419] A second embodiment of a solid-state battery comprising a negative active material comprising 50 wt% of first particles comprising silicon and 50 wt% of second particles comprising tin was tested for specific capacity under an applied pressure of 5 MPa.

[0420] Third Example

[0421] A third example of a solid-state battery comprising a negative active material comprising 100 wt% of particles including tin was tested for specific capacity under an applied pressure of 75 MPa.

[0422] Example 4

[0423] A fourth example of a solid-state battery comprising a negative active material comprising 100 wt% of particles including tin was tested for specific capacity under an applied pressure of 5 MPa. The results of the first, second, third, and fourth examples are shown in Fig. 2.

[0424] Example 5

[0425] A fifth example of a solid-state battery comprising a negative active material comprising 100 wt% of particles including tin was tested for specific capacity under an applied pressure of 5 MPa.

[0426] Example 6

[0427] A sixth embodiment of a solid-state battery comprising a negative active material comprising 80 wt% of first particles containing silicon and 20 wt% of second particles containing tin was tested for specific capacity under an applied pressure of 5 MPa.

[0428] Example 7

[0429] A seventh embodiment of a solid-state battery comprising a negative active material comprising 50 wt% of first particles containing silicon and 50 wt% of second particles containing tin was tested for specific capacity under an applied pressure of 5 MPa.

[0430] Example 8

[0431] An eighth example of a solid-state battery comprising a negative active material comprising 100 wt% of particles including tin was tested for specific capacity under an applied pressure of 5 MPa. The results of Examples 5, 6, 7, and 8 are shown in Fig. 3.

[0432] Description of various features and characteristics

[0433] Various features and characteristics are described herein to provide an understanding of the composition, structure, production, function, and / or operation of the present disclosure, including the disclosed compositions, coatings, and methods. It will be understood that the various features and characteristics of the present disclosure described herein may be combined in any suitable manner, regardless of whether such features and characteristics are explicitly described in combination herein. The inventors and applicants expressly intend that such combinations of features and characteristics are included within the scope of the present disclosure described herein. Accordingly, the claims may be amended to claim any features and characteristics, in any combination, that are explicitly or implicitly described in the specification, or otherwise explicitly or implicitly supported by the specification. Furthermore, applicants reserve the right to amend the claims to affirmatively disclaim features and characteristics that may exist in the prior art, even if such features and characteristics are not explicitly described herein. Accordingly, such amendments will not add new matter to the specification or claims and will comply with the disclosure, sufficiency of disclosure, and supplementary matter requirements of the specification.

[0434] Citation of reference documents

[0435] All patents, publications, or other documents identified in this specification are incorporated by reference in their entirety unless otherwise indicated, but only to the extent that the incorporated material does not conflict with any prior description, definition, statement, illustration, or other disclosure material expressly set forth herein. Accordingly, to the extent necessary, the express disclosure set forth herein shall supersede any conflicting material incorporated by reference. Any material, or portion thereof, incorporated by reference herein but that conflicts with prior definitions, statements, or other disclosure material set forth herein shall be incorporated only to the extent that no conflict arises between the incorporated material and the prior disclosure material. Applicant reserves the right to amend this specification to explicitly cite any subject matter incorporated by reference, or portions thereof. Any amendment to this specification to add such incorporated subject matter shall comply with the description, sufficiency of description, and supplementary matter requirements of the specification.

[0436] Description of various aspects

[0437] While this disclosure provides a description of various specific aspects for the purpose of illustrating various aspects of the present disclosure and / or potential applications thereof, it will be understood that variations and modifications are possible for those skilled in the art. Accordingly, this disclosure is not to be narrowly defined by the specific exemplary aspects provided herein, but rather is to be broadly construed, at least as set forth in the claims.

Claims

1. In a solid-state battery including a cell, the cell: With anode electrode; A negative electrode comprising a negative active material, wherein the negative active material comprises: First particles comprising silicon, and A negative electrode comprising second particles comprising a tin-lithium alloy, wherein the weight concentration of tin in the tin-lithium alloy is greater than the weight concentration of lithium; A solid battery comprising a solid electrolyte positioned between the positive electrode and the negative electrode and configured to enable movement of lithium ions between the positive electrode and the negative electrode, and in contact with at least a portion of the second particles, The first particles and the second particles do not form a combined domain including the silicon and the tin-lithium alloy, but individually form discrete domains at the cathode electrode, The second particles are softer than the first particles and are configured to compensate for a size change of the first particles during a charge and discharge cycle of the solid-state battery, such that when the first particles expand in size, the second particles are compressed in size at a given pressure applied to the solid-state battery, and when the first particles contract in size, the second particles are expanded in size at a given pressure applied to the solid-state battery, thereby allowing the second particles to maintain contact with each other and with the first particles, thereby allowing the solid-state battery to operate at a lower pressure than would be required in the absence of the second particles in the negative electrode. A solid-state battery, wherein a pressure of less than 10 MPa is applied to the solid-state battery.

2. In paragraph 1, The lithium ion diffusion of the above negative electrode is 1 x 10 -14 cm 2 1 x 10 in / s -7 cm 2 A solid-state battery having a range of / s, wherein the negative electrode has a thickness that changes by less than 10% during charge and discharge cycles at a given pressure applied to the solid-state battery.

3. In paragraph 1, A solid battery, wherein the first particles have a first hardness in the range of 6 to 8 Mohs hardness, and the second particles have a second hardness in the range of 1 to 4 Mohs hardness.

4. In paragraph 1, A solid-state battery, wherein the lithium weight concentration of the tin-lithium alloy is configured to vary based on the state of charge of the solid-state battery.

5. In paragraph 1, A solid-state battery, wherein the negative active material does not contain carbon particles, sulfide particles, or oxide particles.

6. In paragraph 1, A solid-state battery wherein the second particles do not contain lithium at the time of battery assembly prior to initial charge and discharge.

7. In paragraph 1, A solid-state battery, wherein the negative electrode comprises more of the first particles than the second particles based on the total weight of the negative electrode active material.

8. In paragraph 1, A solid-state battery, wherein the negative active material is essentially composed of the first particles and the second particles.

9. In paragraph 1, The above negative active material: 10% to 90% by weight of the first particles based on the total weight of the negative active material; and A solid-state battery comprising 10% to 90% by weight of the second particles based on the total weight of the negative active material.

10. In paragraph 1, The above negative active material: 40% to 60% by weight of the first particles based on the total weight of the negative active material; and A solid-state battery comprising 40% to 60% by weight of the second particles based on the total weight of the negative active material.

11. In paragraph 1, A solid-state battery wherein the second particles and the first particles form a bimodal distribution in the negative electrode, the bimodal distribution being configured to reduce the porosity of the negative electrode by having the second particles positioned in the pore spaces within the lattices of the first particles, and the bimodal distribution increasing surface contact during charge and discharge cycles of the solid-state battery, allowing the second particles to maintain contact with each other and with the first particles, thereby allowing the solid-state battery to operate at a lower pressure than would be required in the absence of the bimodal distribution in the negative electrode.

12. In paragraph 1, A solid-state battery, wherein the first particles have a first average particle size in the range of 10 μm to 1,000 μm, and the second particles have a second particle size in the range of 10 nm to 1,000 nm.

13. In paragraph 12, A solid battery, wherein the first particles have a first average particle size, the second particles have a second average particle size, and the second average particle size is less than half of the first average particle size.

14. In paragraph 1, A solid-state battery, wherein the negative electrode has a porosity in the range of 10% to 30% by volume based on the total volume of the negative electrode, the solid-state battery has a C-rate greater than 0.33, the negative electrode is under a pressure in the range of 1 MPa to 5 MPa, and the solid-state battery comprises a specific capacity greater than 100 mAh / g.

15. An electric vehicle comprising a solid-state battery according to paragraph 1.

16. An energy storage system for storing power generated by a wind generator and / or a solar generator, comprising a solid-state battery according to paragraph 1.

17. A method of using a solid-state battery, wherein the solid-state battery comprises a cell, and the cell comprises: With anode electrode; A negative electrode comprising a negative active material, wherein the negative active material comprises: First particles comprising silicon, and A negative electrode comprising second particles comprising a tin-lithium alloy, wherein the weight concentration of tin in the tin-lithium alloy is greater than the weight concentration of lithium; A solid battery comprising a solid electrolyte positioned between the positive electrode and the negative electrode and configured to enable movement of lithium ions between the positive electrode and the negative electrode, and in contact with at least a portion of the second particles, The first particles and the second particles do not form a combined domain including the silicon and the tin-lithium alloy, but individually form discrete domains at the cathode electrode, The second particles are softer than the first particles and are configured to compensate for a size change of the first particles during a charge and discharge cycle of the solid-state battery, such that when the first particles expand in size, the second particles are compressed in size at a given pressure applied to the solid-state battery, and when the first particles contract in size, the second particles are expanded in size at a given pressure applied to the solid-state battery, thereby allowing the second particles to maintain contact with each other and with the first particles, thereby allowing the solid-state battery to operate at a lower pressure than would be required in the absence of the second particles in the negative electrode. A solid battery in which a pressure of less than 10 MPa is applied to the solid battery, The above method is: A method comprising repeatedly charging and discharging the solid battery while the negative electrode is in direct contact with the solid electrolyte, by compensating for size changes in the first particles using the second particles, and maintaining direct contact even after charging and discharging.

18. A method for manufacturing a solid battery cell, the method comprising: Step of depositing the anode layer; A step of depositing a solid electrolyte layer; A step of forming a mixture by combining first particles containing silicon and second particles containing a material configured to form an alloy with lithium, wherein the negative electrode does not contain carbon-based particles, sulfide-based particles, or oxide-based particles, and the second particles are softer than the first particles; A step of depositing the mixture on a cathode layer so that the second particles compensate for the size change of the first particles during a charge and discharge cycle of the solid-state battery, wherein when the size of the first particles expands, the second particles are compressed in size at a given pressure applied to the solid-state battery, and when the size of the first particles contracts, the second particles are expanded in size at a given pressure applied to the solid-state battery, so that the second particles maintain contact with each other and with the first particles, thereby allowing the solid-state battery to operate at a lower pressure than the pressure required when the second particles are absent in the cathode layer; and A step of configuring the solid battery such that the solid electrolyte layer is positioned between the positive electrode layer and the negative electrode layer to enable movement of lithium ions between the positive electrode layer and the negative electrode layer, A method for manufacturing a cell of a solid-state battery, wherein the first particles and the second particles do not form a combined domain including the silicon and the tin-lithium alloy, but individually form discrete domains in the negative electrode layer.

19. In paragraph 18, A method for manufacturing a solid battery cell, wherein the mixture further comprises a solvent and a binder.

20. In paragraph 18, A method for manufacturing a solid-state battery cell, further comprising the step of integrating the solid-state battery into an electric vehicle.

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