Method of manufacturing a solid state battery device

Abstract

A method of manufacturing a solid-state battery device is provided. The method includes continuously supplying a first composite sheet including a cathode layer and a solid electrolyte layer formed on the cathode layer. The method includes continuously supplying an aluminum-containing sheet over the first composite sheet such that the aluminum-containing sheet is disposed on the solid electrolyte layer of the first composite sheet. The method includes continuously roll bonding the aluminum-containing sheet with the first composite sheet to provide a second composite sheet including the cathode layer. The method includes continuously supplying a third composite sheet over the second composite sheet, the third composite sheet including a lithium-containing layer and a conductive layer. The method includes continuously roll bonding the second composite sheet and the third composite sheet such that the lithium-containing layer and the aluminum-containing layer are compressed together to form a pre-lithiated anode.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of priority to U.S. Patent Application No. 63 / 556,019, filed February 21, 2024, and U.S. Patent Application No. 19 / 009,853, filed January 3, 2025, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This invention relates to a method for manufacturing a solid-state battery device. Background Technology

[0004] Secondary batteries

[0005] Rechargeable batteries have gradually become an ideal power source for various electronic devices, such as automobiles, computers, mobile phones, tools, electric scooters, bicycles, electric vehicles, energy storage systems, drones, and other equipment. Among rechargeable batteries, lithium-ion batteries have attracted much attention due to their ability to achieve a favorable balance between voltage and energy density. In addition to their performance advantages, lithium-ion rechargeable batteries can also contribute to addressing climate change by enabling transportation electrification and promoting the integrated use of renewable energy. These batteries help reduce greenhouse gas emissions by powering electric vehicles and storing electricity generated from intermittent renewable energy sources such as solar and wind power. Furthermore, the long cycle life and high energy density of lithium-ion batteries can support the development of smart grids and distributed energy systems, potentially improving overall energy efficiency and reducing dependence on fossil fuels. Previously, lithium rechargeable batteries contained liquid electrolytes, which typically contained lithium salts dissolved in organic solvents. However, there is growing interest in developing all-solid-state lithium rechargeable batteries as an alternative to conventional liquid electrolyte systems. All-solid-state batteries have potential advantages in terms of safety, stability, and energy density. Despite these potential benefits, the development of practical all-solid-state lithium rechargeable batteries still faces several significant challenges.

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

[0007] One challenge in all-solid-state battery design is achieving and maintaining a sufficient lithium-ion diffusion coefficient within the solid electrolyte material. Furthermore, during battery discharge and charging, some components (such as electrodes) may undergo volume changes (e.g., expansion and contraction). These volume changes can generate mechanical stress or lead to contact failures between components within the battery structure. Contact failures between battery components result in degraded charge-discharge performance and overall battery capacity decay. Researchers and engineers in the energy storage field are actively working to address these challenges. Their efforts primarily focus on developing novel materials and battery designs that achieve favorable lithium-ion diffusion coefficients while also accommodating the mechanical stresses associated with battery cycling. Improving the interfacial stability within all-solid-state batteries remains an important research direction. Overcoming the current limitations of all-solid-state battery systems holds promise for significantly improving energy storage capabilities across a wide range of applications.

[0008] Do not acknowledge existing technology

[0009] The discussions in this section are intended to provide background information in relation to the present invention and do not constitute an admission of prior art. Summary of the Invention

[0010] Technical issues

[0011] One aspect of the present invention provides a method for manufacturing battery cells.

[0012] Technical solution

[0013] Multiple aspects of the present invention

[0014] The method includes continuously supplying a first composite sheet, the first composite sheet comprising a positive electrode layer and a solid electrolyte layer formed on the positive electrode layer. The method includes continuously supplying an aluminum-containing sheet over the first composite sheet such that the aluminum-containing sheet is placed on the solid electrolyte layer of the first composite sheet. The method includes continuously rolling the aluminum-containing sheet to the first composite sheet to provide a second composite sheet, the second composite sheet comprising the positive electrode layer, the solid electrolyte layer, and an aluminum-containing layer derived from the aluminum-containing sheet. The method includes continuously supplying a third composite sheet over the second composite sheet, the third composite sheet comprising a lithium-containing layer and a conductive layer such that the lithium-containing layer of the third composite sheet is placed on the aluminum-containing layer of the second composite sheet. The method includes continuously rolling the second and third composite sheets together such that the lithium-containing layer and the aluminum-containing layer are compressed together, thereby forming a pre-lithiated negative electrode while disposed between the conductive layer and the first composite sheet. This suppresses the formation of cracks within the pre-lithiated negative electrode layer compared to rolling the lithium-containing layer and the aluminum-containing layer not disposed between the conductive layer and the composite layer comprising the electrolyte layer and the positive electrode layer.

[0015] In one general aspect, the process of continuously rolling together the aluminum-containing sheet and the first composite sheet to provide the second composite sheet reduces the thickness of the aluminum-containing sheet and the first composite sheet.

[0016] In one general aspect, the process of continuously rolling the second and third composite sheets together reduces the thickness of the aluminum-containing sheet and the first composite sheet.

[0017] In one general aspect, the process of continuously rolling the second composite sheet and the third composite sheet together applies an isostatic pressure of 150 N to 500 N to the second composite sheet and the third composite sheet.

[0018] In one general aspect, the process of continuously rolling the second composite sheet and the third composite sheet together applies a force of 150 N to 500 N to the second composite sheet and the third composite sheet.

[0019] In one general aspect, the method further includes heating the second composite sheet and the third composite sheet while continuously rolling them together.

[0020] In one general aspect, the conductive layer comprises copper.

[0021] In one general aspect, the first composite sheet includes a second aluminum-containing sheet formed above the positive electrode layer.

[0022] In one general aspect, the aluminum-containing sheet comprises aluminum particles and an adhesive, and the method further includes removing a plastic layer from the aluminum-containing sheet.

[0023] In one general aspect, the aluminum-containing sheet comprises aluminum foil.

[0024] In one general aspect, the thickness of the pre-lithiated anode is from 10 μm to 100 μm.

[0025] In one general aspect, the process of continuously rolling together the second composite sheet and the third composite sheet forms a battery cell assembly, and the specific capacity of the battery cell assembly is at least 100 mAh / g.

[0026] In one general aspect, the thickness of the battery cell assembly is less than 1 mm.

[0027] In one general aspect, the cell assembly is subjected to a pressure of 1 MPa to 10 MPa.

[0028] In one general aspect, the C-ratio of the battery cell assembly is at least 0.33.

[0029] In one general aspect, the solid-state battery comprises at least two cell assemblies.

[0030] In one general aspect, the positive electrode layer comprises lithium nickel manganese oxide.

[0031] In one general aspect, the lithium-ion diffusion coefficient in the pre-lithiated anode is 1×10⁻⁶. -14 cm 2 / s to 1×10 - 7 cm 2 / s.

[0032] In one general aspect, the present invention relates to a method comprising repeatedly charging and discharging a battery cell assembly.

[0033] The overview is not restrictive.

[0034] It should be understood that the present invention is not limited to the examples outlined in the invention description. Several other aspects will also be described and illustrated herein. Attached Figure Description

[0035] Figure 1 This is an example of a solid-state battery of the present invention; and

[0036] Figure 2 This is an example of the co-rolling method of the present invention, which can be applied to continuous assembly processes through the rolling process.

[0037] Non-restrictiveness of instances

[0038] The examples described herein illustrate some non-limiting implementations, and such examples should not be construed in any way as limiting the scope of the appended claims. Detailed Implementation

[0039] Examples and Implementation

[0040] The subject matter of the invention will be described and discussed in more detail with reference to the accompanying drawings and specific embodiments and examples, wherein some, but not all, embodiments of the invention are shown. Throughout the text, the same numerals refer to the same elements or components unless otherwise stated. The subject matter of the invention can be implemented in many different forms and should not be construed as being limited to the specific embodiments set forth herein; rather, these embodiments are provided to enable the invention to meet applicable legal requirements. In fact, those skilled in the art to which the subject matter of the invention pertains will conceive of many modifications and other embodiments of the subject matter of the invention. Therefore, it should be understood that the subject matter of the invention is not limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims.

[0041] "One", "one", and "the (that)"

[0042] As used herein, the singular form of a word includes the plural meaning unless the context clearly indicates otherwise. The plural includes the singular form, and vice versa. Therefore, the terms “a,” “an,” and “the” generally include the plural form of the corresponding term. For example, although the invention is described using terms such as “a layer,” “a substrate,” “a battery,” etc., more than one of the aforementioned components and other components (including combinations thereof) may be used.

[0043] "about"

[0044] The term “about” indicates and covers the value indicated and the range above or below that value.

[0045] "Including", "Basically composed of", and "Constituted of"

[0046] The term "comprising" should be interpreted inclusively, not exclusively. Similarly, the terms "including," "containing," and "or" should also be interpreted inclusively unless the context explicitly precludes such an interpretation. The disclosure of embodiments defined by the term "comprising" also includes the disclosure of embodiments "consisting of" and "composed of" the disclosed components. The phrase "consisting of" excludes any unstated elements, steps, or components.

[0047] "and / or"

[0048] The term “and / or” used in the context of “X and / or Y” should be interpreted as “X, Y or X and Y”.

[0049] "Up" and "above"

[0050] As used herein, the terms “on,” “coated on,” “formed on,” “deposited on,” “set on,” etc., indicate coating, forming, covering, depositing, or setting in contact with a surface below or above. On the other hand, the terms “above,” “coated above,” “formed above,” “deposited above,” “set above,” etc., indicate coating, forming, covering, depositing, or setting on or above a surface, but not necessarily in contact with that surface. For example, a layer formed “coated” “above” a substrate layer can be in direct contact with the substrate without intermediate materials; however, this phrase does not preclude the presence of one or more other layers of the same or different composition between the formed layer and the substrate layer.

[0051] Markush Group

[0052] As used herein, the term "the combination thereof" in any Markush-type representation refers to a combination or mixture of one or more elements selected from the group of elements disclosed in the Markush-type representation, and means that one or more elements selected from that group exist. The term "the combination thereof" includes all possible combinations of the elements referred to by the term.

[0053] "between"

[0054] As used in this article, the expression “between” includes endpoint values.

[0055] Numerical range

[0056] Furthermore, all numerical ranges herein should be understood to include all integers or fractions within that range. Moreover, any numerical range referenced herein is intended to encompass all subranges falling within that range, and these numerical ranges should be interpreted as supporting claims for any numerical value or subset of numerical values ​​within that range. For example, the disclosure of "1 to 10" should be understood to support ranges such as "1 to 8", "3 to 7", "1 to 9", "3.6 to 4.6", "3.5 to 9.9", etc. When ranges are given, any endpoint values ​​of these ranges and / or any numerical value within the range may be combined with the ranges of this invention.

[0057] "Including", "for example", and "such as"

[0058] As used herein, terms such as “including,” “for example,” and “like” mean “including / for example / like but not limited to.”

[0059] Combination of implementation methods

[0060] As used herein, the term "example" (especially when listed below) is illustrative only and should not be considered exclusive or comprehensive. Any implementation disclosed herein may be combined with any other implementation disclosed herein unless expressly stated otherwise.

[0061] Particle size

[0062] As used herein, particle size refers to the average particle size (D) measured by a microscope (e.g., optical microscope, electron microscope, scanning electron microscope (SEM), transmission electron microscope (TEM), atomic force microscope (AFM), confocal microscope, X-ray microscope, cryo-electron microscope, Raman microscope, or fluorescence microscope). 50 Particle size can be the diameter of spherical particles, or the length of ellipsoidal or other irregularly shaped particles in the direction of maximum size. As used herein, “D50” refers to the particle size at which 50% of the particles have a smaller diameter.

[0063] Solid-state lithium-ion batteries

[0064] Solid-state batteries can be charged and discharged multiple times for an electrical load. A solid-state battery consists of electrodes (positive and negative) and an electrolyte that allows lithium ions to move between the electrodes. Unlike conventional liquid electrolyte batteries, solid-state batteries do not contain any flowing liquid. A circuit is formed between the electrodes, allowing current to flow between them. During charging of a lithium-ion rechargeable battery, lithium ions are released from the positive electrode and inserted into the active material of the negative electrode. During discharging of a lithium-ion rechargeable battery, lithium ions are released from the negative electrode and inserted into the active material of the positive electrode. Energy transfer occurs as lithium ions migrate back and forth between the electrodes.

[0065] Solid-state battery structure

[0066] The present invention provides a solid-state battery 100, which includes a positive electrode 102, a negative electrode 104, and a solid electrolyte layer 106 between the positive electrode 102 and the negative electrode 104. The above is merely an exemplary example, and the solid-state battery 100 does not necessarily include all of these components. For example, in some configurations (e.g., an anode-less system), the negative electrode 104 may be omitted.

[0067] Optional extra layers

[0068] 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 interface layer, or a combination thereof.

[0069] protective layer

[0070] For example, a protective layer can be disposed between electrodes 102, 104 and the solid electrolyte layer 106, and / or in an anode-less system, the protective layer can be disposed between electrode 102 and current collector 110. The protective layer can also mitigate dendrite formation (especially on the negative electrode side), thereby improving the overall cycle life and safety of the battery. In some cases, the protective layer can help improve the interfacial stability between the electrode and the electrolyte, with the potential to reduce undesirable side reactions. Furthermore, the protective layer can enhance the mechanical properties of the electrode-electrolyte interface, which can help maintain good contact during cycling.

[0071] Protective layer material

[0072] The protective layer can contain materials such as lithium phosphate, lithium titanate, or lithium lanthanum zirconium oxide (LLZO), which 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.

[0073] membrane layer

[0074] In some configurations of all-solid-state batteries 100, a separator layer may also be included. These separator layers can provide additional mechanical support for the battery structure while still allowing efficient ion migration. The separator layer can also be designed as a gradient structure, with properties optimized for contact with the positive and negative electrode materials. For example, such a gradient structure can have different porosities, compositions, or surface properties along the thickness direction of the separator layer. In some aspects, the surface of the separator layer can be functionalized with ion-conducting groups or coatings to improve lithium-ion migration efficiency at the electrode-separator interface. The separator layer can also be designed as a multilayer structure, such as sandwiching a high-mechanical-strength core layer between ion-conducting outer layers; this structure is achieved by integrating different materials optimized for specific functions. The separator layer can also be designed to have self-healing capabilities, for example, by reforming bonds after being subjected to mechanical stress, which helps prevent short circuits caused by dendrite growth.

[0075] Diaphragm material

[0076] Conventional liquid electrolyte batteries typically employ porous polymer separators, while solid-state batteries can use thin ceramic or glass-ceramic layers as separators. Materials used for this purpose can include LLZO, lithium aluminum titanium phosphate (LATP), or lithium aluminum germanium phosphate (LAGP). Other separator materials suitable for solid-state batteries include lithium oxynitride phosphate (LiPON), lithium lanthanum titanate (LLTO), and garnet-type lithium materials (e.g., Li6BaLa2Ta2O). 12 ), sulfide materials (e.g., Li) 10 GeP2S 12 ) and polymer-ceramic composite materials (e.g., composites of polyethylene oxide (PEO) and ceramic fillers).

[0077] Solid-state battery cells

[0078] Figure 1 A cell 101 of a solid-state battery 100 according to one embodiment is shown. The cell 101 includes a positive electrode 102, a negative electrode 104, and a solid electrolyte layer 106 between the positive electrode 102 and the negative electrode 104. The cell 101 may optionally include one or more additional layers, such as a separator layer, a protective layer, a suppression layer, a solid electrolyte interface layer, or a combination thereof.

[0079] Cell structure

[0080] like Figure 1 As shown, the solid-state battery 100 may include a single cell 101. In other instances, the solid-state battery 100 may include multiple cells, such as at least two cells, at least three cells, or at least four cells. Connecting cells in series can increase the voltage of the solid-state battery 100, and connecting cells in parallel can increase the ampere-hour capacity of the solid-state battery 100.

[0081] Battery size

[0082] The width of cell 101 is w1, the length is 11, and the thickness is t1.

[0083] Cell thickness

[0084] The thickness t1 of cell 101 can be or approximately any value within the following range: approximately 100 μm to approximately 5000 μm, for example, approximately 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. m, 360μm, 370μm, 380μm, 390μm, 400μm, 410μm, 420μm, 430μm, 440μm, 450μm, 460μm, 470μm, 480μm, 490μm, 500μm, 510μm, 520μm, 530μm, 540μm, 550μm, 560μm, 570μm, 580μm, 590μm, 600μm, 610μm, 62 0μm, 630μm, 640μm, 650μm, 660μm, 670μm, 680μm, 690μm, 700μm, 710μm, 720μm, 730μm, 740μm, 750μm m, 760μm, 770μm, 780μm, 790μm, 800μm, 810μm, 820μm, 830μm, 840μm, 850μm, 860μm, 870μm, 880μm, 890μm, 900μm, 910μm, 920μm, 930μm, 940μm, 950μm, 960μm, 970μm, 980μm, 990μm, 1000μm, 1100μm, 1200μm, 1300μm, 1400μm, 1500μm, 1600μm, 1700μm, 1800μm, 1900μm, 2000μm, 3000μm, 4000μm 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 within a range formed by selecting any two values ​​within a range of about 100 μm to about 5000 μm (e.g., about 100 μm to about 5000 μm or about 100 μm to about 1000 μm).

[0085] Aspect Ratio of Width

[0086] The width w1 of the battery cell 101 can be substantially greater than the thickness t1 of the battery cell 101. In some embodiments, the aspect ratio of the width w1 to the thickness t1 can be at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, or 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, 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.

[0087] Aspect Ratio of Length

[0088] The length l1 of the battery cell 101 can be substantially greater than the thickness t1 of the battery cell 101. In some embodiments, the aspect ratio of the length l1 to the thickness t1 can be at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, or 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, 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.

[0089] positive electrode

[0090] The positive electrode 102 corresponds to one polarity (e.g., positive polarity) of the solid-state battery 100. During the discharge process of the solid-state battery 100, the positive electrode 102 constitutes the positive electrode. The positive electrode 102 is suitable for the diffusion of lithium ions between the current collector 108 and the solid electrolyte layer 106. The positive electrode 102 is electrically connected to the current collector 108.

[0091] Positive position

[0092] In some embodiments, the positive electrode 102 is formed above and in direct contact with the current collector 108. In other embodiments, another functional layer may be provided between the positive electrode 102 and the current collector 108.

[0093] Positive electrode material

[0094] The positive electrode 102 enables reversible insertion and extraction of lithium ions. For example, the positive electrode 102 may contain only a positive electrode active material. In other examples, the positive electrode 102 may optionally contain one or more of conductive carbon, solid electrolyte material, and binder. Optionally, the positive electrode 102 may also contain additives, such as oxidation stabilizers, reduction stabilizers, flame retardants, heat stabilizers, antifogging agents, thickeners, plasticizers, ionic conductivity enhancers, binders (described in detail below), dispersants, wetting agents, tackifiers, crosslinking agents, colorants, etc., or combinations thereof.

[0095] Examples of additives

[0096] Examples of such additives may include: butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT) as oxidative stabilizers; ascorbic acid or sodium sulfite as reducing stabilizers; aluminum hydroxide or magnesium hydroxide as flame retardants; phenolic compounds or phosphites as heat stabilizers; polyethylene glycol or silica nanoparticles as antifogging agents; carboxymethyl cellulose (CMC) or xanthan gum as thickeners; dibutyl phthalate or triethyl citrate as plasticizers; ceramic fillers or ionic liquids as ionic conductivity enhancers; polyvinylpyrrolidone or sodium dodecyl sulfate as dispersants; polysorbate or poloxamer as wetting agents; silanes or titanates as tackifiers; peroxides or aziridines as crosslinking agents; and carbon black or metal oxides as colorants.

[0097] Positive electrode active material

[0098] Positive electrode active materials may include: lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and Li[Ni a Co b Mn c M 1 d O2 (where M) 1 For each element selected from the group consisting of Al, Ga, In, or combinations thereof, 0.3 ≤ a < 1.0, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.5, 0 ≤ d ≤ 0.1, and a + b + c + d = 1), Li (Li e M 2 f-e-f M 3 f’ )O2-g A g (where 0≤e≤0.2, 0.6≤f≤1, 0≤f'≤0.2, 0≤g≤0.2, M) 2 Including manganese and at least one element selected from the group consisting of Ni, Co, Fe, Cr, V, Cu, Zn, and Ti, M 3 The element is selected from at least one element chosen from the group consisting of Al, Mg, and B, and A is selected from at least one element chosen from the group consisting of P, F, S, and N, or the above-mentioned compound having one or more transition metals substituted; lithium manganese oxide, for example, with the chemical formula Li 1+h Mn 2-h Compounds represented by O4 (where 0 ≤ h ≤ 0.33), LiMnO3, LiMn2O3, LiMnO2, etc.; lithium copper oxide (Li2CuO2); vanadium oxides, such as LiV3O8, V2O5, or Cu2V2O7; and compounds with the chemical formula LiNi. 1-i M 4 i O2 (where M) 4 =Co, Mn, Al, Cu, Fe, Mg, B or Ga, 0.01≤i≤0.3) represents nickel-site lithium nickel oxide; chemical formula LiMn 2-j M 5 j O2 (where M) 5 =Co, Ni, Fe, Cr, Zn or Ta, 0.01≤j≤0.1) or Li2Mn3M 6 O8 (where M) 6 Lithium manganese composite oxides represented by Fe, Co, Ni, Cu or Zn; LiMn2O4 in which lithium is partially substituted by alkaline earth metal ions; disulfides; LiFe3O4, Fe2(MoO4)3, etc., or combinations thereof.

[0099] Phosphate materials

[0100] Besides the aforementioned positive electrode active materials, the positive electrode can also contain other types of materials. For example, lithium iron phosphate (LiFePO4) can be used as a positive electrode active material due to its excellent thermal stability and long cycle life. Other materials include lithium manganese iron phosphate (LiMn...). x Fe 1-x Other phosphate materials 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) can also be used.

[0101] Layered oxide materials

[0102] Positive electrode active materials can also include layered oxide materials with various compositions, such as Li(Ni) 1-x- y Co x Mn y O2 (NCM) or Li(Ni) 1-x-y Co x Al y O2 (NCA), in which the ratio of Ni, Co, Mn and Al can be adjusted to optimize performance characteristics. For example, NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 High-nickel-content NCM materials, such as those containing O2, can be used to achieve higher energy densities. In some cases, the cathode active material can contain spinel structures (e.g., LiNi). 0.5 Mn 1.5 O4), this structure enables high-voltage operation. Alternatively, materials with a lithium hydroxyphosphorus iron oxide structure (such as LiFeSO4F or LiVPO4F) can be used, which have the potential for high energy density and good thermal stability.

[0103] Composite or hybrid cathode materials

[0104] Composite or mixed cathode materials containing two or more active materials can also be used. For example, a mixture of layered oxides and spinel materials can be used to balance energy density and power performance. As another example, lithium iron phosphate can be mixed with one or more of the above-mentioned cathode active materials. In some embodiments, the cathode active material may contain a surface-modified version of the above-mentioned compounds, the surface modification being designed to improve stability, conductivity, or other performance indicators.

[0105] New materials

[0106] The positive electrode active material can also include novel materials, such as disordered rock salt structures (e.g., Li3NbO4-like materials), lithium-rich anti-perovskite structures (e.g., Li3OCl), cationic disordered oxides (e.g., Li-Mn-VO systems), or high-entropy oxides. These materials can provide an ideal combination of high capacity and structural stability. In some cases, dopants or substituents can be added to the positive electrode active material to further modulate its electrochemical properties.

[0107] Particle properties of positive electrode active materials

[0108] The positive electrode active material can be in granular form. The particle size of the positive electrode active material can be from approximately 1 nm to approximately 1000 μm, for example, approximately any of the following values: 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. 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, 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 some embodiments, the particle size of the positive electrode active material can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​from about 1 nm to about 1000 μm (e.g., from about 10 nm to about 1000 μm). In the positive electrode 102, the voids between the positive electrode active material particles can be filled with a solid electrolyte material.

[0109] The content of positive electrode active material in the positive electrode

[0110] The content 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, a high level of positive electrode active material can be included in the positive electrode 102. For example, based on the total weight of the positive electrode 102, the content of the positive electrode active material in the positive electrode 102 may be approximately or greater than 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 98 wt%, or 99 wt%. In some embodiments, the content of the positive electrode active material in the positive electrode 102 may be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​from greater than 0 to about 100 wt% (e.g., from about 40 wt% to about 98 wt%).

[0111] Conductive material in the positive electrode

[0112] There are no particular restrictions on the conductive material in the positive electrode 102, as long as it is conductive and does not cause any chemical change in the corresponding all-solid-state battery 100. For example, the conductive material may include graphite, such as natural or artificial graphite; carbon black, such as acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermally cracked carbon black; conductive fibers, such as carbon fibers or metal fibers; carbon nanotubes (CNTs), including single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs); metal powders, such as fluorocarbons, 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; graphene, metal nanowires (e.g., silver nanowires), indium tin oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), conductive ceramics (e.g., titanium nitride or titanium carbide), etc., or combinations thereof.

[0113] The content of conductive material in the positive electrode

[0114] Based on the total weight of the positive electrode 102, the content of conductive material in the positive electrode 102 is or approximately 1 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt%. In some embodiments, the content of conductive material in the positive electrode 102 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from approximately 1 wt% to approximately 30 wt%.

[0115] Adhesive materials

[0116] Adhesives may include a variety of adhesive polymers, such as polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene propylene diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, polyacrylic acid, polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), ethylene-vinyl acetate copolymer (PEVA), polyvinyl acetate (PVA), chitosan, guar gum (GG), xanthan gum, carrageenan, pectin, water-soluble polymers, lignin, polymers in which hydrogen atoms are replaced by lithium, sodium, or calcium, various copolymers thereof, or combinations thereof.

[0117] Other adhesive materials

[0118] In addition to the aforementioned adhesive materials, other types of adhesive materials can be used in the positive electrode to improve its performance and stability. For example, water-soluble adhesives such as sodium alginate, gelatin, or polyacrylamide can be used to improve the environmental friendliness of the electrode manufacturing process. These adhesives can also provide advantages in electrode flexibility and bond strength. In some cases, to simultaneously improve the mechanical integrity and conductivity of the electrode, conductive adhesives such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) or polyaniline (PANI) can be used.

[0119] Novel adhesive system

[0120] Novel adhesive systems (such as self-healing polymers or supramolecular assemblies) can be incorporated to improve the long-term stability and cycle life of the battery. Furthermore, composite adhesives combining multiple polymers or incorporating inorganic nanoparticles can be used to adjust the mechanical, thermal, and electrochemical properties of the electrodes. In some embodiments, to reduce the environmental impact of battery production and disposal, bio-derived or biodegradable adhesives, such as cellulose derivatives or chitosan, can be employed.

[0121] The content of binder in the positive electrode

[0122] Based on the total weight of the positive electrode 102, the binder content in the positive electrode 102 is or approximately 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt%. In some embodiments, the binder content in the positive electrode 102 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from approximately 1 wt% to approximately 30 wt%.

[0123] solid electrolyte materials

[0124] The solid electrolyte material in the positive electrode 102 can be configured to be the same as the material of the solid electrolyte layer 106 discussed below. The solid electrolyte material in the positive electrode 102 can be the same as or different from the material of the solid electrolyte layer 106.

[0125] Content of solid electrolyte material in the positive electrode

[0126] Based on the total weight of the positive electrode 102, the content of solid electrolyte material in the positive electrode 102 is approximately 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt%. In some embodiments, the content of solid electrolyte material in the positive electrode 102 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, from approximately 1 wt% to approximately 30 wt%.

[0127] Thickness of the positive electrode

[0128] The thickness t2 of the positive electrode 102 can be or approximately any value within the range of 0 to 1000 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 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, etc. 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, 1000 μm. In some embodiments, the thickness t2 of the positive electrode 102 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​greater than 0 to about 1000 μm (e.g., about 10 μm to about 1000 μm).

[0129] Porosity of the positive electrode

[0130] Based on the total volume of the positive electrode 102, the porosity of the positive electrode 102 can be any value within the range of 0 to 20 volume%, such as 0 volume%, 1 volume%, 2 volume%, 3 volume%, 4 volume%, 5 volume%, 6 volume%, 7 volume%, 8 volume%, 9 volume%, 10 volume%, 11 volume%, 12 volume%, 13 volume%, 14 volume%, 15 volume%, 16 volume%, 17 volume%, 18 volume%, or any other volume% within the range of 0 to 20 volume%. In some embodiments, the porosity of the positive electrode 102 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of 0 to 20 volume% (e.g., 0 volume% to about 18 volume%).

[0131] Lithium-ion diffusion coefficient of the positive electrode

[0132] The lithium-ion diffusion coefficient of cathode 102 can be greater than or approximately greater than 0 to 1 × 10⁻⁶. -7 cm 2 Any value within the range of / s, for example, 1×10 -14 cm 2 / s, 1×10 -13 cm 2 / s, 1×10 -12 cm 2 / s, 1×10 -11 cm 2 / s, 1×10 -10 cm 2 / s, 1×10 - 9 cm 2 / s, 1×10 -8 cm 2 / s or 1×10 -7 cm 2 / s. In some embodiments, the lithium-ion diffusion coefficient of the positive electrode 102 can be within a range formed by selecting any two values ​​listed above, or it can be greater than 0 to 1 × 10⁻⁶. - 7 cm 2 / s (e.g., 1×10) -14 cm 2 / s to approximately 1×10 -7 cm 2 Within the range of / s, select any two values ​​to form a range.

[0133] Positive current collector

[0134] The current collector 108 collects the electrical energy generated by the positive electrode 102 and supports the positive electrode 102.

[0135] Materials for positive electrode current collectors

[0136] The material of the current collector 108 is not particularly limited, as long as it enables the positive electrode 102 to attach, has suitable conductivity, and does not cause significant chemical changes in the solid-state battery 100 within the voltage range of the solid-state battery 100. For example, the current collector 108 may be made of or contain a variety of materials, such as metals, conductive carbon, or conductive ceramics, but is not limited thereto. The metal of the current collector 108 may include one or more of the following: aluminum, aluminum alloys, copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, iron, iron alloys (e.g., steel, stainless steel), silver, silver alloys, gold, platinum, palladium, chromium, molybdenum, tungsten, tantalum, niobium, zirconium, vanadium, manganese, cobalt, indium, tin, lead, bismuth, or combinations thereof, but is not limited thereto.

[0137] Geometry of the current collector

[0138] To optimize the performance of the current collector 108 and its integration with the positive electrode 102, the current collector 108 can also be configured with a variety of other geometries, and its size can be determined according to specific shape factors (e.g., bag-shaped, cylindrical, and / or prismatic shape factors).

[0139] Shape of the positive current collector

[0140] By forming a fine surface irregularity structure on the surface of the current collector 108, the adhesion between the positive electrode 102 and the current collector 108 can be improved. The current collector 108 can have various shapes, such as a membrane, sheet, foil, mesh, porous body, foam, non-woven fabric, or a combination thereof.

[0141] Examples of current collector shapes and sizes

[0142] For example, the current collector 108 can be configured as a mesh or grid, which provides enhanced mechanical support while maintaining a high surface area for electrode attachment. In some embodiments, the current collector 108 can be designed with a corrugated or wavy pattern, potentially increasing the contact area with the positive electrode material and improving overall conductivity. The current collector 108 can also be made into a perforated sheet to allow for better electrolyte permeation and ion migration. In some cases, the current collector 108 can be formed into a three-dimensional structure, such as an interconnected fiber network or honeycomb structure, which can enhance the structural integrity of the electrode assembly while promoting efficient current collection.

[0143] Thickness of the positive current collector

[0144] The thickness t3 of the current collector 108 can be or approximately any value within the range of 0 to 500 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 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. The thickness t3 of the current collector 108 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​greater than 0 to 500 μm (e.g., from about 5 μm to about 500 μm). The values ​​are 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, or 500 μm. In some embodiments, the thickness t3 of the current collector 108 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​greater than 0 to 500 μm (e.g., from about 5 μm to about 500 μm).

[0145] Method for manufacturing positive electrode

[0146] The positive electrode 102 can be obtained through various methods.

[0147] Dry powder coating process

[0148] For example, a dry powder coating process can be used to mix the positive electrode active material, conductive additives, and binder in a dry state, and then directly coat them onto the current collector 108 using electrostatic deposition or mechanical pressing. This method can reduce environmental impact by reducing the use of solvents.

[0149] 3D printing

[0150] In some cases, additive manufacturing techniques (such as 3D printing) can be used to fabricate the positive electrode 102. This method allows for precise control of the electrode structure and porosity, potentially improving electrode performance and energy density. Depending on the specific material and desired electrode performance, various 3D printing methods can be employed, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW).

[0151] electrospinning

[0152] Another method for manufacturing the positive electrode 102 involves electrospinning. In this process, a solution containing a positive electrode active material, conductive additives, and a polymer binder is extruded through a nozzle under the influence of an electric field to form nanofibers. These fibers can be directly collected on the current collector 108 to form an electrode structure with high porosity and increased surface area.

[0153] Casting

[0154] In some embodiments, a casting process can be used to prepare the positive electrode 102. This technique involves spreading a slurry of electrode material onto a moving carrier film using a doctor blade, followed by drying and calendering. The resulting electrode strip can then be laminated onto the current collector 108.

[0155] Spraying

[0156] Alternatively, spraying technology can be used to prepare the positive electrode 102. In this method, a fine mist of electrode slurry is sprayed onto the current collector 108 using compressed air or ultrasonic atomization. This method can produce a thin and uniform electrode layer, and is particularly suitable for large-scale production.

[0157] Cryogenic casting

[0158] In some cases, cryogenic casting can be used to manufacture the positive electrode 102. This process involves freezing a slurry of electrode material, followed by the sublimation of ice to form a porous structure. The resulting porous electrode can then be sintered and attached to the current collector 108.

[0159] Sol-gel method

[0160] For some applications, the sol-gel method can be used to prepare the positive electrode 102. This method involves forming a colloidal suspension (sol) and then transforming it into a gel-like network containing the positive electrode active material and other components. This gel can be coated onto the current collector 108, followed by heat treatment to form the final electrode structure.

[0161] Slurry-based processes

[0162] For example, the positive electrode active material can be mixed with a solvent and optionally a binder, conductive material and dispersant to form a slurry. The slurry is then coated (e.g., applied) onto the current collector 108, followed by pressing and drying to obtain the positive electrode 102.

[0163] Coating method for positive electrode slurry

[0164] The coating of the slurry on the positive electrode 102 may include the use of techniques selected from the group consisting of: slot coating, gravure coating, spin coating, spray coating, roller coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, heat transfer printing, letterpress printing, intaglio printing, offset printing, and combinations thereof.

[0165] Double-layer slot coating

[0166] In some embodiments, dual-slit coating (DLD) technology can be used to prepare the positive electrode 102. This method simultaneously coats two different electrode materials onto the current collector 108 through a single channel. The DLD process can create a gradient structure within the electrode, potentially optimizing both the electrochemical performance and mechanical properties of the positive electrode. Furthermore, this technology can introduce functional intermediate layers or protective coatings during electrode fabrication, thereby potentially improving the overall performance and lifespan of the battery.

[0167] Solvent for positive electrode slurry

[0168] Solvents used for forming the positive electrode 102 may include water and / or organic solvents such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, dimethylacetamide, dimethyl sulfoxide (DMSO), isopropanol, and combinations thereof. The amount of solvent used should be sufficient to dissolve and disperse the electrode components (e.g., positive electrode active material, binder, and conductive material) considering factors such as slurry coating thickness, productivity, and combinations thereof. Other solvents that may be used include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0169] Solvent-free methods

[0170] In some aspects of the invention, solvent-free methods (e.g., dry powder processing or melt extrusion) can be used to prepare the positive electrode 102, which reduces the use of liquid solvents and can provide environmental and cost advantages.

[0171] Dispersant for positive electrode slurry

[0172] The dispersant used for forming the positive electrode 102 may include aqueous dispersants and / or organic dispersants, such as N-methyl-2-pyrrolidone. Other available dispersants may include polyvinylpyrrolidone (PVP), carboxymethyl cellulose (CMC), sodium dodecyl sulfate (SDS), Triton X-100, polyethylene glycol (PEG), polyacrylic acid (PAA), and various surfactants such as polysorbate or poloxamer.

[0173] Drying technology of positive electrode slurry

[0174] The slurry for cathode 102 can be dried by irradiation with heat, an electron beam (E-beam), gamma rays, or ultraviolet light (G-line, H-line, I-line), or a combination thereof, causing the solvent to evaporate. For example, the slurry can be vacuum dried at room temperature. Although the solvent is removed by evaporation through the drying step, other components do not evaporate and remain intact to form cathode 102.

[0175] Other drying techniques

[0176] In addition to the drying techniques mentioned above, other methods can also be used to dry the positive electrode 102, such as infrared (IR) drying, microwave drying, or freeze drying.

[0177] Combination of drying technologies

[0178] In some implementations, a combination of various drying techniques can 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.

[0179] Negative electrode overview

[0180] The negative electrode 104 corresponds to a polarity different from that of the positive electrode 102 in the solid-state battery 100 (e.g., negative polarity). During the discharge process of the solid-state battery 100, the negative electrode 104 constitutes the negative electrode. The negative electrode 104 is suitable for the diffusion of lithium ions between the current collector 110 and the solid electrolyte layer 106.

[0181] negative electrode position

[0182] The negative electrode 104 is electrically connected to the current collector 110. In some embodiments, the negative electrode 104 is formed above the current collector 110 and is in direct contact with the current collector 110. In other embodiments, another functional layer may be provided between the negative electrode 104 and the current collector 110.

[0183] Anode-free system

[0184] In some embodiments, as described above, the all-solid-state battery 100 can employ an anode-less system. In this structure, the negative electrode 104 can be omitted, and lithium metal can be directly deposited onto the current collector 110 during charging. This method can improve the energy density of the battery, eliminate the need for a separate negative electrode material, and also reduce the overall thickness of the battery structure.

[0185] negative electrode material

[0186] The negative electrode 104 enables reversible insertion and extraction of lithium ions. For example, the negative electrode 104 may contain only the negative electrode active material. In other examples, the negative electrode 104 may contain conductive particles, binders, or combinations thereof.

[0187] Additives for the negative electrode

[0188] Optionally, the negative electrode 104 may also contain additives such as oxidation stabilizers (such as butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tert-butyl hydroquinone), reduction stabilizers (such as ascorbic acid, sodium sulfite, isoascorbic acid, sodium metabisulfite), flame retardants (such as aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine cyanurate), heat stabilizers or light stabilizers (such as phenolic compounds, phosphites, hindered amine light stabilizers, ultraviolet absorbers such as benzophenone or benzotriazole), antifogging agents (such as polyethylene glycol, silica nanoparticles, glycerol, sorbitol), thickeners (such as carboxymethyl cellulose, xanthan gum), etc., or combinations thereof.

[0189] Other additives for the negative electrode

[0190] In addition, conductive additives such as carbon black, graphene or carbon nanotubes can be added to improve conductivity, while binder modifiers such as styrene-butadiene rubber or polyacrylic acid can improve adhesion and mechanical stability. Functional additives such as fluoroethylene carbonate or vinylene carbonate can also be included to promote the formation of a stable solid electrolyte interface layer on the surface of the negative electrode.

[0191] Materials of the negative electrode active material

[0192] The negative electrode active material is made of or contains the following various materials: such as alkali metals, alkaline earth metals, Group 3B metals, transition metals, metalloids, their alloys, conductive carbon, etc., or combinations thereof, but not limited to this. In some embodiments, the negative electrode active material may contain silicon, silicon alloys, lithium, lithium alloys, conductive carbon, etc., or combinations thereof, but not limited to this. In some embodiments, the lithium alloy is made of a lithium alloy containing silicon, chlorine, etc. or combinations thereof, or contains these materials. A lithium metal thin film can be used as the negative electrode active material.

[0193] Other negative electrode active materials

[0194] The negative electrode active material may include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, etc.; metal materials capable of forming alloys with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys, Al alloys, etc.; metal oxides capable of doping and de-doping lithium ions such as SiO x (0 < x < 2), SnO2, vanadium oxides or lithium vanadium oxides; and composite materials containing the above metal materials and carbonaceous materials such as Si-C composite materials or Sn-C composite materials.

[0195] Carbonaceous materials

[0196] Carbon-based materials can include low-crystallinity carbon, high-crystallinity carbon, or combinations thereof. Representative examples of low-crystallinity carbon are soft carbon or hard carbon; representative examples of high-crystallinity carbon are high-temperature calcined carbon, such as amorphous, plate-like, sheet-like, spherical, or fibrous natural or artificial graphite, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesophase carbon microspheres, mesophase pitch, coke derived from petroleum or coal tar pitch, or combinations thereof.

[0197] Metal-carbon composite materials

[0198] Alternatively, according to some aspects of the invention, the negative electrode 104 may comprise a metal-carbon composite negative electrode material, such as a silver-carbon mixture or composite, wherein silver particles are composited between amorphous and / or crystalline carbon particles. Silver is used here as an example, but other metals, including, for example, tin and / or zinc, may also be used. Silicon may be used instead of silver.

[0199] Other materials for negative electrode active materials

[0200] In addition to the materials mentioned above, the negative electrode active material may also include: titanium compounds (such as lithium titanate (Li4Ti5O)). 12 Materials such as titanium dioxide (TiO2) or molybdenum oxide (MoO2) exhibit excellent cycle stability and high-rate performance. Other promising materials include transition metal oxides, such as molybdenum oxide (MoO2). x ), iron oxide (FeO) x ) or nickel oxide (NiO) x These materials can provide high theoretical capacity. In some cases, composite materials combining different active materials can be used, such as silicon-graphite composites or tin-carbon composites, to fully utilize the advantages of multiple materials while mitigating their individual limitations.

[0201] Dendrite formation

[0202] When the negative electrode 104 is composed of or contains lithium or a lithium alloy, dendrites may form on the negative electrode 104. Dendrites are metallic lithium structures formed when excess lithium ions accumulate on the surface of the negative electrode 104. The formed dendrites may damage the solid electrolyte layer 106, reduce the capacity of the solid-state battery 100, and / or otherwise cause other adverse performance issues in the solid-state battery 100. Dendrite formation is a major challenge for lithium-ion batteries because these structures can grow through the electrolyte, potentially leading to short circuits and safety risks. The growth rate and morphology of dendrites can be affected by factors such as current density, temperature, and the properties of the electrolyte-electrode interface.

[0203] Advantages of solid electrolytes in suppressing dendrite formation

[0204] Solid electrolytes offer several advantages over liquid electrolytes in suppressing dendrite formation. The mechanical strength of solid electrolytes can provide a physical barrier to prevent lithium metal penetration, thus helping to inhibit dendrite growth. Furthermore, the uniform ion distribution in solid electrolytes can promote more uniform lithium deposition, reducing the likelihood of localized dendrite nucleation. Some solid electrolytes can also form stable interfaces with lithium metal anodes, further suppressing dendrite formation. However, while solid electrolytes can significantly reduce the risk of dendrite growth, they cannot completely eliminate it. Current research aims to develop advanced solid electrolyte materials with enhanced dendrite suppression capabilities.

[0205] Shape of negative electrode active material

[0206] The negative electrode active material can be in particulate form or in continuous monomer form (e.g., thin film or sheet).

[0207] Particle size

[0208] In embodiments where the negative electrode active material is in particulate form, the particle size of the negative electrode active material can be any value in the range of about 10 nm to about 1000 μm, such as 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, etc. 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, 940 nm, 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, 160μm, 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, 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, 970μm, 980 μm, 990 μm, or 1000 μm. In some embodiments, the particle size of the negative electrode active material can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of about 10 nm to about 1000 μm (e.g., about 10 nm to about 1000 μm).

[0209] Content of negative electrode active material in negative electrode

[0210] The content of the negative 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 negative electrode 104, a high level of negative electrode active material can be included in the negative electrode 104. For example, based on the total weight of the negative electrode 104, the content of the negative electrode active material in the negative electrode 104 may be approximately or greater than 70% by weight, 80% by weight, 90% by weight, 95% by weight, 98% by weight, 99% by weight, or 100% by weight. In some embodiments, the content of the negative electrode active material in the negative electrode 104 may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, approximately 70% by weight to approximately 100% by weight.

[0211] Materials of binder in negative electrode

[0212] Adhesives may include a variety of adhesive polymers, such as polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene propylene diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, polyacrylic acid, polymers in which hydrogen atoms are replaced by lithium, sodium or calcium, various copolymers thereof, or combinations thereof.

[0213] Material examples of binders in negative electrodes

[0214] In addition to the adhesives mentioned above, other adhesives suitable for the negative electrode may include polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), ethylene-vinyl acetate copolymer (PEVA), polyvinyl acetate (PVA), alginate, chitosan, guar gum, xanthan gum, carrageenan, pectin, gelatin, lignin, and various water-soluble polymers or their derivatives. In some cases, to simultaneously improve adhesion and conductivity within the negative electrode, conductive polymers such as polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene) (PEDOT) may be used as adhesives.

[0215] The content of binder in the negative electrode

[0216] Based on the total weight of the negative electrode 104, the binder content in the negative electrode 104 can be or approximately 0 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, or 30 wt%, or any other weight percentage within the range of 0 to 30 wt%. In some embodiments, the binder content in the negative electrode 104 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of 0 to 30 wt% (e.g., from about 0 wt% to about 30 wt%).

[0217] Thickness of the negative electrode

[0218] The thickness of the negative electrode 104 can be or approximately 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, or 100 μm. In some embodiments, the thickness t4 of the negative electrode 104 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​from 10 μm to about 100 μm (e.g., from about 10 μm to about 100 μm or from about 10 μm to about 20 μm).

[0219] Porosity of the negative electrode

[0220] Based on the total volume of the negative electrode 104, the porosity of the negative electrode 104 can be approximately 0% by volume, 1% by volume, 2% by volume, 3% by volume, 4% by volume, 5% by volume, 6% by volume, 7% by volume, 8% by volume, 9% by volume, 10% by volume, 11% by volume, 12% by volume, 13% by volume, 14% by volume, 15% by volume, 16% by volume, 17% by volume, or 18% by volume, or any other volume percentage within the range of 0 to 18%. In some embodiments, the porosity of the negative electrode 104 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of 0% to approximately 18% by volume.

[0221] Lithium-ion diffusion coefficient of the negative electrode

[0222] The lithium-ion diffusion coefficient of the 104 negative electrode can be 1×10⁻⁶ or approximately 1×10⁻⁶. -14 cm 2 / s, 1×10 -13 cm 2 / s, 1×10 -12 cm 2 / s, 1×10 -11 cm 2 / s, 1×10 -10 cm 2 / s, 1×10 -9 cm 2 / s, 1×10 -8 cm 2 / s or 1×10 -7 cm 2 / s. In some embodiments, the lithium-ion diffusion coefficient of the negative electrode 104 can be within a range formed by selecting any two values ​​listed above, or it can be within a range of 1×10. -14 cm 2 / s to approximately 1×10 -7cm 2 Within the range of / s, select any two values ​​to form a range.

[0223] Negative electrode current collector

[0224] The current collector 110 collects the electrical energy generated by the negative electrode 104 and supports the negative electrode 104.

[0225] Materials for negative electrode current collectors

[0226] The material of the current collector 110 is not particularly limited, as long as it enables the negative electrode 104 to attach, has suitable 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 contain metal or conductive carbon, but is not limited to these materials.

[0227] Metallic materials for current collectors

[0228] The metal of the current collector 110 may include one or more, or combinations thereof, selected from the group consisting of aluminum, aluminum alloys, copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, iron, iron alloys (e.g., steel, stainless steel), silver, and silver alloys, but is not limited thereto.

[0229] Shape of negative electrode current collector

[0230] By forming a fine surface irregularity on the surface of the current collector 110, the adhesion between the negative electrode 104 and the current collector 110 can be improved. The current collector 110 can have various shapes, such as a membrane, sheet, foil, mesh, porous body, foam, nonwoven fabric, or a combination thereof. In addition to the above shapes, the current collector 110 can also be configured as a honeycomb structure, perforated sheet, woven or nonwoven mesh, sintered porous body, or three-dimensional interconnected network structure. These different shapes can be adjusted to optimize the surface area, mechanical strength, and current collection efficiency of the current collector 110.

[0231] Design of negative electrode current collector

[0232] In addition, the current collector 110 can be designed to adapt to different shape factors of solid-state batteries, such as pouch cells, cylindrical cells, or prismatic cells, each of which can provide advantages in terms of packaging efficiency, thermal management, and overall battery performance.

[0233] Thickness of negative electrode current collector

[0234] The thickness t5 of the current collector 110 may be or be about 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, 46 μm, 47 μm, 48 μm, 49μm, 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, or 500 μm. In some embodiments, the thickness t5 of the current collector 110 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​from about 1 μm to about 500 μm (e.g., from about 5 μm to about 500 μm).

[0235] Method for manufacturing the negative electrode

[0236] The negative electrode 104 can be obtained by a variety of methods, such as atomic deposition, extrusion, calendering, slurry processing, or combinations thereof. In addition to the methods mentioned above, several other technologies can also be used to manufacture the negative electrode 104, including dry electrode processes. These alternative methods can offer advantages in terms of environmental impact, cost-effectiveness, and scalability.

[0237] Dry powder coating

[0238] Dry powder coating can be used as an alternative to the slurry method. In this process, the negative electrode active material, conductive additives, and binder are mixed in a dry state and then directly coated onto the current collector 110 using electrostatic deposition or mechanical pressing. This method can reduce the use of solvents and potentially reduce environmental impact.

[0239] 3D printing

[0240] Additive manufacturing technologies (such as 3D printing) can be used to fabricate the negative electrode 104. Depending on the specific material and desired electrode properties, various 3D printing methods can be employed, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW). This method allows for precise control over the electrode structure and porosity.

[0241] electrospinning

[0242] Electrospinning is another potential method for manufacturing the negative electrode 104. In this process, a solution containing the negative electrode active material, conductive additives, and polymer binder is extruded through a nozzle under the influence of an electric field to form nanofibers. These fibers can be directly collected on the current collector 110 to form an electrode structure with high porosity and increased surface area.

[0243] Casting

[0244] Casting can be used to prepare the negative electrode 104. This technique involves spreading an electrode material slurry onto a moving carrier film using a doctor blade, followed by drying and calendering. The resulting electrode film can then be laminated onto the current collector 110.

[0245] Spraying

[0246] Spray coating technology can be used to prepare the negative electrode 104. A fine mist of electrode slurry is sprayed onto the current collector 110 using compressed air or ultrasonic atomization. This method can produce a thin and uniform electrode layer, making it particularly suitable for large-scale production.

[0247] Cryogenic casting

[0248] Cryo casting is another potential method for manufacturing the negative electrode 104. This process involves freezing an electrode material slurry, followed by the sublimation of ice to form a porous structure. The resulting porous electrode can then be sintered and attached to the current collector 110.

[0249] Sol-gel method

[0250] In some cases, the sol-gel method can be used to prepare the negative electrode 104. This method involves forming a colloidal suspension (sol) and then transforming it into a gel-like network containing the negative electrode active material and other components. This gel can be coated onto the current collector 110, followed by heat treatment to form the final electrode structure.

[0251] vapor deposition

[0252] For some applications, physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques can be used to directly produce thin-film anodes on the current collector 110. These methods can produce highly uniform and dense electrode layers, which may be particularly advantageous for certain types of solid-state batteries.

[0253] Alloying and ball milling

[0254] Mechanical alloying and high-energy ball milling can be used to prepare composite anode materials, which are then pressed into electrodes or coated onto current collector 110 using one of the methods described above. This technique is particularly useful for preparing nanostructured or amorphous anode materials with enhanced electrochemical properties.

[0255] Slurry method

[0256] For example, the negative electrode active material can be mixed and stirred with a solvent and optionally a binder and dispersant to form a slurry. The slurry is then coated (e.g., applied) onto the current collector 110, followed by pressing and drying to obtain the negative electrode 104.

[0257] Coating method of negative electrode slurry

[0258] The coating methods for the negative electrode 104 slurry can include techniques selected from the group consisting of: slot coating, gravure coating, spin coating, spray coating, roller coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, letterpress printing, intaglio printing, offset printing, and combinations thereof. In addition to the above techniques, other methods for coating the negative electrode slurry onto the current collector include doctor blade coating, dip coating, and meniscus coating.

[0259] Double-layer slot coating

[0260] Alternatively, a double-slit coating technique can be used, which allows two different electrode materials to be simultaneously coated onto the current collector through a single channel. This method has the potential to create a gradient structure within the electrode, thereby optimizing both electrochemical performance and mechanical properties.

[0261] Solvent for negative electrode slurry

[0262] Solvents used for forming the negative electrode 104 may include water and / or organic solvents such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, dimethylacetamide, dimethyl sulfoxide (DMSO), isopropanol, and combinations thereof. The amount of solvent used should be sufficient to dissolve and disperse the electrode components (e.g., negative electrode active material and binder) considering slurry coating thickness, productivity, etc., or combinations thereof. Other usable organic solvents include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0263] Solvent-free methods

[0264] In some implementations, solvent-free methods (such as dry powder processing or melt extrusion) can be used to prepare the negative electrode 104. These methods do not require the use of liquid solvents and offer environmental and cost advantages.

[0265] Dispersant for negative electrode slurry

[0266] The dispersant used to form the negative electrode 104 may include aqueous dispersants and / or organic dispersants, such as N-methyl-2-pyrrolidone. Other examples of aqueous dispersants may include sodium dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP), and carboxymethyl cellulose (CMC), while other organic dispersants may include Triton X-100, polyethylene glycol (PEG), and various surfactants such as polysorbate or poloxamer.

[0267] Dispersant-free method

[0268] In some implementations, methods that do not require dispersants can be used to prepare the negative electrode 104, such as dry powder processing or certain additive manufacturing techniques.

[0269] Drying technology of negative electrode slurry

[0270] The negative electrode 104 slurry can be dried by irradiation with heat, electron beams (E-beams), gamma rays, or ultraviolet light (G-lines, H-lines, I-lines), causing the solvent to evaporate. For example, the slurry can be vacuum dried at room temperature. Although the drying step removes the solvent through evaporation, other components do not evaporate and remain intact to form the negative electrode 104.

[0271] Other drying techniques

[0272] Besides the drying techniques mentioned above, several other methods can also be used to dry negative electrode slurries. Depending on the specific materials, production requirements, and desired electrode performance, these other techniques can offer various advantages.

[0273] Infrared (IR) drying

[0274] Infrared (IR) drying can be used to rapidly heat the electrode surface, promoting efficient solvent evaporation. This method is particularly effective for thin electrode coatings and allows for precise control of the drying process.

[0275] Microwave drying

[0276] Microwave drying is another option, which can heat the electrode material in bulk, potentially achieving uniform drying across the entire electrode thickness. In some cases, convection drying and microwave drying can be combined to simultaneously optimize drying speed and uniformity.

[0277] freeze-drying

[0278] Freeze-drying (also known as lyophilization) can be used for specific electrode formulations. The process involves freezing the slurry and then sublimating the solvent under vacuum conditions. Freeze-drying helps maintain the porous structure of the electrode, which can be advantageous for electrolyte permeation and ion migration.

[0279] Supercritical CO2 drying

[0280] Supercritical CO2 drying is an advanced technique applicable to specialized electrode materials. The method involves replacing the solvent with liquid CO2, subsequently placing the CO2 in a supercritical state, and then venting it. This method helps preserve the fine nanostructures within the electrode, and is particularly useful for aerogel electrodes.

[0281] Two-step drying

[0282] In some cases, a two-step drying process can be employed. For example, a preliminary drying process can be carried out at a lower temperature to remove the main solvent, followed by a high-temperature step to remove residual solvent and potentially initiate the desired chemical reaction within the electrode material.

[0283] Ultrasonic drying

[0284] For specific electrode formulations, ultrasonic drying can also be considered. This technique utilizes high-frequency acoustic waves to agitate solvent molecules, potentially accelerating the drying process and improving solvent removal from the porous structure within the electrode.

[0285] Overview of solid electrolyte layers

[0286] The solid electrolyte layer 106 facilitates the diffusion of lithium ions between the positive electrode 102 and the negative electrode 104. The solid electrolyte layer 106 provides a conductive pathway for the migration of charge carriers between the positive electrode 102 and the negative electrode 104. The solid electrolyte layer 106 is electrically connected to both the positive electrode 102 and the negative electrode 104.

[0287] Location of solid electrolyte layer

[0288] In some embodiments, a solid electrolyte layer 106 is formed above and in direct contact with the positive electrode 102 or the negative electrode 104. In some embodiments, the solid electrolyte layer 106 is in direct contact with both the positive electrode 102 and the negative electrode 104. In other embodiments, an additional functional layer may be provided between the solid electrolyte layer 106 and the positive electrode 102 and / or the negative electrode 104.

[0289] Materials of solid electrolyte layers

[0290] The solid electrolyte layer 106 is capable of transporting lithium ions. The material of the solid electrolyte layer 106 is not particularly limited, as long as it can adhere to adjacent layers, has suitable conductivity, and does not cause significant chemical changes in the corresponding solid-state battery 100 within its voltage range. For example, the solid electrolyte layer 106 may comprise, but is not limited to, various inorganic solid electrolytes, polymer solid electrolytes, and / or polymer gel electrolytes. Alternatively or optionally, the solid electrolyte layer 106 may comprise, but is not limited to, ceramic electrolytes, glass electrolytes, organic-inorganic hybrid electrolytes, and nanostructured electrolytes.

[0291] Inorganic solid electrolytes

[0292] Inorganic solid electrolytes can include crystalline solid electrolytes, amorphous solid electrolytes, glass-ceramic solid electrolytes, or combinations thereof, but are not limited to these. Inorganic solid electrolytes can be sulfide-based, oxide-based, or combinations thereof. Besides sulfide and oxide-based inorganic solid electrolytes, other types of inorganic solid electrolytes can include halide electrolytes, nitride electrolytes, and borate electrolytes. For example, lithium-rich anti-perovskites (LiRAP) such as lithium oxychloride (Li3OCl) and lithium oxybromooxy (Li3OBr), lithium nitride (Li3N), and lithium borohydride (LiBH4) have been studied as potential solid electrolyte materials for lithium-ion batteries.

[0293] Sulfide solid electrolytes

[0294] Sulfide solid electrolytes contain sulfur (S) and have the ionic conductivity of Group I or Group II metals in the periodic table. They can include Li-PS type glasses or Li-PS type glass ceramics.

[0295] Examples of sulfide solid electrolytes

[0296] For example, sulfide-based solid electrolytes can include lithium sulfides, silicon sulfides, germanium sulfides, and boron sulfides. Specific examples of inorganic solid electrolytes can include Li... 3.833 Sn 0.833 As 0.166 S4, Li4SnS4, Li3.25 Ge 0.25 P 0.75 S4, Li2S-P2S0, B2S3-Li2S, 3+y PO 4-x N x ), thiolated LISICON (Li 3.25 Ge 0.25 P 0.75 S4), Li2O-Al2O3-TiO2-P2O5 (LATP), Li2S-P2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5 , Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2, Li2S-GeS2-ZnS, Li 10 GeP2S 12 (LGPS), Li7P3S 11 , Li6PS5Cl, Li6PS5Br, Li6PS5I, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 Li 11 Si2PS 12 etc., or combinations thereof.

[0297] Doped variants

[0298] In some cases, to further improve ionic conductivity or stability, doped variants of these materials (e.g., Al-doped Li) can be employed. 10 GeP2S 12 Or Sb-doped Li6PS5Cl).

[0299] Oxide solid electrolytes

[0300] Oxide-based solid electrolyte materials contain oxygen (O) and have the ionic conductivity of metals in Group I or Group II of the periodic table.

[0301] Examples of oxide-based solid electrolyte materials

[0302] Oxide-based solid electrolyte materials may include at least one selected from the group consisting of: LLTO compounds, Li6La2CaTa2O 12 Li6La2ANb2O 12 (A is Ca or Sr), Li2Nd3TeSbO 12 Li3BO 2.5 N 0.5 Li9SiAlO8, LAGP compounds, LATP compounds, Li 1+x Ti 2-x Al x Si y (PO4) 3-y (0≤x≤1, 0≤y≤1), LiAl x Zr 2-x (PO4)3(0≤x≤1, 0≤y≤1), LiTi x Zr 2-x (PO4)3 (0≤x≤1, 0≤y≤1), LISICON-type compounds, LIPON-type compounds, perovskite-type compounds, NASICON-type compounds, and LLZO-type compounds or derivatives (e.g., Al-doped Li7La3Zr2O). 12 Ta-doped Li7La3Zr2O 12 Lithium-rich anti-perovskites such as Li3OCl and Li3OBr have also been studied as potential oxide-based solid electrolytes.

[0303] Composite oxide electrolyte

[0304] In some cases, to fully utilize the advantages of different oxide systems, composite oxide electrolytes combining multiple oxide materials (such as LLZO-LATP composite materials) can be used.

[0305] Polymer solid electrolyte

[0306] Polymer solid electrolytes are complexes of electrolyte salts and polymer resins, exhibiting lithium-ion conductivity. Polymer solid electrolytes may include polyether polymers, polycarbonate polymers, acrylate polymers, polysiloxane polymers, phosphazene polymers, polyethylene derivatives, epoxyalkane derivatives, phosphate / ester polymers, polylyzed lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, polymers containing groups that can dissociate into ions, polyethylene imine (PEI), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene succinate (PES), biopolymers (e.g., chitosan and cellulose derivatives), or combinations thereof.

[0307] Polymer resin for polymer solid electrolytes

[0308] Polymer solid electrolytes may comprise polymer resins, such as branched copolymers (comprising a polyethylene oxide (PEO) backbone copolymerized with comonomers comprising amorphous polymers such as PMMA, polycarbonate, polydimethylsiloxane (PDMS), and / or phosphazene), comb polymers, crosslinked polymer resins, polyethylene glycol (PEG), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyethylene oxide-polypropylene oxide copolymer (PEO-PPO), polyethylene imine (PEI), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), various block copolymers or graft copolymers comprising these materials, or combinations thereof.

[0309] Polymer gel electrolyte

[0310] Polymer gel electrolytes can be formed by adding an organic electrolyte containing an organic solvent and an electrolyte salt, an ionic liquid, a monomer, or an oligomer to a polymer resin or a combination thereof. Polymer resins used for polymer gels may include polyether polymers, PVC polymers, PMMA polymers, polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), or combinations thereof.

[0311] Examples of polymer gel electrolytes

[0312] To optimize the electrochemical and physical properties of solid electrolytes, examples of polymeric gel electrolytes suitable for solid-state batteries include gel electrolytes based on polyethylene oxide (PEO), polymethyl methacrylate-ethyl acrylate copolymer (PMMA-EA), polyacrylonitrile-methyl methacrylate copolymer (PAN-MMA), polyvinyl acetate (PVAc), polyethylene glycol diacrylate (PEGDA), polyvinylpyrrolidone (PVP), polyethylene glycol methyl ether acrylate (PEGMEA), polyethylene glycol methyl ether methacrylate (PEGMEMA), polyionic liquid (PIL), polyethylene glycol-polypropylene glycol copolymer (PEG-PPG), polyvinyl alcohol-ethylene copolymer (PVA-PE), polyacrylamide (PAM), poly(2-hydroxyethyl methacrylate) (PHEMA), polyethylene glycol-polyethylene oxide copolymer (PEG-PEO), and polymethyl methacrylate (PMAA).

[0313] Electrolyte salts

[0314] The electrolyte salt is an ionizable lithium salt, which can be represented as Li + X - X -It can include anions 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 - wait.

[0315] Examples of lithium salts

[0316] For example, lithium salts can be any one selected from the group consisting of: LiTFSI, LiCl, LiBr, LiI, LiClO4, lithium tetrafluoroborate (LiBF4), LiB 10 Cl 10Lithium hexafluorophosphate (LiPF6), LiAsF6, LiSbF6, LiAlCl4, LiSCN, LiCF3CO2, LiCH3SO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC4F9SO3, LiC(CF3SO2)3, (CF3SO2)2NLi, lithium chloroborate, lower aliphatic carboxylic acid lithium salts, lithium 4-phenylborate imide, lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalate)borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 4,5-dicyano-2-(trifluoromethyl)imidazolium (LiTDI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(fluorosulfonyl)imide (LiFSI), or combinations thereof. Electrolyte salts may include any combination of the salts described herein.

[0317] Electrolyte salt content

[0318] Based on the total weight of the solid electrolyte layer 106, the content of electrolyte salts in the solid electrolyte layer 106 can be or approximately 0 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, 300 parts, 310 parts, 320 parts, 330 parts, 340 parts, 350 parts, 360 parts, 370 parts, 380 parts, 390 parts, or 400 parts. In some embodiments, the content of electrolyte salts in the solid electrolyte layer 106, based on the total weight of the solid electrolyte layer 106, can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​from about 0 parts to about 400 parts or from about 60 parts to 400 parts.

[0319] ionic conductivity of solid electrolyte layer

[0320] The solid electrolyte layer 106 can possess suitable reduction stability and / or ionic conductivity. Since the solid electrolyte layer 106 primarily functions to transport lithium ions between the electrodes, it can therefore possess ideal ionic conductivity, which is approximately or greater than, for example, 10⁻⁶. -7 S / cm, 10 -6 S / cm, 10 -5 S / cm or 10 -4 S / cm.

[0321] Thickness of solid electrolyte layer

[0322] The thickness t6 of the solid electrolyte layer 106 may be or be about 1 μm, 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, 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 1000 μm. In some embodiments, the thickness t6 of the solid electrolyte layer 106 can be within a range formed by selecting any two numbers listed above, or within a range formed by selecting any two numbers from 0 to about 1000 μm (e.g., about 5 μm to about 1000 μm, about 30 μm to about 100 μm, or about 30 μm to about 50 μm).

[0323] semi-finished products

[0324] Figure 1 The shown cell 101 may be provided as a semi-finished product. In some embodiments, the cell 101 is stored, transported, and / or delivered to distributors, customers, etc., who complete the manufacturing of a battery assembly or product containing the cell 101. In other embodiments, the cell 101 is a finished battery assembly or product.

[0325] Battery sealing

[0326] The casing 112 of the solid-state battery can be sealed to complete the manufacture of the solid-state battery 100, enabling it to function as a battery. The sealing process can employ various techniques to ensure that internal components are protected from external environmental factors and to maintain the integrity of the battery structure. For example, methods such as laser welding, ultrasonic welding, or adhesive bonding can be used to achieve an airtight seal for the casing 112. In some cases, the sealing process may also include introducing a protective atmosphere or removing air to create a vacuum environment within the casing. This sealing step helps prevent moisture ingress, as moisture can degrade the performance of sulfide-based solid electrolytes. Furthermore, the sealing process can incorporate safety features such as pressure relief mechanisms to address potential gas accumulation issues during battery operation.

[0327] After the battery is sealed

[0328] After proper sealing, the solid-state battery 100 undergoes final quality control testing, including electrical testing, leak detection, and visual inspection. Following these tests, the solid-state battery 100 can be packaged and sold as a finished product, and integrated into various electronic devices, electric vehicles, and energy storage systems, such as energy storage systems for storing electrical energy generated by wind turbines and / or solar generators.

[0329] Battery Structure

[0330] Solid-state batteries 100 are offered in a variety of configurations to suit different applications and device requirements. In some cases, the battery can be made in a cylindrical form, which can be advantageous for certain types of portable electronic devices or automotive applications. Alternatively, solid-state batteries 100 can be made in a prismatic form, allowing for more efficient use of space in devices with rectangular form factors. In other cases, a pouch form can be adopted, offering flexibility in shape and the potential to reduce the overall weight of the battery. The pouch form is particularly suitable for solid-state batteries because it makes it easier to apply and control uniform pressure inside the battery.

[0331] Construction choice

[0332] The choice of configuration can be determined by factors such as intended use, space constraints, thermal management requirements, and manufacturing considerations. In some implementations, hybrid or custom configurations combining different forms of elements can be employed as needed. The diversity of battery form factors enables all-solid-state batteries to be integrated into a wide range of products, from small wearable devices to large energy storage systems.

[0333] Voltage

[0334] Solid state battery 100 is configured to have an output voltage of at or about 1 V, 2 V, 3 V, 4 V, 5 V, 6 V, 7 V, 8 V, 9 V, 10 V, 11 V, 12 V, 13 V, 14 V, 15 V, 16 V, 17 V, 18 V, 19 V, 20 V, 21 V, 22 V, 23 V, 24 V, 25 V, 26 V, 27 V, 28 V, 29 V, 30 V, 35 V, 40 V, 45 V, 48 V, 50 V, 55 V, 60 V, 65 V, 70 V, 75 V, 80 V, 85 V, 90 V, 95 V, 96 V, 100 V, 110 V, 120 V, 130 V, 140 V, 150 V, 160 V, 170 V, 180 V, 190 V, 200 V, 210 V, 220 V, 230 V, 240 V, 250 V, 260 V, 270 V, 280 V, 290 V, 300 V, 310 V, 320 V, 330 V, 340 V, 350 V, 360 V, 370 V, 380 V, 390 V, 400 V, 410 V, 420 V, 430 V, 440 V, 450 V, 460 V, 470 V, 480 V, 490 V, or 500 V. In some embodiments, the output voltage of the solid-state battery 100 can be within a range formed by selecting any two numbers listed above, or within a range formed by selecting any two numbers from 0 to about 500 V (e.g., from 1 V DC to about 500 V DC).

[0335] capacity

[0336] The solid-state battery 100 can be configured to have the following capacities: approximately or greater than 100 mAh / g, 110 mAh / g, 120 mAh / g, 130 mAh / g, 140 mAh / g, 150 mAh / g, 160 mAh / g, 170 mAh / g, 180 mAh / g, 190 mAh / g, 200 mAh / g, 210 mAh / g, 220 mAh / g, 230 mAh / g, 240 mAh / g, 250 mAh / g, 260 mAh / g, 270 mAh / g, 280 mAh / g, 290 mAh / g, or 300 mAh / g. In some embodiments, the capacity of the solid-state battery 100 may be within a range formed by selecting any two of the numbers listed above, or may be within a range formed by selecting any two of the numbers from 0 to 300 mAh / g or from 0 to about 300 mAh / g (e.g., from about 100 mAh / g to about 300 mAh / g).

[0337] Calculation of volume expansion rate

[0338] The solid-state battery 100 can be configured to have an ideal volumetric expansion rate. The volumetric expansion rate can be calculated by comparing the change in thickness after the first charge-discharge cycle with the initial thickness. The volumetric expansion rate is the ratio of the change in thickness to the initial thickness. The first charge-discharge cycle is performed as follows: the battery is charged at 0.1C CC-CV, cut off at 4.25V to 4.4V and then at 0.02C; then discharged at 0.1C CC, cut off at 3V. The volumetric expansion rate is calculated using Equation 1 below, where A represents the thickness before charge-discharge and B represents the thickness after charge-discharge. The thickness can be measured using a Mauser micrometer or a scanning electron microscope (SEM).

[0339] Equation 1: Volume expansion rate = [(BA) / A] × 100 C-fold The C-rate used in this article refers to the discharge rate of the battery relative to its maximum capacity. For example, a 1C rate means that the discharge current can completely discharge the battery in one hour. That is, for a battery with a capacity of 20 amp-hours, the discharge current at a 1C rate is 20 amps.

[0340] Battery C-rate

[0341] The C-rate of the solid-state battery 100 can be, 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 some embodiments, the C-rate of the solid-state battery 100 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, approximately 0.33 to approximately 5.

[0342] Other examples of volume expansion rate

[0343] Other methods for measuring and calculating the volume expansion rate of solid-state batteries may include volume expansion measurement methods (e.g., gas specific gravity bottle method), in-situ dilatometer method, X-ray tomography, strain gauge measurement method, optical methods (e.g., digital image correlation or laser interferometry), pressure-based methods, and electrochemical strain microscopy.

[0344] conflict

[0345] The additional features, implementation methods, and examples discussed below will apply to various aspects of the invention discussed above. However, in the event of any conflict between the information discussed above and the information discussed below, the information in the preceding section shall prevail.

[0346] How to use solid-state batteries

[0347] This article provides a method for using a solid-state battery. The method involves repeatedly charging and discharging the solid-state battery. The negative electrode is in direct contact with the solid electrolyte, and this direct contact is substantially maintained after charging and discharging by utilizing a second particle to compensate for size changes in the first particle.

[0348] Manufacturing method of solid-state battery cells

[0349] This article provides a method for manufacturing solid-state battery cells. The method includes, for example... Figure 2 The first composite sheet 220 is continuously provided as shown.

[0350] Composition of the first composite sheet

[0351] The first composite sheet 220 may include a solid electrolyte layer 204 formed on the positive electrode layer 204. Optionally, the first composite sheet 220 may include additional layers, such as... Figure 2 As shown in detailed region A, a conductive layer 208 is formed on the positive electrode layer 204 on the side 204a opposite to the side 204b on which the solid electrolyte layer 206 is formed.

[0352] Positive electrode layer

[0353] The positive electrode layer 202 can be configured to form the positive electrode 102. For example, the positive electrode layer 202 can contain the same material as the positive electrode 102 described herein. In some embodiments, the positive electrode active material comprises lithium nickel manganese oxide.

[0354] solid electrolyte layer

[0355] The solid electrolyte layer 206 can be configured to form the solid electrolyte layer 106. For example, the solid electrolyte layer 206 can contain the same material as the solid electrolyte layer 106 described herein.

[0356] current collector

[0357] The conductive layer 208 can be configured to form the current collector 108. For example, the conductive layer 208 can contain the same material as the current collector 108 described herein. In some embodiments, the conductive layer 208 can contain an aluminum sheet.

[0358] The shape of the first composite sheet

[0359] The first composite sheet 220 can be supplied as a single flat sheet, in roll form, or can be manufactured in situ. For example, as Figure 2 As shown, the first composite sheet 220 can be formed by continuously supplying a positive electrode layer 204, a solid electrolyte layer 206, and an optional current collector layer 208, and by using a roller 222 to roll these layers together.

[0360] Supply aluminum sheet

[0361] The method may include continuously supplying an aluminum-containing sheet 224 over the first composite sheet 220, such that the aluminum-containing sheet 224 is placed on the solid electrolyte layer 206 of the first composite sheet 220. For example, the aluminum-containing sheet 224 may be in direct contact with one side 204b of the solid electrolyte layer.

[0362] Materials containing aluminum sheets

[0363] The aluminum sheet 224 may comprise aluminum or an aluminum alloy. In some embodiments, the aluminum sheet 224 comprises aluminum foil. In many embodiments, the aluminum sheet 224 comprises aluminum particles and an adhesive, and may have a plastic layer attached to the aluminum sheet 224 to facilitate handling of the aluminum sheet 224.

[0364] Aluminum layer with plastic material

[0365] The method may include removing the plastic layer from the aluminum sheet 224 before placing the aluminum sheet 224 on the solid electrolyte layer 206 of the first composite sheet 220.

[0366] Roll forming of aluminum sheet and first composite sheet

[0367] The method may include continuously roll-bonding an aluminum-containing sheet 224 to a first composite sheet 220 to provide a second composite sheet 226, the second composite sheet 226 comprising a positive electrode layer 204, a solid electrolyte layer 206, the aluminum-containing sheet 224, and optionally a current collector 108. For example, a roller 236 may facilitate the roll-bonding of the aluminum-containing sheet 224 to the first composite sheet 220.

[0368] Roller Pressing Overview

[0369] Roll bonding is a process that joins two or more sheets of material together by bringing them into contact with each other and passing them between rollers under pressure and optionally at a certain temperature. Roll bonding can also be a welding process that forms a new material layer with uniform bonding force along the surface of the sheets.

[0370] Thickness reduction

[0371] Roll forming can reduce the thickness of two or more sheets. For example, using roller 236 for roll forming can reduce the thickness of aluminum sheet 224 and the thickness of first composite sheet 220.

[0372] Pressure of roller pressing

[0373] The roll bonding process using roller 236 may include applying an isostatic pressure to the aluminum sheet 224 and the first composite sheet 220, which may be, approximately, or at least 150 N, 200 N, 250 N, 300 N, 350 N, or 400 N. In some embodiments, the applied pressure may be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of approximately 150 N to 500 N (e.g., approximately 200 N to 500 N).

[0374] Supply of lithium-containing layers

[0375] The method may include continuously supplying a third composite sheet 230 over the second composite sheet 226, the third composite sheet 230 comprising a lithium-containing layer 232 and a conductive layer 234, such that the lithium-containing layer 232 of the third composite sheet 230 is positioned on the aluminum-containing sheet 224 of the second composite sheet 228. The lithium-containing layer 232 is disposed between the aluminum-containing sheet 224 and the conductive layer 234.

[0376] current collector

[0377] The conductive layer 226 can be configured to form the current collector 110. For example, the conductive layer 226 can contain the same material as the current collector 110 described herein. In some embodiments, the conductive layer 226 can contain copper or a copper alloy.

[0378] Lithium-containing layer

[0379] The lithium-containing layer 232 may contain lithium or a lithium alloy. For example, based on the total weight of the lithium-containing layer 232, the content of elemental lithium in the lithium-containing layer 232 is approximately or at least 80% by weight, 85% by weight, 90% by weight, 95% by weight, 98% by weight, or 99% by weight. In some embodiments, the lithium content in the lithium-containing layer 232 may be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​from 80% by weight to about 100% by weight (e.g., from about 90% by weight to about 100% by weight).

[0380] Roll forming the second and third composite sheets

[0381] The method may include continuously rolling and bonding a second composite sheet 228 and a third composite sheet 230 together, such that a lithium-containing layer 232 and an aluminum-containing sheet 224 are compressed together to form a pre-lithiated negative electrode 238, wherein the lithium-containing layer 232 and the aluminum-containing sheet 224 are disposed between the conductive layer 234 and the first composite sheet 220. For example, the pre-lithiated negative electrode 238 may comprise a metal alloy (e.g., an aluminum-lithium alloy) formed from the lithium-containing layer 232 and the aluminum-containing layer 224.

[0382] Advantages of the method

[0383] Compared to roll bonding of the lithium-containing and aluminum-containing layers not positioned between the conductive layer and the composite layer containing the electrolyte layer and the positive electrode layer, roll bonding of the second composite sheet 228 and the third composite sheet 230 can significantly suppress the formation of cracks within the pre-lithiated negative electrode 238. Individual layers in these structures may be too fragile to be roll bonded individually.

[0384] Thickness reduction

[0385] Roll forming can reduce the thickness of two or more sheets. For example, using roll forming with roll 240 can reduce the thickness of aluminum sheet 224 and the thickness of first composite sheet 220. Each layer can have a greater thickness before roll forming for processing, while roll forming can still reduce each layer to the required thickness.

[0386] Pressure of roller pressing

[0387] Roller bonding using roller 240 may include applying isostatic pressure to the second composite sheet 226 and the third composite sheet 230, which may be, approximately, or at least 150 N, 200 N, 250 N, 300 N, 350 N, or 400 N. In some embodiments, the applied pressure may be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of 150 N to 500 N (e.g., approximately 200 N to 500 N).

[0388] Temperature of roll forming

[0389] During continuous roll forming, the second composite sheet 228 and the third composite sheet 230 can be heated. For example, the second composite sheet 228 and the third composite sheet 230 can be heated to about or at least 30°C, 50°C, 60°C, 75°C, 80°C, 90°C, 100°C, 120°C, 130°C, or 150°C. In some embodiments, the heating temperature of the second composite sheet 228 and the third composite sheet 230 can be within a range formed by selecting any two values ​​listed above, or within a range formed by selecting any two values ​​within the range of 30°C to 200°C (e.g., about 50°C to 150°C).

[0390] Size of pre-lithiated anode

[0391] The pre-lithiated anode 238 can have the same thickness t1 as the anode 104.

[0392] Cell size

[0393] Cell 201 may have the same width w1, length l1, and thickness t1 as cell 101. For example, the thickness of cell 201 may be less than 1 mm.

[0394] Pressure applied to the battery

[0395] The pressure exerted on each layer of the cell 201 and / or solid-state battery 100 can be or approximately 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, or 10 MPa. In some embodiments, the pressure exerted on each layer of the cell 201 and / or solid-state battery 100 can be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, approximately 1 MPa to approximately 10 MPa or 1 MPa to 5 MPa.

[0396] Included combinations and characteristics

[0397] This specification describes various features and characteristics to facilitate understanding of the composition, structure, manufacture, function, and / or operation of the invention, including the disclosed components, coatings, and methods. It should be understood that the various features and characteristics of the invention described herein can be combined in any suitable manner, whether or not they are explicitly described as combinable in this specification. The inventors and applicant expressly intend that combinations of these features and characteristics be included within the scope of protection of the invention as described herein. Therefore, the claims may be modified to reference any feature and characteristic explicitly or inherently described in this specification, or any feature and characteristic otherwise explicitly or inherently supported in this specification, in any combination thereof. Furthermore, the applicant reserves the right to amend the claims to explicitly exclude features and characteristics that may exist in the prior art, even if such features and characteristics are not explicitly described in this specification. Therefore, any such amendments will not add new content to the specification or claims and will comply with the requirements of drafting, adequate disclosure, and addition of content.

[0398] By incorporating via reference

[0399] The entire contents of any patent, publication, or other document referenced in this specification are incorporated herein by reference only, unless otherwise stated, but only to the extent that the incorporated material does not conflict with the existing descriptions, definitions, statements, illustrations, or other disclosed material expressly set forth in this specification. Therefore, where necessary, the disclosure expressly set forth in this specification takes precedence over any conflicting material incorporated by reference. Any material or portion thereof incorporated by reference in this specification that conflicts with existing definitions, statements, or other disclosed material set forth herein shall be incorporated only to the extent that the incorporated material does not conflict with the existing disclosure. The applicant reserves the right to amend this specification to expressly reference any subject matter or portion thereof incorporated by reference. Amending this specification to add such incorporated subject matter will meet the requirements of specification drafting, adequate disclosure, and addition of content.

[0400] Explanation from all aspects

[0401] While various specific aspects of the invention have been described to illustrate its various aspects and / or its potential applications, it should be understood that various changes and modifications will occur to those skilled in the art. Therefore, the invention herein should be understood to be at least as broad as the scope defined by the claims, and not narrowly defined by the specific illustrative aspects provided herein.

Claims

1. A method for manufacturing a battery cell, the method comprising: A first composite sheet is continuously supplied, the first composite sheet comprising a positive electrode layer and a solid electrolyte layer formed on the positive electrode layer; Aluminum-containing sheets are continuously supplied above the first composite sheet, such that the aluminum-containing sheets are placed on the solid electrolyte layer of the first composite sheet; The aluminum-containing sheet is continuously rolled together with the first composite sheet to provide a second composite sheet, the second composite sheet comprising the positive electrode layer, the solid electrolyte layer and an aluminum-containing layer derived from the aluminum-containing sheet; A third composite sheet is continuously supplied above the second composite sheet. The third composite sheet includes a lithium-containing layer and a conductive layer, such that the lithium-containing layer of the third composite sheet is placed on the aluminum-containing layer of the second composite sheet, and the lithium-containing layer is disposed between the aluminum-containing layer and the conductive layer; and The second composite sheet and the third composite sheet are continuously rolled together, so that the lithium-containing layer and the aluminum-containing layer are compressed together, thereby forming a pre-lithiated negative electrode while being disposed between the conductive layer and the first composite sheet.

2. The method as described in claim 1, wherein, The process of continuously rolling the second composite sheet and the third composite sheet together, thereby compressing the lithium-containing layer and the aluminum-containing layer together and forming a pre-lithiated negative electrode while it is disposed between the conductive layer and the first composite sheet, suppresses the formation of cracks in the pre-lithiated negative electrode layer compared to the process of rolling the lithium-containing layer and the aluminum-containing layer not disposed between the conductive layer and the composite layer containing the electrolyte layer and the positive electrode layer.

3. The method as described in claim 1, wherein, The process of continuously rolling the aluminum-containing sheet and the first composite sheet together to provide the second composite sheet reduces the thickness of the aluminum-containing sheet and the first composite sheet.

4. The method of claim 1, wherein, The process of continuously rolling the second composite sheet and the third composite sheet together reduces the thickness of the aluminum-containing sheet and the first composite sheet.

5. The method of claim 1, wherein, The process of continuously rolling the second composite sheet and the third composite sheet together applies an isostatic pressure of 150 N to 500 N to the second composite sheet and the third composite sheet.

6. The method of claim 1, wherein, The process of continuously rolling the second composite sheet and the third composite sheet together applies a force of 150 N to 500 N to the second composite sheet and the third composite sheet.

7. The method of claim 1, further comprising heating the second composite sheet and the third composite sheet while continuously rolling them together.

8. The method of claim 1, wherein, The conductive layer contains copper.

9. The method of claim 1, wherein, The first composite sheet includes a second aluminum-containing sheet formed above the positive electrode layer.

10. The method of claim 1, wherein, The aluminum-containing sheet comprises aluminum particles and an adhesive, and the method further includes removing a plastic layer from the aluminum-containing sheet.

11. The method of claim 1, wherein, The aluminum-containing sheet comprises aluminum foil.

12. The method of claim 1, wherein, The thickness of the pre-lithiated anode is 10 μm to 100 μm.

13. The method of claim 1, wherein, The process of continuously rolling together the second composite sheet and the third composite sheet forms a battery cell assembly, and the specific capacity of the battery cell assembly is at least 100 mAh / g.

14. The method of claim 13, wherein, The thickness of the battery cell assembly is less than 1 mm.

15. The method of claim 13, wherein, The pressure exerted on the battery cell assembly is between 1 MPa and 10 MPa.

16. The method of claim 13, wherein, The C-ratio of the battery cell assembly is at least 0.

33.

17. A solid-state battery comprising at least two cell assemblies as described in claim 13.

18. An electric vehicle or an energy storage system for storing electrical energy generated by a wind turbine and / or a solar generator, comprising the solid-state battery of claim 17.

19. A method of using a battery cell assembly, the method comprising repeatedly charging and discharging the battery cell assembly, wherein, Each cell in the assembly is prepared by a method including the following processes: A first composite sheet is continuously supplied, the first composite sheet comprising a positive electrode layer and a solid electrolyte layer formed on the positive electrode layer; Aluminum-containing sheets are continuously supplied above the first composite sheet, such that the aluminum-containing sheets are placed on the solid electrolyte layer of the first composite sheet; The aluminum-containing sheet is continuously rolled together with the first composite sheet to provide a second composite sheet, the second composite sheet comprising the positive electrode layer, the solid electrolyte layer and an aluminum-containing layer derived from the aluminum-containing sheet; A third composite sheet is continuously supplied above the second composite sheet. The third composite sheet includes a lithium-containing layer and a conductive layer, such that the lithium-containing layer of the third composite sheet is placed on the aluminum-containing layer of the second composite sheet, and the lithium-containing layer is disposed between the aluminum-containing layer and the conductive layer; and The second composite sheet and the third composite sheet are continuously rolled together, so that the lithium-containing layer and the aluminum-containing layer are compressed together, thereby forming a pre-lithiated negative electrode while being disposed between the conductive layer and the first composite sheet.

20. A battery cell prepared by a method comprising the following processes: A first composite sheet is continuously supplied, the first composite sheet comprising a positive electrode layer and a solid electrolyte layer formed on the positive electrode layer; Aluminum-containing sheets are continuously supplied above the first composite sheet, such that the aluminum-containing sheets are placed on the solid electrolyte layer of the first composite sheet; The aluminum-containing sheet is continuously rolled together with the first composite sheet to provide a second composite sheet, the second composite sheet comprising the positive electrode layer, the solid electrolyte layer and an aluminum-containing layer derived from the aluminum-containing sheet; A third composite sheet is continuously supplied above the second composite sheet. The third composite sheet includes a lithium-containing layer and a conductive layer, such that the lithium-containing layer of the third composite sheet is placed on the aluminum-containing layer of the second composite sheet, and the lithium-containing layer is disposed between the aluminum-containing layer and the conductive layer; and The second composite sheet and the third composite sheet are continuously rolled together, so that the lithium-containing layer and the aluminum-containing layer are compressed together, thereby forming a pre-lithiated negative electrode while being disposed between the conductive layer and the first composite sheet.

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