Electrode material having mixed particle sizes

Abstract

To provide a new thin film positive electrode having a feature of a specific size required for a high performance solid-state battery.SOLUTION: The present invention relates to an electrochemical device and a material thereof. More specifically, a low porosity electrode comprising large and small particles is provided. The large particles comprise an electrochemically active material. The small particles comprise an ion-conducting electrolyte material. In some examples, the large particles and small particles are characterized by a dispersity of 0.5 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field] 【0001】 (Cross-reference of related applications) This application is incorporated herein by reference in its entirety for all purposes. Patent application filed on June 4, 2014, for "Electrode Materials with Mixed Particle Sizes" This application claims priority from U.S. Provisional Patent Application No. 62 / 007,416, titled "TICLE SIZES". be. [Background technology] 【0002】 (Background of the invention) This disclosure relates to electrochemical devices and materials thereof. In particular, this disclosure relates to electrochemical electrodes. This addresses several challenges related to the fabrication and electrode packing configurations of nanoscale and / or solid electrodes. ru. 【0003】 Consumer electronic devices (e.g., mobile phones, tablets, and laptop computers) and As electric vehicles (e.g., plug-in hybrids and BEVs) have become more widespread, these Higher performance energy storage devices required to power electronic equipment and vehicles Demand for rechargeable lithium (Li) ion batteries is also increasing. While rechargeable batteries (i.e., lithium-ion batteries) are common in consumer electronics, conventional batteries still... However, there are limitations in terms of energy density and output for widespread adoption in other applications (e.g., automobiles). There are too many of them. Solid-state lithium-ion rechargeable batteries consist entirely of solid constituent materials and have high theoretical energy. It has ghee density and output characteristics, and therefore depends on and includes a liquid electrolyte. It is an attractive alternative to batteries. 【0004】 Ionic conductivity is generally lower in solids than in liquids. Therefore, all ion conduction paths are solid. In order to achieve high output in a solid-state battery that passes through the body, the ion conduction pathway should be reduced. Furthermore, the intrinsic ionic conductivity of the constituent solid material should be increased. This requires considerable effort. Nevertheless, these problems have not been resolved, and solid-state batteries still suffer from low power output issues. [Overview of the Initiative] [Problems that the invention aims to solve] 【0005】 Therefore, a solid electrochemical electrode (e.g., a thin film positive electrode) and its constituent material components (e.g., Nanostructured and nano-ordered active materials and catholites. A series of problems exist in the related fields concerning the method of causing r). For example, a novel thin-film positive electrode having specific size characteristics required for high-performance solid-state batteries This disclosure describes a method for fabrication. This disclosure, in part, describes, for example, such nanostructuring and nanoorganization. This document describes a series of positive electrodes, their fabrication and use, and other solutions to problems in related fields. . [Means for solving the problem] 【0006】 (Summary of the invention) In one embodiment, a solid electrochemical electrode is described herein, and the solid electrochemical electrode is 0. It has a first particle size distribution characterized by a first dispersion degree of 25 or less and a first median diameter. , a first plurality of electrochemically active materials; and a second dispersion degree of 0.25 or less and a second medium It has a second particle size distribution characterized by its central diameter, wherein the second central diameter is equal to the first central diameter. It contains a second set of ion-conducting particles, the largest of which is one-third or less in diameter. 【0007】 In a second embodiment, a solid electrochemical electrode is described herein, and the solid electrochemical electrode is , an active material characterized by a first particle size distribution having a first central particle size; a second central particle It comprises a catholite material characterized by a second particle size distribution having a diameter; the active material The volume ratio to the solite material is 99:1 to 1:1; and the second median grain size of the first median grain size The particle size ratio to particle size is at least 3:1. 【0008】 In a third embodiment, an electrochemical cell is described herein, the electrochemical cell is an Ano Anode current collector; anode in direct contact with the anode current collector; anode directly in contact with the anode An electrolyte in contact with the anode, wherein the anode current collector and the electrolyte The electrolyte is placed between the two and characterized by an ionic conductivity of at least 1e-4 S / cm. The electrolyte and a solid positive electrode in direct contact with the electrolyte, wherein the solid positive electrode is a first An active material characterized by a first particle size distribution having a median particle size; having a second median particle size It contains a catholite material characterized by a second particle size distribution; the active material is catholite The volume ratio to the material is 99:1 to 1:1; and the second median particle size of the first median particle size is The particle size ratio is at least 3:1. 【0009】 In the fourth and fifth embodiments, the method for fabricating and using the electrochemical electrodes described above is described herein. It will be listed. [Brief explanation of the drawing] 【0010】 (Brief explanation of the drawing) [Figure 1]Figure 1 shows an example of an electrode having a mixed particle size of active material and catholite. 【0011】 [Figure 2] Figure 2 shows an example of an electrode having a mixed particle size of active material and catholite. 【0012】 [Figure 3] Figure 3 shows an example of a percolation network of a catholite material in a solid cathode. 【0013】 [Figure 4] Figure 4 shows an example of the penetration threshold as a function of the size (diameter) ratio of the larger particles to the smaller particles for a randomly packed electrode having a mixed particle size of active material (large particles) and catholite (small particles). 【0014】 [Figure 5] Figure 5 shows an example of the penetration threshold as a function of the size ratio of the larger particle size to the smaller particle size of a compressed electrode. 【0015】 [Figure 6] Figure 6 shows the random packing density as a function of the size ratio of larger particle sizes to smaller particle sizes. 【0016】 [Figure 7] Figure 7 shows the permeation thresholds for aggregates of large and small particles in the electrode, renormalized with respect to the total proportion of the container volume occupied by the smaller particles. 【0017】 [Figure 8] Figure 8 shows the percentage of the 2D cross-sectional area occupied by small particles as a function of the volume of small particles in electrodes with large and small particle sizes. 【0018】 [Figure 9]Figure 9 shows the ratio of the normalized 2D cross-sectional area as a function of the penetration threshold of the 2% compressed electrode. 【0019】 [Figure 10] Figure 10 shows the proportion of larger particles in contact with penetrating particles as a function of the proportion of smaller particles. 【0020】 [Figure 11] Figure 11 shows an SEM image illustrating an electrode material containing substantially uncompressed large and small particles. The large particles (1102) are nickel-cobalt aluminum oxide (NCA), and the small particles (1101) are LSTPS sulfide electrolyte. 【0021】 [Figure 12] Figure 12 is an SEM image illustrating electrode material containing large and small particles after a compression process. The large particles (1202) are nickel-cobalt aluminum oxide (NCA), and the small particles (1201) are LSTPS sulfide electrolyte. 【0022】 [Figure 13] Figure 13 shows an example of a cathode assembly having a large-particle cathode active material, a small-particle catholite ion conductor that is necked to form a penetration network, and an electron-conducting additive. 【0023】 [Figure 14] Figure 14 shows an example of a cathode-packed configuration, where (left) a monodisperse collection of large particles is mixed with a Gaussian distribution of small particles, or (right) a Gaussian distribution of large particles is mixed with a Gaussian distribution of small particles. In either case, the ratio of the larger particle size (diameter) to the smaller particle size is 4. 【0024】 [Figure 15]Figure 15 shows examples of cathode-packed configurations, where (left) a monodisperse collection of large particles is mixed with a monodisperse collection of small particles, in which case the ratio of large particle size (diameter) to small particle size is 4; or (right) a monodisperse collection of large particles is mixed with a monodisperse collection of small particles, in which case the ratio of large particle size (diameter) to small particle size is 2. 【0025】 [Figure 16] Figure 16 shows a plot of conductivity as a function of the size ratio of larger particle size to smaller particle size in three examples of cathodes, where the size ratio of larger particle size (oxide) to smaller particle size (sulfide catholite) was 20:1, 5:1, or 1:1. In each sample, the volume ratio of larger particle size (oxide) to smaller particle size (sulfide catholite) was 80:20. 【0026】 [Figure 17] Figure 17 shows a scanning electron microscope (SEM) image of an example of a cathode with a size ratio of 20:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite). 【0027】 [Figure 18] Figure 18 shows a scanning electron microscope (SEM) image of an example of a cathode with a size ratio of 20:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite). 【0028】 [Figure 19] Figure 19 shows a scanning electron microscope (SEM) image of an example of a cathode with a size ratio of 5:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite). 【0029】 [Figure 20] Figure 20 shows a scanning electron microscope (SEM) image of an example of a cathode with a size ratio of 5:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite). 【0030】 [Figure 21] Figure 21 shows an SEM image of an example of a cathode with a size ratio of 1:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite). 【0031】 [Figure 22] Figure 22 shows an SEM image of an example of a cathode with a size ratio of 1:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite). 【0032】 [Figure 23] Figure 23 shows a scanning electron microscope (SEM) image of an example of a cathode with a size ratio of 20:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite), and the weight ratio of larger particle size (Al2O3) to smaller particle size (LSTPS sulfide catholite) was 80:18. 【0033】 [Figure 24] Figure 24 shows a scanning electron microscope (SEM) image of an example of a cathode with a size ratio of 20:1 between larger particle size (Al2O3) and smaller particle size (LSTPS sulfide catholite), and the weight ratio of larger particle size (Al2O3) to smaller particle size (LSTPS sulfide catholite) was 44:54. 【0034】 [Figure 25] Figure 25 shows an example of the particle size distribution of ground LSTPS and Al2O3 used in specific examples of this specification. 【0035】 [Figure 26] Figure 26 shows an example of the particle size distribution of ground LSTPS and NCA used in specific examples of this specification. 【0036】 [Figure 27] Figure 27 shows a plot of conductivity as a function of the volume fraction of catholite at various large-to-small particle size ratios. [Modes for carrying out the invention] 【0037】 (Detailed description of the invention) The following description assumes that a person skilled in the art has prepared and used the examples and embodiments described herein. These are presented so that they can be incorporated in relation to specific uses. Various modifications The decorative and various uses in different applications will be immediately apparent to those skilled in the art and are defined herein. The general principles can be applied to a wide range of embodiments. Therefore, the present invention is applicable to the embodiments presented. This specification is not intended to be limited to the manner of application, but rather to encompass the principles and novelty disclosed herein. The broadest range that matches the characteristics should be recognized. 【0038】 Reader's attention is submitted together with this specification and made available for public inspection together with this specification. This applies to all documents and papers, and the contents of all such documents and papers are by reference. These are incorporated herein. Unless otherwise expressly stated, each disclosed feature This is merely one example of a series of general equivalent or similar characteristics. 【0039】 Furthermore, "means for" or "means for" that perform a specific function. Any element in a claim that does not explicitly describe the "process" is defined in Section 112(f) of the U.S. Patent Act. This should not be interpreted as a provision specifying a particular "means" or "process." The use of "process of ~" or "operation of ~" in the claims of this book is prohibited under Article 112 of the United States Patent Act. This is not intended to be an exercise of the provisions of Article (f). 【0040】 When used, left, right, forward, backward, up, down, forward direction, reverse direction, clockwise, and counterclockwise. The notation "ri" is used merely for convenience and does not imply any specific direction. Please note that this is not intended to be the case. Rather, these are the various aspects of the object. It is used to indicate the relative position and / or direction between parts. 【0041】 (I. Definition) As used herein, the phrase “at least one element selected from the group” This includes a single element from the group, two or more elements from the group, or a combination of elements from the group. At least one element selected from the group consisting of A, B, and C is, for example, A only, B only, Or C only, and A and B, and A and C, and B and C, and A, B and C, or A, B This includes all other combinations of C. 【0042】 As used herein, the term "electrochemical cell" is used, for example, "battery cell." This refers to the positive electrode, the negative electrode, and the ions (for example,) that are in direct contact with them and between them. Li + It includes an electrolyte that conducts ) but electrically insulates the positive and negative electrodes. In some embodiments, A battery may include multiple positive electrodes and / or multiple negative electrodes enclosed within a single container. 【0043】 As used herein, the term “positive electrode” refers to the electrode that is directed toward the battery during discharge. Positive ions, for example, Li + This refers to the electrodes in a secondary battery through which conduction, inflow, or movement occurs. As used herein, the term "negative electrode" refers to the point from which the battery discharges. Ions, for example, + Li-metal electrode refers to an electrode in a secondary battery from which lithium leaks or moves. and conversion chemical electrodes (i.e., active materials; for example, NiF xIn a battery composed of an electrode having a conversion chemical substance is called a positive electrode. In some common usages a cathode is used instead of the positive electrode, and an anode is used instead of the negative electrode. When a Li-secondary battery is charged, Li ions move from the positive electrode (e.g., NiF x ) to the negative electrode (Li-metal ). When the Li-secondary battery is discharged, Li ions move from the negative electrode to the positive electrode . 【0044】 As used herein, the phrase "sulfide electrolyte" refers to an inorganic solid material that conducts Li + ions but is substantially electrically insulating. Some of the sulfide electrolytes described herein contain lithium, phosphorus, and sulfur, and any one, two, or three additional elements . Some of these sulfide electrolytes are referred to herein as LXPS materials, where L refers to lithium , P refers to phosphorus, S refers to sulfur, and X refers to any one, two, or three additional elements . Examples of LXPS materials are incorporated herein by reference in their entirety for all purposes, e.g., "Li MP S A (M = Si, Ge, and / or Sn B S C (M = Si, Ge, AND / OR Sn))" for a solid catholyte or electrolyte for a battery using Li MP S A MP B S C (M = Si, Ge, AND / OR Sn)), an international application PCT / US1 4 / 38283; also found in U.S. Patent No. 8,697,292 granted to Kanno et al. 【0045】 As used herein, the term "sulfide electrolyte" is not limited to... The following are included: LSS, LTS, LXPS, LXPSO, where X is Si, Ge, Sn, As, Al; LATS; And S is S, Si, or a combination thereof; T is Sn. 【0046】 As used herein, "LXPS" is derived from the formula Li a MP b S c Casola is characterized by This refers to a material, where M is Si, Ge, Sn, and / or Al, and 2≦a≦8, 0.5≦b≦2.5 , 4 ≤ c ≤ 12. "LSPS" is given by equation L a SiP b S c This refers to electrolyte materials characterized by, In the formula, 2≦a≦8, 0.5≦b≦2.5, and 4≦c≦12. LSPS is given by formula L a SiP b S c Characterized by This refers to an electrolyte material, where 2≦a≦8, 0.5≦b≦2.5, 4≦c≦12, and d<3. LXPS material is incorporated herein by reference, for example, in its entirety on May 16, 2014. Application "Li A MP B S C Solid cassolite or electrolytic battery using (M=Si, Ge, and / or Sn) Quality(SOLID STATE CATHOLYTE OR ELECTROLYTE FOR BATTERY USING Li A MP B S C (M=Si, Ge, A This can be seen in the international application PCT / US2014 / 038283, named "ND / OR Sn))". M is Sn and Si. If both of these are present, the LXPS material is called LSTPS. Thus, "LSTPSO" refers to LSTPS that are doped with or contain the present oxygen. In the example, "LSTPSO" is an LSTPS material with an oxygen content of 0.01 to 10 atomic percent. "LSPS" stands for L This refers to an electrolyte material having the chemical components i, Si, P, and S. As used herein, "LSTPS" refers to an electrolyte material having the chemical components Li, Si, P, Sn, and S. As used, "LSPSO" refers to an LSPS that is doped with or contains the present oxygen. In some cases, "LSPSO" refers to LSPS material with an oxygen content of 0.01 to 10 atomic percent. As used in the text, "LATP" is an electrolyte material having the chemical components Li, As, Sn, and P. This refers to the chemical components Li, As, Ge, and P used herein. This refers to an electrolyte material. As used herein, "LXPSO" is a Li a MP b S c O d by This refers to a catholite material characterized as such, where M is Si, Ge, Sn, and / or Al. Furthermore, 2 ≤ a ≤ 8, 0.5 ≤ b ≤ 2.5, 4 ≤ c ≤ 12, and d < 3. "LXPSO" is the LXPS defined above. This refers to LPS that is doped with 0.1 to approximately 10 atomic percent oxygen. "LPSO" refers to LPS as defined above. Furthermore, it is doped with oxygen at a concentration of 0.1 to approximately 10 atoms. 【0047】 As used herein, "LSS" is represented as Li2S-SiS2, Li-SiS2, or Li-S-Si. Lithium silicon sulfide, which can be formed, and / or essentially Li This refers to a catholite composed of , S, and Si. LSS is a catholite of the formula Li x Si y S z Electrolysis characterized by This refers to a material, where in the formula 0.33≦x≦0.5, 0.1≦y≦0.2, 0.4≦z≦0.55, and at most 10 May contain atomic percent oxygen. LSS also refers to electrolyte materials containing Li, Si, and S. Some examples So, LSS is a mixture of Li2S and SiS2. In some examples, the Li2S:SiS2 ratio is 90:10, 8 Mole ratios of 5:15, 80:20, 75:25, 70:30, 2:1, 65:35, 60:40, 55:45, or 50:50 LSS is a compound, for example, Li x PO y Li x BO y , Li4SiO4, Li3MO4, Li3MO3, PS x , and and / or lithium halides, for example, but not limited to LiI, LiCl, LiF, or It can be doped with LiBr, in the formula, 0 <x≦5、かつ0<y≦5である。 【0048】 As used herein, "LTS" is represented as Li2S-SnS2, Li2S-SnS, and Li-S-Sn. Lithium tin sulfide compounds that can be used, and / or Essentially, it refers to a catholite composed of Li, S, and Sn. This compound is Li x Sn y S z It could be, In the equation, 0.25 ≤ x ≤ 0.65, 0.05 ≤ y ≤ 0.2, and 0.25 ≤ z ≤ 0.65. In some examples, LTS is A mixture of Li2S and SnS2 in molar ratios of 80:20, 75:25, 70:30, 2:1, or 1:1. LTS may contain up to 10 atomic percent oxygen. LTS is Bi, Sb, As, P, B, Al, Ge, Ga, It can be doped with and / or In. As used herein, "LATS" means on The term LTS used refers to lithium, and further contains arsenic (As). In LTS, L refers to lithium. A represents arsenic, T represents tin, and S represents sulfur. 【0049】 As used herein, "LPS" refers to an electrolyte having the chemical components Li, P, and S. Refers to. As used herein, "LPSO" means doped with or containing the present O. This refers to LPS containing [something]. In some cases, "LPSO" refers to LPS material with an oxygen content of 0.01 to 10 atomic percent. Yes, LPS is Li x P y S z This refers to an electrolyte material that can be characterized by the formula, where 0.33 ≤ x ≤ 0. 0.67, 0.07 ≤ y ≤ 0.2, and 0.4 ≤ z ≤ 0.55. LPS is also formed from a mixture of Li2S:P2S5. This also refers to electrolytes characterized by the products produced, where the molar ratios are 10:1, 9:1, and 8:1. The ratios are 7:1, 6:1, 5:1, 4:1, 3:1, 7:3, 2:1, or 1:1. LPS is also Li2S:P2S This also refers to the electrolyte characterized by the product formed from the mixture of 5, which is a reactant or precursor. The composition is 95 atomic percent Li2S and 5 atomic percent P2S5. LPS is also derived from a mixture of Li2S:P2S5. It also refers to the electrolyte characterized by the product formed, and the amount of reactants or precursors is Li2S It is 90 atomic percent Li2S and 10 atomic percent P2S5. LPS is also formed from a mixture of Li2S:P2S5 This also refers to electrolytes characterized by their specific properties, and the amount of reactants or precursors is 85 atomic percent for Li2S. P2S5 is present at 15 atomic percent. LPS is also characterized by products formed from a mixture of Li2S:P2S5. This also refers to the electrolytes that are identified, and the amounts of reactants or precursors are 80 atomic percent for Li2S and 20 atomic percent for P2S5. It is %. LPS is also characterized by products formed from a mixture of Li2S:P2S5. This also refers to electrolytes, and the amounts of reactants or precursors are 75 atomic percent for Li2S and 25 atomic percent for P2S5. LP S also refers to an electrolyte characterized by products formed from a mixture of Li2S:P2S5. The amounts of reactants or precursors are 70 atomic percent of Li2S and 30 atomic percent of P2S5. LPS also contains Li2 The term also refers to an electrolyte characterized by a product formed from a mixture of S:P2S5, or reactants or The amounts of precursors are 65 atomic percent Li2S and 35 atomic percent P2S5. LPS is also a mixture of Li2S:P2S5. This also refers to electrolytes characterized by the products formed from the compound, and the amount of reactants or precursors. It consists of 60 atomic percent Li2S and 40 atomic percent P2S5. 【0050】 As used herein, LPSO is the above and formula Li x P y S z O w Characterized by The electrolyte material is included, where 0.33≦x≦0.67, 0.07≦y≦0.2, 0.4≦z≦0.55, and 0≦w≦0.15 Furthermore, LPSO refers to the above-defined LPS having an oxygen content of 0.01 to 10 atomic percent. In some cases, the oxygen content is 1 atom%. In other cases, the oxygen content is 2 atom%. In some other examples, the oxygen content is 3 atoms. In some other examples, the oxygen content is 4 atoms. It is %. In other examples, the oxygen content is 5 atoms %. In some other examples, the oxygen content is 6 It is expressed as an atomic percentage. In some cases, the oxygen content is 7 atomic percent. In other cases, the oxygen content is 8 atomic percent. It is an atomic percent. In some other examples, the oxygen content is 9 atomic percent. In some examples, the oxygen content The amount is 10 atomic percent. 【0051】 As used herein, the term “necked” refers to, for example, a solid solution. , bonding of particles in polymers, solid matrices, or solvent matrices This refers to the properties of the particles. Like neck-type electrolyte particles, these particles are in contact with each other or on the surface. Through sharing, sufficient ion conduction pathways are formed from particle to particle and through the particles. They are in contact. The neck type shares a surface, an edge, or a corner with the other. It may include particles that are bonded to each other by means of a polymer, solvent, etc. When mixed with other solid components, it forms a permeable network. 【0052】 As used herein, the term "degree of dispersion" refers to standard techniques, e.g., dynamic This refers to the width of the particle size distribution as measured by light scattering. Mathematically, the particle distribution is approximately logarithmic. regular 【number】 In this case, the degree of variance of the distribution is σ. The degree of variance scale expressed numerically in this application. The degree is the best fit log-normal distribution for experimentally measured particle size distribution. This refers to the degree of variance (σ) of the distribution. The variance value (σ) can be calculated using the formula above. 【0053】 As used herein, the term "sulfide-based electrolyte" means an ion (e.g., Li +) conducts electrical conductivity and electrically insulates the positive and negative electrodes of an electrochemical cell (e.g., a secondary battery). This refers to an electrolyte containing an inorganic material with sulfur suitable for [a certain purpose]. Examples of sulfide-based electrolytes are given above. Examples include LXPS, LSTPS, LPSO, and related sulfides. Examples of sulfide-based electrolytes include 201 The "LI" application filed on May 15, 2014, was published on November 20, 2014, as International Publication No. 2014 / 186634. A MP B S C Solid phosphate or electrolyte for batteries using (M = SI, GE, and / or SN) E CATHOLYTE OR ELECTROLYTE FOR BATTERY USING LI A MP B S C (M = SI, GE, AND / OR SN)) It is described in international application PCT / US14 / 38283, which is titled "". 【0054】 As used herein, the terms “solid cassolite” or “cassolite” are used in this specification. The term refers to the cathode (i.e., positive electrode) active material (e.g., lithium, lithium cobalt acid). Cobalt oxide, or lithium manganese cobalt oxide, or lithium nickel aluminum cobalt It is tightly mixed with or surrounded by metal fluorides (which optionally contain oxides) It refers to an ion conductor. 【0055】 As used herein, the terms “nanostructure” or “nano-dimensional” refer to a structure. This refers to composite materials in which components are separated by nanoscale dimensions. For example, a nanoscale composite material Examples include Li-containing compounds, such as LiF, and Fe-containing compounds, such as Fe. Here, the Fe region and the LiF region are visually contrasting regions in various nanoscale regions. When measured by TEM microscopy based on the identification of the region, it is approximately 1-100 nm, or 2-50 nm, or 1-10 nm. or have a median physical dimension of 2-5 nm, or 5-15 nm, or 5-20 nm. 【0056】 As used herein, the term "electrolyte" means an ionic conductive and electrically insulating substance. This refers to the materials. The electrolyte is an ion, for example, Li + It enables conduction in the electrolyte at the same time It is useful for electrically insulating the positive and negative electrodes of a secondary battery. 【0057】 As used herein, the term "anolite" means anode material or a It is mixed with the node current collector, or superimposed on them, or stacked on them. This refers to layers of ion-conducting material. 【0058】 As used herein, the term "green film" refers to garnet material, garnet A precursor, binder, solvent, carbon, dispersant, or combination thereof of the set material is selected. This refers to an unsintered film containing at least one element. 【0059】 As used herein, the term “to make” means to form an object that is made. Or it refers to a process or method that brings about the formation. For example, fabricating an energy storage electrode. This refers to a process, step, or method that results in the formation of electrodes for an energy storage device. Including the method. The final result of the process constituting the fabrication of the energy storage electrode is a functional electrode. It is the generation of materials. 【0060】 As used herein, the term “energy storage electrode” means, for example, “energy storage electrode.” For use in ghee storage devices, for example, in rechargeable lithium batteries or Li-secondary batteries. This refers to an electrode suitable for rechargeable batteries. As used herein, such an electrode is a rechargeable battery. It can conduct electrons and lithium ions necessary for charging and discharging the battery. 【0061】 As used herein, the phrase “to provide” means the supply or production of something that is provided. It refers to completion, presentation, or delivery. 【0062】 As used herein, the term "conductive additive" refers to a substance that improves the conductivity of the cathode. This refers to a material that is mixed with a cathode active material to increase its activity. Examples include, but are limited to, However, carbon, and various forms of carbon, such as Ketjenblack, VGCF, acetylene Chilen black, graphite, graphene, nanotubes, nanofibers, and These are some possible combinations. 【0063】 As used herein, the phrase “apply pressure” means an external device, for example This refers to the process by which a calender or uniaxial press induces pressure in another material. 【0064】 As used herein, the term "approximately" refers to the allowable margin of error in numbers accompanied by the word "approximately". It refers to the volume. In some cases, the word "approximately" indicates a number where an error is acceptable. This includes a range of ±5-10%. For example, evaporating a solvent at approximately 80°C is equivalent to 79°C, 80°C, etc. This includes evaporating the solvent at °C or 81°C. 【0065】 As used herein, the term "lithium-filled garnet electrolyte" means garnet This refers to oxides characterized by a crystalline structure related to a net crystal structure. (Lithium-filled garnet) is the formula Li A La B M' c M'' D Zr E O F 、Li A La B M' C M'' D Ta E O F 、or Li A La B M' C M'' D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 13, and M' and M'' are each, independently in each case, Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me'' e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f < 13, and Me'' is a metal selected from Nb, Ta, V, W, Mo, or Sb), and contains a compound as described herein . The garnet used herein also includes the above garnet doped with Al2O3 . The garnet used herein includes the above garnet doped such that Al 3+ replaces Li + . As used herein, lithium-filled garnet, and garnet usually, but not limited to, Li La3(Zr 7.0 La3(Zr t1 + Nb t2 + Ta t3 )O 12 + 0.3 Containing 5Al2O3; wherein the ratio of La:(Zr / Nb / Ta) is 3:2, (t1 + t2 + t3 = subscript 2). Also, the garnet used in this specification is not limited but, Li is x La3Zr2O 12 + yAl2O3 (where x ranges from 5.5 to 9; and y ranges from 0 to 1) is included. In some examples, x is 7 and y is 1.0. In some examples, x is 7 and y is 0.35. In some examples, x is 7 and y is 0.7. In some examples, x is 7 and y is 0.4. Also, the garnet used in this specification is , not limited, but Li x La3Zr2O 12 + yAl2O3 is included. 【0066】 As used in this specification, the garnet does not include YAG - garnet (i.e., yttrium aluminum garnet, or for example, Y3Al5O garnet, or for example, Y3Al5O 12 ). As used in this specification the garnet does not include silicate garnets such as pyrope, almandine, sp essartine, grossular, hessonite, or cinnamon stone, tschabolaite, u varovite, and andradite, as well as solid solutions of pyrope - almandine - spess arite (spessarite) and uvarovite - grossular - andradite. The garnet in this specification does not include nesosilicates having the general formula X3Y2(SiO4)3 (where X is Ca, Mg, Fe, and / or Mn ; and Y is Al, Fe, and / or Cr). 【0067】 As used in this specification, the term "porous" refers to pores such as nanopores, mesopores , or refers to a material containing micropores. 【0068】 (II. Size) In some examples, the configurations and nanostructures of the positive electrodes of various rechargeable batteries are described herein. In some of these examples, the positive electrode is the active material (intercalation chemistry). ) Cathode material, conversion chemical cathode material, or combination thereof), together with the active material Catholite material (small-sized ceramic, acid) is ground, crushed, and mixed. It comprises an electrolyte material (a compound or sulfide), and any binder and electron conductive additive. In the example of the part, at least the cathode active material and the catholite material are large cathode active material The particle size (diameter) ratio to the particle size of the smaller catholite particles is at least 3:1. It is crushed in this way. In some cases, this size ratio (large particle size: small particle size) is less Both 3:1, or at least 3.5:1, or at least 4:1, or at least 4.5:1, or less At least 5:1, or at least 5.5:1, or at least 6:1, or at least 6.5:1, is at least 7:1, at least 7.5:1, or at least 8:1, or at least 8.5:1, and is at least 9:1, or at least 9.5:1, or at least 10:1, or at least 10.5 :1, or at least 11:1, or at least 11.5:1, or at least 12:1, or less 12.5:1, or at least 13:1, or at least 13.5:1, or at least 14:1, or is at least 14.5:1, or at least 15:1, or at least 15.5:1, or at least 1 6:1, or at least 16.5:1, or at least 17:1, at least 17.5:1, or less 18:1, or at least 18.5:1, or at least 19:1, or at least 19.5:1, and at least 20:1, at least 20.5:1, or at least 21:1, or at least 21.5:1 , or at least 22:1, or at least 22.5:1, or at least 23:1, or at least 23.5:1, or at least 24:1, or at least 24.5:1, or at least 25:1, At least 25.5:1, or at least 26:1, or at least 26.5:1, or at least 27 :1, or at least 27.5:1, or at least 28:1, or at least 28.5:1, or less At most 29:1, or at least 29.5:1, or at least 30:1. In some cases, The size ratios (larger particle size:smaller particle size) are 3:1, 3.5:1, 4:1, 4.5:1, 5:1, and 5.5:1. , 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1 , 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15.5:1, 16:1 , 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1, 20:1, 20.5:1, 21:1 , 21.5:1, 22:1, 22.5:1, 23:1, 23.5:1, 24:1, 24.5:1, 25:1, 25.5:1, 26:1 , 26.5:1, 27:1, 27.5:1, 28:1, 28.5:1, 29:1, 29.5:1, or 30:1. In these examples, the cathode-active particles are large particles. In some of these examples, the catholite Particles are small particles. 【0069】 In some examples, the configurations and nanostructures of the positive electrodes of various rechargeable batteries are described herein. It can be. In some of these examples, the positive electrode includes an active material, a catholite material that is ground, pulverized, and mixed together with the active material, and any binder and electronic conduction additive. In some examples, at least the cathode active material and the catholite material are pulverized such that the particle size (diameter) ratio of the large cathode active material to the small particle size of the catholite is at least 3:1 or more. In some examples, at least the cathode active material and the catholite material are pulverized such that the particle size (diameter) ratio of the large cathode active material to the small particle size of the catholite is at least 3:1 or more. In some examples, at least the cathode active material and the catholite material are pulverized such that the particle size (diameter) ratio of the large cathode active material to the small particle size of the catholite is at least 3:1 or more. In some examples, the active material is NCA and has a D of 250 - 400 nm, 1 - 2 μm, or 5 - 6 μm. 50 In these examples, the catholite has a D of 250 - 300 nm. 50 have In some examples, positive electrodes of various rechargeable 【0070】 In some examples, positive electrodes of various rechargeable 50 batteries containing an active material having a particle D diameter of 1 - 5 or 5 μm are described herein. In some of these examples, the catholite has a particle D diameter of 1 μm. 50 In some of these examples, the catholite has a particle D 50 diameter of 300 nm. have 【0071】 (III. Materials) As demonstrated in Example 1, infiltration is achieved at a low volume fraction when the size ratio of the particle size of the large positive electrode active material to the particle size of the small catholite is about 4:1 or more. In some examples, as described herein, the positive electrode active material is LiMPO4 (M = Fe, Ni, Co, Mn ), Li Ti x O y (where x is 0 - 8, y is 1 - 12, z is 1 - 24), LiMn2O4, LiMn z Ni 2a O4 (where a a O4 (where a (0-2), LiCoO2, Li(NiCoMn)O2, Li(NiCoAl)O2, and nickel-cobalt aluminum Selected from the group consisting of monoxides (NCAs), which are selected from the interlayer oxide materials. Some other examples Therefore, the positive electrode active material includes a metal fluoride conversion chemical material, and also contains FeF2, NiF2, FeO x F 3-2x Selected from the group consisting of FeF3, MnF3, CoF3, CuF2 materials, and alloys or combinations thereof. In some other examples, the cathode active material is a combination of intercalated oxides and converted chemical metal fluorides. Includes 【0072】 In certain cases, the cathode-active material is a nanoscale transformation chemical material (e.g., FeF3). A suitable cathode-active material was published in U.S. Patent Application Publication No. 2014 / 0170493 on June 19, 2014. The patent application filed on June 19, 2013, for "Nanostructured materials for electrochemical conversion reactions" was published. A US non-specialized patent with the name "RED MATERIALS FOR ELECTROCHEMICAL CONVERSION REACTIONS" Approved application No. 13 / 922,214; also, application filed on February 25, 2015, "including both interlayer material and conversion material" Hybrid electrodes with both interaction and conversion mat International application number PCT / US2015 / 017584, named "ERIALS"; also filed on December 23, 2014 Lithium-rich nickel manganese cobalt oxide (LR-NMC) U.S. Provisional Patent Application No. 62 / 096,510, titled "MANGANESE COBALT OXIDE (LR-NMC)") It is included. The full disclosures of these applications are by reference for any purpose whatsoever. All of the contents are incorporated herein. 【0073】 In certain cases, the cathode active material is NCA and has a median particle size of approximately 5-6 μm. In certain cases, the catholite needs to maintain a particle size ratio of at least 4:1 or higher. This would be catholite with a particle size of less than 1.5 μm (e.g., 1.2–1.5 μm). 【0074】 In certain cases, the cathode active material is NCA and has a median particle size of approximately 5-6 μm. In certain cases, the catholite needs to maintain a particle size ratio of at least 4:1 or higher. This would be catholite with a particle size of less than 1.5 μm (e.g., 1.2–1.5 μm). 【0075】 In a specific example, the cathode active material is FeF3 and has a median particle size of approximately 300 nm. In certain cases, catholites that need to maintain a particle size ratio of at least 4:1 or higher are It is likely a catholite with a particle size of less than 80 nm (e.g., 60-80 nm). 【0076】 In certain cases, the cathode active material is NCA and has a median particle size (D) of approximately 4-10 μm. 50 ) has In this particular example, the particle size ratio must be maintained at least 20:1 or higher. The catholite is likely to be a catholite with a particle size of less than 500 nm (e.g., 200 nm). 【0077】 In certain examples, the positive electrode active material includes a composite material of FeF3, carbon, and an ion conductor. The diameter of the composite material is 1 μm. In this particular example, the particle size ratio is at least 20:1. Catholites that need to be maintained at a particle size ratio of 4:1 or 1:1 are, for example, It is likely a catholite with a particle size of approximately 50 nm, 250 nm, or 1 μm. 【0078】 In certain examples, the positive electrode active material includes a composite material of FeF3, carbon, and an ion conductor. The diameter of the composite material is 10 μm. In this particular example, the particle size ratio is at least 20:1. The catholites that need to be maintained at a particle size ratio of 4:1 or 1:1 are approximately 500 each. It is likely a catholite with a particle size of nm, 2.5 μm, or 10 μm. 【0079】 In certain examples, the positive electrode active material includes a composite material of FeF3, carbon, and an ion conductor. The diameter of the composite material is 100 μm. In this particular example, the particle size ratio is at least 20:1. The catholites that need to be maintained at a particle size ratio of 4:1 or 1:1 are each approximately 5 μm It is likely a catholite with a particle size of m, 25 μm, or 100 μm. 【0080】 (IV. Method) This disclosure relates to electrochemical devices and materials thereof. More details are provided herein. The embodiment describes a low porosity electrode containing large and small particles. The large particles are It contains electrochemically active materials. The small particles are ion-conducting materials, for example, sulfide-based or This includes garnet-type catholites (e.g., lithium-filled garnet). In some cases, Large and small particles are characterized by a dispersion degree of 0.5 or less. Other embodiments They also exist. 【0081】 In some examples, methods for forming electrode materials are described herein, and such methods include a first plurality A step of preparing particles and a second plurality of particles, wherein the first plurality of particles are less than 10 μm Characterized by a first central diameter, the second plurality of particles have at least 5e~4S / cm Characterized by ionic conductivity, the first central diameter is at least 3 times the second central diameter. The ratio is doubled, and the first plurality of particles and the second plurality of particles are characterized by a dispersion degree of less than 0.25. The process is characterized by: mixing the first plurality of particles and the second plurality of particles to form a mixed material. The process includes: a step of depositing the mixture inside an electrode; and a step of compressing the electrode. . 【0082】 In some examples, methods including a step of drying the mixed materials are described herein. 【0083】 In some examples, the method described herein includes the step of depositing a mixed material onto a substrate. 【0084】 In some cases, a method is described herein in which a mixing step is performed before the deposition step. . 【0085】 In some examples, methods including a step of calcining the mixed materials are described herein. 【0086】 In these examples where materials are pulverized, various pulverization techniques can be used. For example, Grinding technologies include dry grinding, planetary milling, freeze grinding, jet grinding, and wet grinding. The group consisting of formula grinding, or grinding using beads and / or a media mill can be selected. can. 【0087】 As explained above, solid-state battery devices can be useful in a variety of applications. For example, Solid-state batteries, which have a solid electrolyte material, have advantages over conventional batteries that utilize liquid electrodes. These advantages may include safety and high-temperature operation performance. For efficient operation, various components of a solid-state battery must possess specific characteristics, such as high conductivity. It is desirable that it has a rate, energy density, and capacitance. More specifically, solid-state batteries The electrodes require an active material that is mixed with a high-speed lithium-ion conductive material for high power capacity. This may be the case. The electrodes further include electron conduction components, as well as binders for bonding and adhering the electrodes. This may be necessary. The efficient packing of these solids is essential for fabricating high-energy-density electrodes. This can be extremely important. The embodiments described herein are useful for high-energy-density electrodes. It should be understood that this includes a structure and algorithm that provides an efficient packed electrode configuration. 【0088】 If the various components of a solid electrode are not efficiently packed, the introduction of wasted volume results in less However, voids can be formed in the air that reduce energy density. In addition to a low porosity, casora The absence of a thread penetration network results in low ionic conductivity, which leads to low power output. It is possible. In addition, the absence of a osmotic network in the catholites may lead to electrochemical changes in the ions. Reduced access to the active material can lead to a decrease in energy capacity. 【0089】 In some examples, methods including the following steps are described herein: In the first step, sulfidation A material electrolyte is prepared. The sulfide electrolyte may include any sulfide electrolyte described herein. The electrolyte is subjected to a pulverization technique in the second step, for example, by wet pulverization, which reduces the particle size. In the third step, the pulverized electrolyte is centrifuged and processed to reduce the solvent. In some cases, this process involves grinding the electrolyte with a liquid grinding solvent of approximately 50 w / w% solid / This involves the evaporation of the solvent to form a liquid mixture. Depending on the grinding conditions, various sizes and distributions can be obtained. The particle size can be achieved. Next, the pulverized electrolyte is a cathode active material (or substitute, For example, when mixed with Al2O3, this active material has a known specified particle size. In this process, the binder and any carbon are mixed with the electrolyte and active material. In the first step, the mixture of materials is mixed. In the next step, the mixed mixture is cast using casting technology (e.g. For example, a film can be made using a slot die, draw coating, or doctor blade. It is poured in. In the next step, for example, a hot plate or oven (depending on the solvent used) The cast film is then dried at 40-200°C. In some cases, this method is used with calendering. The method further includes applying pressure or compression to the dried film using the technique. 【0090】 (V. Electrode configuration with mixed particle sizes) Figure 1 is a simplified diagram illustrating an electrode material according to one embodiment of the present invention. This figure is simply a simplified diagram. This is an example, and the scope of the patent claims should not be excessively limited. A person skilled in the art would know that many You will understand the variations, substitutes, and changes. As shown in Figure 1, The electrode material 100 contains large particles 102 and small particles 101. The relative size and ratio between the larger and smaller particles are not depicted to an accurate scale, and are simply An example is provided. Larger particles are electrochemically active materials. Smaller particles The particles are ion-conducting materials. For example, larger particles are conversion chemical materials, e.g. For example, all of their contents are incorporated herein by reference for all purposes, 20 Filed on June 19, 2013, and published as US Patent Application Publication No. 2014 / 0170493 on June 19, 2014, the US non-provisional patent application No. 13 / 922,214 named "NANOSTRUCTURED MATERIALS FOR ELECTROCHEMICAL CONVERSION REACTIONS"; also, the international application No. PCT / US2015 / 017584 named "HYBRID ELECTRODES WITH BOTH INTERCALATION AND CONVERSION MATERIALS" filed on February 25, 2015; and also, the US provisional patent application No. 62 / 096,510 named "LITHIUM RICH NICKEL MANGANESE COBALT OXIDE (LR-NMC)" filed on December 23, 2014. For example, the electrochemically active materials include, but are not limited to, iron fluoride materials, copper fluoride materials, nickel fluoride materials, and / or other types of materials. The small-sized particles include a solid electrolyte or a catholyte material. In certain embodiments, the small-sized particles are an ion-conductive electrolyte material including Li X P S O (where X = Si, Ge, Al, Sn, and combinations thereof, and 5 ≦ a ≦ 15, 0 ≦ b ≦ 3, 1 ≦ c ≦ 4, 6 ≦ S ≦ 18, 0 < e ≦ 5). For example, the ion-conductive electrolyte material is, for all purposes, incorporated herein by reference in its entirety, the "Li filed on May 15, 2014. 、電気化学的に活性な材料としては、限定されるものではないが、フッ化鉄材料、フッ化 銅材料、フッ化ニッケル材料、及び / 又は他のタイプの材料を挙げらることができる。小 さいサイズの粒子は、固体電解質又はカソライト材料を含む。特定の実施態様では、小さ いサイズの粒子は、Li a X b P c S d O e (式中、X=Si、Ge、Al、Sn、及びこれらの組み合わせ、 かつ5≦a≦15、0≦b≦3、1≦c≦4、6≦S≦18、0<e≦5)を含むイオン伝導性電解質材料 であり得る。例えば、イオン伝導性電解質材料は、あらゆる目的のために参照によりそれ ぞれの全内容が本明細書に組み入れられる、2014年5月15日出願の「Li AMP B S C (M = Si, Ge 、and / or Sn) for a solid catholyte or electrolyte for a battery (SOLID STATE CATHOLYTE O R ELECTROLYTE FOR BATTERY USING Li A MP B S C (M = Si, Ge, AND / OR Sn))」 under the name of International Application No. PCT / US14 / 38283; also described in U.S. Patent No. 8,697,292 granted to Kanno et al. In various embodiments, the relative median diameter of the large particles (electrochemically active material) is at least three times larger than the relative median diameter of the small particles (ion conductive material). For example, the large particles can have a central diameter of 1 - 10 μm or about 0.1 - 1 μm, and the small particles can have a central diameter of about 200 nm - 2 μm or about 50 - 200 nm. 【0091】 As used herein, D 50 is a measure of the volume-averaged median particle size. 【0092】 In conventional batteries, the electrochemically active material consists of particles of a size sufficient to substantially charge and discharge in a given time at a given current. The gaps in the conventional active material are wetted with a liquid electrolyte that provides a high lithium ion conductivity on the surface of the active material. In a solid battery, the liquid must be replaced with a solid catholyte material having an ion conductivity equivalent to that of the liquid. The electrodes herein are engineered such that the catholyte penetrates the electrodes with a minimum volume consumption to conduct lithium ions throughout the cathode. The cathode is Because it does not contribute to energy density, the total volume of the catholite is the same as the volume of the catholite in a field where no catholite exists at all. It tends to decrease energy density compared to a combination. 【0093】 In the electrochemical cells described herein, the porosity does not contribute to energy storage, Minimized by either the selection of particle size ratio or by compression means as described herein. In an electrochemical cell, high ionic conductivity is maintained for passing through small particles, while for larger particles... The volume occupied should be made as large as possible. This allows for the volume occupied by small particles to be reduced while maintaining high ionic conductivity through the electrodes. It should be made as small as possible. In the electrochemical cells described herein, the volume of the gaps is possible It should be made as small as possible. Also, in the electrochemical cell described herein, small particles The proportion of small particles contributing to the permeation network relative to the total amount should be as large as possible. It should be. In the electrochemical cells described herein, a small particle penetration network is used. The proportion of larger particles that come into contact should be as large as possible. 【0094】 In the example of electrochemical electrodes described herein, the catholite is the space between the large particles of the active material. It contains small particles that efficiently fill the spaces between larger particles. They fill the gaps and, at the same time, provide ion conduction pathways through the electrodes. Large electrochemically active particles Since the element primarily contributes to the energy capacity, it preferably occupies more than 50% of the total volume of the electrode material. The small-sized particles preferably make up less than 20% of the total volume of the electrode material. Electrode materials containing small-sized particles can be compressed and have a porosity of less than 25%. Please understand that it has [this characteristic]. 【0095】 The size and distribution of both large and small particles for electrode materials are important for solid-state battery devices. It should be understood that this affects the performance. For example, the electrodes according to the embodiments of this specification 80% of the total energy capacity can be charged within 2 hours. (Large particles and small particles) Both the absolute and relative dispersion of the child are configured to suit the performance characteristics of the electrode material. For example, the dispersion of large and small particles is determined by the ionic conductivity and electronic conductivity of the electrode material. and adjust the recharge characteristics. According to various embodiments, large and small particles of the electrode material The dispersion of both particles is less than 0.25. For example, a pair of particles is distributed in a Gaussian pattern. 【number】 If such a distribution has the variance (σ), then the degree of dispersion (σ) of the distribution is the standard deviation of the distribution. In another example, particle fraction The fabric follows an approximately log-normal distribution. 【number】 In this case, the degree of dispersion of the distribution is σ. In various embodiments, small particles and large The particles are mixed homogeneously. Desired dispersion and size ratio of large and small particles. So, the proportion of small particles that contribute to the permeation network (for example, ions) is over 80%. It is possible. The proportion of large particles that come into contact through the penetration network can exceed 80%. For example, the measure of dispersion expressed numerically in this application is the experimentally measured particle size distribution. This refers to the degree of variance of the optimal log-normal distribution for a given value. For example, the variance value (σ) can be calculated using the above formula. It can be calculated. It has been understood that various variance values ​​can be used depending on the specific implementation. Yes. As described above, dispersion values of less than 0.25 for both large and small particles are suitable for specific applications. In some embodiments, dispersion values of less than 0.5 for both large and small particles are used in the formation of the catholite material. In addition to the large particles of the electrochemically active material and the small particles of the ion conductive material, the electrode material may further include an electron conductive additive and / or a binder material. For example, the electron conductive additive may include acetylene black, carbon black, graphene, graphite, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotube, ketjen black, and / or others. The binder material may include rubber, polymer, and / or other types of materials. Figure 2 is a simplified diagram illustrating an electrode material according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. As shown in Figure 2, the electrochemically active material is larger than the ion conductive particles that fill the space between the electrochemically active materials. For example, the electrochemically active material includes a cathode active material, and the ion conductive particles include electrolyte (or catholite) particles. 【0096】 Yes. As described above, dispersion values of less than 0.25 for both large and small particles are suitable for specific applications. In some embodiments, dispersion values of less than 0.5 for both large and small particles are used in the formation of the catholite material. In addition to the large particles of the electrochemically active material and the small particles of the ion conductive material, the electrode material may further include an electron conductive additive and / or a binder material. For example, the electron conductive additive may include acetylene black, carbon black, graphene, graphite, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotube, ketjen black, and / or others. The binder material may include rubber, polymer, and / or other types of materials. Figure 2 is a simplified diagram illustrating an electrode material according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. As shown in Figure 2, the electrochemically active material is larger than the ion conductive particles that fill the space between the electrochemically active materials. For example, the electrochemically active material includes a cathode active material, and the ion conductive particles include electrolyte (or catholite) particles. Figure 3 is a simplified diagram illustrating a permeation network according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. In Figure 3, the electrode material In addition to the large particles of the electrochemically active material and the small particles of the ion conductive material, the electrode material may further include an electron conductive additive and / or a binder material. For example, the electron conductive additive may include acetylene black, carbon black, graphene, graphite, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotube, ketjen black, and / or others. The binder material may include rubber, polymer, and / or other types of materials. Figure 2 is a simplified diagram illustrating an electrode material according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. As shown in Figure 2, the electrochemically active material is larger than the ion conductive particles that fill the space between the electrochemically active materials. For example, the electrochemically active material includes a cathode active material, and the ion conductive particles include electrolyte (or catholite) particles. 【0097】 Figure 2 is a simplified diagram illustrating an electrode material according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. As shown in Figure 2, the electrochemically active material is larger than the ion conductive particles that fill the space between the electrochemically active materials. For example, the electrochemically active material includes a cathode active material, and the ion conductive particles include electrolyte (or catholite) particles. This is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. As shown in Figure 2, the electrochemically active material is larger than the ion conductive particles that fill the space between the electrochemically active materials. For example, the electrochemically active material includes a cathode active material, and the ion conductive particles include electrolyte (or catholite) particles. Figure 3 is a simplified diagram illustrating a permeation network according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. In Figure 3, the electrode material This is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. 【0098】 Figure 3 is a simplified diagram illustrating a permeation network according to an embodiment of the present invention. This figure is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. This is merely an example and should not unduly limit the scope of the claims. Those skilled in the art will understand numerous variations, alternatives, and modifications. In Figure 3, the electrode material This is demonstrated using only ion-conducting particles; large electrochemically active materials are small particles. Removed from the image to better illustrate the infiltration network of this child. Ionic conductivity The material allows for the penetration of substances, such as lithium ions, into the electrodes during charge-discharge cycles. Therefore, it is suitable as a catholite material. 【0099】 Figure 4 shows the penetration threshold (ρ) of randomly packed electrode materials. S * , here ρ S These are small particles Volume (V s The ratio of the total particle volume to the total particle volume, V s / (V s +V l ) vs. large particles and small This is a simplified graph illustrating the particle size (diameter) ratio between particles. This figure is merely an example. The scope of the patent claims should not be excessively limited. A person skilled in the art would know that there are many variations. You will understand the options, alternatives, and changes. Figure 4 shows the infiltration threshold ρ S * And, the large in the electrode This illustrates the relationship between the size ratio of a particle and a smaller particle. For example, the size of the graph A particle-to-cement ratio of 6 means that the central diameter of a larger particle is approximately 6 times larger than the central diameter of a smaller particle. In general, the permeation threshold ρ S * It decreases as the size ratio increases. However, Even with a small size ratio, penetration is achieved through numerous small contacts that cannot provide effective conduction. This is possible. For example, if contact with a contact radius of less than 1 nm is ignored, the penetration threshold increases. The sensitivity to size ratio is significantly reduced. Figure 4 shows seven saturations where particles are packed without compression. This illustrates the penetration threshold of a sample distribution. ρ S *It is understood that it is determined to be within the range. I want to. If the size ratio is 6, ρ S * It is within the range of approximately [0 to 0.12]. is, ρ S * Since this is typically greater than 0.15, ρ less than 0.12 S * It is lower than expected. Please understand. For example, Figure 4 is ρ S * The ratio decreases with size and increases with dispersion. This indicates that. 【0100】 Figure 5 shows the large and small particles of the compressed-filled material according to the embodiments described herein. This is a simplified graph illustrating the size ratio between offspring. This figure is merely an example and does not represent a patent claim. The scope should not be excessively limited. A person skilled in the art will know that there are many variations, alternatives You will understand the substitutes and changes. As can be seen from Figure 5, the compression of the particles reduces the penetration threshold. The value changes. More specifically, the penetration thresholds of the seven distributions change with a slight compression of 2%. This illustrates why a decrease and subsequent compression are desirable. 【0101】 Figure 6 illustrates the random packing density related to particle size ratio according to the embodiments described herein. This is a simplified diagram. This diagram is merely an example and should not excessively limit the scope of the patent claims. No. Those skilled in the art will understand the numerous variations, substitutes, and modifications. In Figure 6, φ rcp = Total volume of particles / Volume of container. For example, φ rcp =1 means the volume of the container is This means it is completely filled. If the size ratio is 1, it means the most densely packed random spheres Large packing, φ rcpIt is known to be approximately 0.64. Figure 6 shows the random close-packed portion of the osmosis system. This indicates φ rcp It can be seen that this can increase with size ratio and decrease with dispersion. For size ratios greater than 1, the diameter must be greater than 0.64. rcp This value can be achieved, and this is the electrode This illustrates the advantage of having a size difference between the catholite particles and the active particles inside. As mentioned, it would be desirable for the electrode material to have a high packing density. 【0102】 Figure 7 shows the total volume of the container occupied by smaller particles for different particle size ratios. This is a simplified graph illustrating the renormalized penetration threshold. This figure is merely an example. Therefore, the scope of the patent claims should not be excessively limited. A person skilled in the art would know that there are many variations. You will understand substitutions, alternatives, and changes. More specifically, on the vertical axis in Figure 7... Product φ rcp ρ S * The value of is the small particle φ at the penetration threshold. s The entire volume of the container occupied by This shows the result. For the example in Figure 7, a 2% compression (volume) is used for packing, and the result is less than 1 nm. R C Contact with is ignored. The compression described herein reduces the size of the simulation box to 2 A % reduction means that the overlap between particles becomes approximately 2%. This is the netting of the particles. This is a necking model. The graph shows the penetration threshold, φ s The size ratio and dispersion are approximately This indicates that it is constant. The graph shows that small particles occupy more than 14% of the total volume of the container. In summary, this suggests that penetration occurs with a sufficiently low degree of dispersion and a sufficiently high size ratio. 【0103】 In some examples, compression is applied to the electrodes. The compression is applied to rollers with a diameter of 90 mm and 100 m. Line pressure of 8 for electrode strips that are 110 mm or more, or 120 mm or more, and less than 300 mm wide. Calculator mills are used at pressures of MPa, 9 MPa, 10 MPa, and above 11 MPa, with a feed rate of less than 5 cm / s. It can be added by (ng camp). 【0104】 Figure 8 shows the small particles as a function of volume according to the embodiments described herein. This illustrates the proportion of the 2D cross-sectional area occupied by the child. This figure is merely an example and is not patentable. The scope of the claims should not be excessively limited. A person skilled in the art would know that there are many variations. They will understand the alternatives and modifications. As shown in Figure 8, the cross-sectional area φ 2D There are 7 Regarding the distribution, the volume ρ occupied by small particles S It is shown on the vertical axis as a function of Figure 8 shows that the cross-sectional area occupied by the infiltrated particles is approximately ρ S It increases linearly with, and This is almost the same for all distributions except for the size ratio 2 and the truncated distribution. This indicates something. 【0105】 In the drawings of this specification, δ is the degree of dispersion and η is the median particle size ratio (d l / d s ) 【0106】 Figure 9 shows the normalized 2D function of the penetration threshold of the electrode at 2% compression according to an embodiment of the present invention. This diagram illustrates the proportion of the cross-sectional area. This diagram is merely an example and does not unduly limit the scope of the claims. It should not be done. A person skilled in the art would understand that there are many variations, substitutes, and modifications. It will be understood. Variable φS This is a 2D cross-section of the volume of a 3D container occupied by all the small particles. Refers to the proportion of the surface. Variable φ 2D It is occupied by small particles that are part of the penetration network. This refers to the ratio of the volume of the 3D container to the volume of the 2D cross-section. Figure 9 shows the volume of small particles ρ S As a function of φ, S This shows the ratio of the cross-sectional area normalized by the ratio φ. 2D / φ S All of the small particles If it contributes to the infiltration cluster, it is equal to 1. As shown in the graph, the size ratio is 2 and Except for the truncation distribution, almost all small particles are ρ S If >0.20, infiltration cluster This contributes to ρ. S If >0.20, φ 2D ≒φ S The idea that this is a good approximation It shows the picture. 【0107】 Figure 10 shows the infiltration particles as a function of the proportion of small particles, according to the embodiments described herein. This illustrates the relationship with the proportion of larger particles that come into contact with the surface. This figure is merely an example and is not patentable. The scope of the claims should not be excessively limited. A person skilled in the art would know that there are many variations. You will understand substitutes and changes. In these examples, the material in the graph has a volume of 2% It is compressed. More specifically, the graph shows that for the seven distributions, ρ S As a function of small This shows the proportion of larger particles that came into contact with the penetrating particles. The data is near the penetration threshold (ρ S In cases where approximately 10-15%, almost all of the larger particles are in contact with the smaller penetrating particles. It is showing. 【0108】 Figure 11 illustrates an electrode material containing substantially uncompressed large and small particles. This is an SEM image. As can be seen from Figure 11, the large and small particles are homogeneously mixed. Then, the larger particle comes into contact with the smaller particle. In Figure 11, the larger particle has a central diameter of approximately 5 μm. The particles have a diameter, and the smaller particles have a central diameter of approximately 300 nm. 【0109】 Figure 12 illustrates an electrode material containing large and small particles after undergoing a compression process. This is an SEM image. As can be seen from Figure 12, the small particles fill the gaps between the larger particles. It is fully satisfied. As illustrated, the larger particles have a central diameter of approximately 5 μm, and the smaller particles have a central diameter of approximately 5 μm. The rhizoid particles have a central diameter of approximately 300 nm. The interporation ratio of the illustrated electrodes is as expected. It has been measured to be less than 20%. In some cases, the compression process is uniaxial compression or Karen Contains dermil. 【0110】 Figure 13 shows an example of the electrode material shown in Figure 11. In Figure 13, the average size is the largest. The largest particles are the cathode-active material particles. The next largest particles in average size are the catholites. These are particles. Finally, the particles with the smallest average size are electron-conducting additives. 【0111】 The above is a complete description of a particular embodiment, but various modifications, alternative structures, and equivalents may be possible. It can be used. Therefore, the above description and examples are in accordance with the attached claims. This should not be interpreted as a limitation of the scope of the present invention as defined by [the specified method]. 【0112】 (VI. Electrochemical electrodes) In some examples, the description herein includes a first plurality of particles of an electrochemically active material. This relates to a solid electrode in an electrochemical device, wherein the first particle has a first dispersion degree of 0.25 or less. It has a first particle size distribution characterized by a first central diameter. In some examples, the first The central diameter is approximately 10 nm to 10 μm. In certain cases, the first central diameter is approximately 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 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, 16 0 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 26 0 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 36 0 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 46 These are 0 nm, 470 nm, 480 nm, 490 nm, or 500 nm. In certain examples, the first central diameter is Approximately 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, or It is 10 μm. In some examples, the electrode comprises a second plurality of particles of an ion-conducting material. The second particle is characterized by a second dispersion degree of 0.25 or less and a second median diameter. It has a diameter distribution, and the second central diameter is less than one-third of the first central diameter. 【0113】 In some examples, the electrode has a proportion of a second particle volume that is less than 20% of its total particle volume and does so. 【0114】 In some examples, the electrode is characterized by a porosity of less than 20 v / v%. In certain examples , the porosity is less than 15 v / v%. In certain other examples, the porosity is less than 10 v / v%. 【0115】 In some examples, the ion-conductive material in the electrode is Li a X b P c S d O e which includes, where X = Si, Ge, Al , Sn, and combinations thereof, and 5 ≦ a ≦ 15, 0 < b ≦ 3, 1 ≦ c ≦ 4, 6 ≦ S ≦ 18, 0 < e ≦ 5. In some examples, X is Si. In other examples, X is Si and Sn. In some other examples, X is Sn. In still other examples, X is Ge. In some examples, X is Si and Ge . 【0116】 In some examples, the electrodes herein can be charged within 2 hours until they have a capacity that is 80% or more of the electrode capacity. 【0117】 In some examples, the electrodes herein further include an electron-conductive additive selected from acetylene black, graphene, graphite, carbon black, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotube, ketjen black, or combinations thereof. 【0118】 In some examples, the electrodes herein further include a binder material, and the binder material includes rubber and / or polymer. 【0119】 In some cases, the electrodes described herein contribute to the penetration network at a rate exceeding 80%. It further includes a penetration network composed of two particle parts. In some examples, the second particle 80% of them are bound to the penetration network. In some other examples, 85% of the second particle is bound to the penetration network. It is joined to the network. In some other examples, 90% of the second particle is joined to the penetration network. They combine. In some other examples, 95% of the second particle combines with the penetration network. In other examples, 100% of the second particle is bound to the penetration network. In some examples, The finely detailed electrode further includes a penetration network, and the first part of the multiple particle portion exceeds 80%. It contacts the penetration network at a certain rate. 【0120】 In some examples, the description herein is characterized by a first particle size distribution having a first median particle size. An active material to be attached; and characterized by a second particle size distribution having a second median particle size. This concerns solid electrochemical electrodes containing catholite materials; and the catholite material is the active material. The volume ratio is 99:1 to 1:1; and the particle size ratio of the first median particle to the second median particle. The ratio is at least 3:1 or greater. 【0121】 In some cases, the description herein refers to solid energy having a dispersion degree of 0.25 or less in the first particle size distribution. This concerns vapor-based chemical electrodes. 【0122】 In some cases, the description herein refers to solid energy having a second particle size distribution with a dispersion degree of 0.25 or less. This concerns vapor-based chemical electrodes. 【0123】 In some cases, the description herein applies to solid electrochemical electrodes having a porosity of less than 20% by volume. Regarding that. 【0124】 In some cases, the description herein relates to solid-state electrochemical electrodes further comprising electron-conducting additives. The electron-conducting additive is acetylene black, carbon black, activated carbon, C6 5. Contains C45, VGCF, carbon fiber, carbon nanotubes, and / or Ketjenblack. In some of these examples, the electrochemical cell further comprises a binder material, and the binder The material is selected from rubber or polymer. 【0125】 In some cases, the description herein refers to solids in which the catholite material forms a permeable network. This concerns electrochemical electrodes. 【0126】 In some cases, the description herein states that more than 80% of the catholite particles in the electrode are permeable to the network. This concerns solid-state electrochemical electrodes bonded within a cubic cavity. [Examples] 【0127】 (VII. Examples) In the embodiments described herein, unless otherwise specified, the solid electrolyte described herein The subscript values ​​represent the elemental molar ratios of the precursor chemicals used in the preparation of the requested composition. The actual empirical elemental molar ratios of electrolytes may differ from those determined by analytical techniques. There are differences depending on the technology, for example, between X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy. . 【0128】 (Example 1: Filling ratio) In this embodiment, various packing scenarios were examined, and the packing density and permeability conductivity were determined. As shown in Figure 14, one filling scenario involved two particle sizes in the electrode. As shown on the left of 14, the larger sized particles (1401, cathode active material) are single The dispersed, small-sized particles are Gaussian for small particle size (1402, catholite ion conductor). It included a distribution. As shown on the right side of Figure 14, another scenario was considered, and it was large Both the large and small size particles had a Gaussian particle size distribution. The ratio of the diameter of the particles to the diameter of the smaller particles is 4 in each example in this embodiment. It was fixed in place. 【0129】 In this embodiment, in the second aspect, other filling scenarios are also considered, and the filling density and immersion The permeability was determined. As shown in Figure 15, one filling scenario involves two electrodes. It contained particle size. As shown in Figure 15, larger sized particles (1501, cathode active) were present. Both the material and the small-sized particles (1502, catholite ion conductor) are monodisperse particles. It was a collection of diameters. As shown on the left side of Figure 15, one scenario was fixed at 4. The particles exhibited a particle size (diameter) ratio of larger particles to smaller particles. Figure 15 As shown on the right, another scenario is a large-sized particle fixed at 2 It had a particle size (diameter) ratio relative to smaller particles. 【0130】 (Example 2: Conductivity as a function of particle size ratio) In this example, Al2O3 and LSTPS were independently ground to 5-6 μm and 200-250 nm, respectively. This was done. At these sizes, the ratio of large to small particle sizes is approximately 20:1. In this study, Al2O3 and LSTPS were independently ground to 1.25–1.5 μm and 200–250 nm, respectively. At these sizes, the ratio of large to small particle sizes is approximately 5:1. A third batch. Al2O3 and LSTPS were then independently ground to the same size, 200-250 nm. At these sizes, the ratio of large particle size to small particle size is approximately 1:1. In this example, ions The conductivity was measured. Al2O3 was used as a substitute for the cathode active material. 【0131】 Electrode preparations generally consist of a slurry containing pulverized Al2O3, LSTPS, a binder, and a solvent. Prepared by supplying - the slurry to a substrate (e.g., Al or stainless steel) The material was poured and dried on the substrate. The resulting dried material was then pressed using a uniaxial press at approximately 200-300 MPa. The material was compressed to the specified pressure. In this example, the particle size of the LSTPS was set to 250-300 nm. 50 Set to A The particle size of l2O3 was changed to obtain the particle size ratio described above. 【0132】 Each sample was placed in contact with a Li-containing electrode, and the conductivity of the electrode mixture was observed. These results are shown in Figure 16. 【0133】 As shown in Figure 16, the particle size ratios of larger particles to smaller particles are 20:1 and 5:1. The electrode formulation has a higher particle size ratio of larger particles to smaller particles than the electrode formulation with a 1:1 ratio. It was observed that the particles had measurable ionic conductivity. Electrode formulations with a diameter ratio of 1:1 have a particle size ratio of at least 5:1 for larger particles to smaller particles. It had a conductivity value that was almost two orders of magnitude lower than the electrode formulation above. In this embodiment, large grains Electrode formulations with a particle size ratio of at least 5:1 to the smallest particle size have a flow rate of approximately 5-7e-6 S / cm. σ i It was observed that it possessed (ionic conductivity). The trend shown in the data in Figure 16 Based on this, the highest permeability conductivity for a particle size ratio of 4:1 or greater to smaller particle size is determined. It was decided. 【0134】 As shown in Figure 17, the Al2O3 particles (1702) have a particle size of approximately 4-6 μm, and the LSTPS particles The particle (1701) had a roughly 250 nm particle size. As shown in Figure 18, Al2O3 particles. (1802) and LSTPS particles (1801) are homogeneously mixed. LSTPS particles (1801) are Al2O3 The surface is made significantly more neck-shaped than the particle (1802), or shares the surface, or has a surface Contact is observed. In this way, the LSTPS particle (1801) is Li + Ions conduct It is observed that a permeation network forms within the electrode formulation. 【0135】 As shown in Figure 19, the Al2O3 particles (1902) have a roughly particle size of approximately 0.75 to 4 μm, and LS The TPS particles (1901) had a roughly 250 nm particle size. As shown in Figure 20, Al2O3 The particles (2002) and LSTPS particles (2001) are homogeneously mixed. The LSTPS particles (2001) are mutual It is observed that it forms a neck-like structure, creating a permeable network. 【0136】 As shown in Figure 21, the Al2O3 particles (2102) have a roughly 250 nm particle size, and the LSTPS particles The particle (2101) had a roughly 250 nm particle size. As shown in Figure 22, Al2O3 particles. (2202) and LSTPS particles (2201) are homogeneously mixed. LSTPS particles (2201) are approximately 5-2 It is observed that the particles are neck-like only within a small region of 0 μm. 2202) and LSTPS particles (2201) allow for the formation of a penetration network to a similar extent as in Figure 18. do not. 【0137】 As shown in Figure 27, related experiments were conducted to investigate the relationship between the volume of catholite in the electrode. The change in conductivity was observed numerically. To achieve a high energy density in the electrochemical cell... Therefore, the majority of the positive electrode should be made of the active material, and a portion of the positive electrode should be made of the catholite material. It should be done (a small amount of catholite). Figure 27 shows that in catholite, which has a low volume ratio, The change in conductivity of an electrode with a particle size ratio of 1:1 to a small particle size is greater than the change in conductivity of an electrode with a large particle size. Show that the particle size ratio to particle size is at least two orders of magnitude smaller than the conductivity of electrodes with a particle size ratio of 5:1 or higher. Yes, they are. 【0138】 (Example 3: Increasing the amount of larger particle size filling) As described above, the small size of sulfide catholite particles is large particle size: small particle size Infiltration networks tend to form when the ratio is at least 4:1 or greater. In the example, the larger particles represent the cathode active material, thus representing the cathode active material in the electrode preparation. To maximize the amount of [the substance] and to ensure high ionic conductivity, a sufficient amount of catholite particles are used. It is desirable to maintain this. Figures 23 and 24 show the Al2O3:LSTPS with a particle size ratio of 20:1. This shows electrode formulations of Al2O3 particles (2302 and 2402) and LSTPS particles (2301 and 2401). As shown in Figures 23 and 24, Al2O3 particles (2302 and 2402) and LSTPS particles (2301 The LSTPS particles (2301 and 2401) are homogeneously mixed. The LSTPS particles (2301 and 2401) are neck-shaped relative to each other. It is observed that this is the case. In Figure 23, the volume ratio of Al2O3:LSTPS particles is 80:20. In Figure 24, the volume ratio of Al2O3:LSTPS particles was 44:54. The value of Al2O3:LSTPS particles A higher value suggests a greater likelihood of improved mixing engineering. 【0139】 (Example 4: Grinding of electrode particles) In the examples herein, Al2O3 and LSTPS are used to adjust the electrode having a specific Al2O3:LSTPS particle size ratio. The mixture is ground to various sizes to prepare the compound. In one example, the particles are as shown in Figure 25. It was pulverized as if it had been crushed. 【0140】 As shown in Figure 25, the Al2O3:LSTPS particles in this embodiment have the following size It was crushed in this way: [Table 1] 【0141】 (Example 5: Grinding of electrode particles) In the examples herein, nickel-cobalt aluminum oxide (NCA) and LSTPS are particularly The electrodes are ground to various sizes in order to prepare electrode formulations with a specific NCA:LSTPS particle size ratio. In one embodiment, the particles were ground as shown in Figure 26. 【0142】 As shown in Figure 26, the NCA:LSTPS particles in this embodiment have the following sizes: It was crushed in this way: [Table 2] 【0143】 The embodiments described above have been explained in some detail to clarify understanding, but certain changes It will be clear that the and modifications can be carried out within the scope of the attached claims. Please note that there are numerous alternative ways to implement the process, system, and equipment. Therefore, this embodiment should be considered illustrative rather than restrictive, and this embodiment is not limited to this. The details should not be limited to those shown in the specification. This application provides an invention having the following configuration: (Composition 1) It has a first particle size distribution characterized by a first dispersion degree of 0.25 or less and a first median diameter. A plurality of first particles of an electrochemically active material; and It has a second particle size distribution characterized by a second dispersion index of 0.25 or less and a second median diameter. an ion-conducting material wherein the second central diameter is at most one-third or less of the first central diameter. A solid electrode for an electrochemical device containing a second set of particles. (Configuration 2) The electrode according to configuration 1 contains a second particle with a volume fraction of less than 20% of the total particle volume of the electrode. very. (Composition 3) The electrode according to configuration 1, characterized by a porosity of less than 20 volume percent. (Composition 4) The ion-conducting material is Li a X b P c S d O e The formula includes, where X = Si, Ge, Al, Sn, and these The combination is such that 5≦a≦15, 0 <b≦3、1≦c≦4、6≦s≦18、及び0<e≦5である, the electrode described in configuration 1. (Composition 5) The aforementioned ion-conducting material is Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-Li3MO4, Li2S-SiS2- The formula includes elements selected from the group consisting of Li3MO3, Li2S-P2S5-LiI, and LATS, where M is Si The electrode according to configuration 1, wherein the element is selected from the group consisting of P, Ge, B, Al, Ga, and In. (Composition 6) The electrode according to configuration 1, wherein more than 80% of the electrode capacity can be charged within 2 hours. (Composition 7) The material further contains an electronically conductive additive, wherein the electronically conductive additive is acetylene black, carbon Black, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotubes, Ketchenb The electrode according to configuration 1, including a rack or a combination thereof. (Composition 8) The product further comprises a binder material, the binder material being selected from rubber or polymer. , the electrode described in configuration 1. (Composition 9) The penetration network further comprises the second plurality of particles, with a penetration rate of more than 80%. An electrode according to configuration 1 that contributes to the permeable network. (Composition 10) The total ionic conductivity of the electrode is higher than 1% of the conductivity of the bulk ion-conducting material. The electrode described in Part 1. (Composition 11) The penetration network further comprises the first plurality of particles, with a penetration rate of more than 80%. An electrode according to configuration 1 that contacts the permeable network. (Composition 12) The configuration according to configuration 1, wherein the second central diameter is at most one-quarter of the first central diameter. electrode. (Composition 13) The configuration according to configuration 1, wherein the second central diameter is at most one-fifth or less of the first central diameter. electrode. (Composition 14) The configuration according to configuration 1, wherein the second central diameter is at most one-tenth or less of the first central diameter. electrode. (Composition 15) The configuration according to configuration 1, wherein the second central diameter is at most 1 / 20th of the first central diameter. electrode. (Composition 16) An active material characterized by a first particle size distribution having a first median particle size; The invention includes a catholite material characterized by a second particle size distribution having a second median particle size, A solid-state electrochemical electrode; The volume ratio of the active material to the catholite material is 99:1 to 1:1; and The particle size ratio of the first median particle size to the second median particle size is at least 3:1. Solid-state electrochemical electrode. (Composition 17) The electrode according to configuration 16, wherein the first particle size distribution has a dispersion degree of 0.25 or less. (Composition 18) The electrode according to configuration 16 or 17, wherein the second particle size distribution has a dispersion degree of 0.25 or less. (Composition 19) The electrode according to configuration 16, having a porosity of less than 20 volume percent. (Composition 20) The material further contains an electronically conductive additive, wherein the electronically conductive additive is acetylene black, carbon Black, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotubes, Ketchenb The electrode according to configuration 16, including a rack or a combination thereof. (Composition 21) The product further comprises a binder material, the binder material being selected from rubber or polymer. , the electrode described in configuration 16. (Composition 22) The electrode according to configuration 16, wherein the catholite material forms a permeation network. (Composition 23) More than 80% of the catholite material in the electrode is bonded within the permeation network. The electrode described in configuration 22. (Composition 24) Anode current collector; The anode connected to the anode current collector; A solid electrolyte connected to the anode, wherein the anode is the anode current collector It is placed between the ion transfer device and the solid electrolyte, and the solid electrolyte has an ion transfer rate of at least 1e-4 S / cm. A solid electrolyte characterized by its conductivity; and A cathode connected to a solid electrolyte, comprising a mixed electrode material, wherein the mixed electrode material However, it includes a first plurality of particles and a second plurality of particles, wherein the first plurality of particles are less than 10 μm in size. Characterized by a first central diameter, the second plurality of particles have at least 5e-4S / cm of io Characterized by conductivity, the first central diameter is at least 3 times larger than the second central diameter. Twice as large, and the first plurality of particles and the second plurality of particles are dispersed by a degree of dispersion of less than 0.25 Characterized battery devices. (Composition 25) The mixed electrode material is compressed such that the porosity is less than 25% by volume of the cathode. The device described in configuration 24. (Composition 26) The mixed electrode material is characterized by its total volume, and the second plurality of particles are the total A device described in configuration 24 that accounts for less than 25% of the product. (Composition 27) The device according to configuration 24, wherein the first plurality of particles include a conversion chemical material. (Composition 28) The device according to configuration 24, wherein the second plurality of particles include a solid electrolyte material. (Composition 29) Anode current collector; The anode that is in direct contact with the anode current collector; The electrolyte in direct contact with the anode, wherein the anode is the anode current collector It is placed between the ion and the electrolyte, and the electrolyte has an ionic conductivity of at least 1e-4 S / cm. The electrolyte is characterized as such; and An electrochemical cell comprising a solid positive electrode in direct contact with the electrolyte, wherein the solid positive electrode is: An active material characterized by a first particle size distribution having a first median particle size; A catholite material characterized by a second particle size distribution having a second median particle size, comprising ; The volume ratio of the active material to the catholite material is 99:1 to 1:1; and The particle size ratio of the first median particle size to the second median particle size is at least 3:1. Electrochemical cell. (Composition 30) The cell according to configuration 29, wherein the first particle size distribution has a dispersion degree of 0.25 or less. (Composition 31) The cell according to configuration 29 or 30, wherein the second particle size distribution has a dispersion degree of 0.25 or less. (Composition 32) The cell according to configuration 29, wherein the positive electrode has a porosity of less than 20 volume percent. (Composition 33) The cell according to configuration 29, wherein the catholite material forms a permeation network. (Composition 34) More than 80% of the catholite material in the positive electrode is bonded within the permeation network. Cells listed in configuration 33. (Composition 35) A method for forming an electrode material: A step of preparing a first plurality of particles and a second plurality of particles, wherein the first plurality of particles , characterized by a first central diameter of less than 10 μm, the second plurality of particles are at least Characterized by an ionic conductivity of 5e-4 S / cm, the first central diameter is greater than the second central diameter. The first plurality of particles and the second plurality of particles are at least three times larger, and the first plurality of particles and the second plurality of particles are less than 0.25 The process, characterized by its degree of dispersion; A step of mixing the first plurality of particles and the second plurality of particles to form a mixed material; A step of depositing the mixed material inside the electrode; and The method comprising the step of compressing the electrode. (Composition 36) The method according to configuration 35, further comprising the step of drying the mixed material. (Composition 37) The method according to configuration 35, further comprising the step of depositing the mixed material onto a substrate. (Composition 38) The method according to configuration 35, wherein the mixing step is performed before the depositing step. (Composition 39) The method according to configuration 35, further comprising the step of firing the mixed material. (Composition 40) It has a first median diameter characterized by a first dispersion degree of 0.5 or less and a first median particle size. a first plurality of electrochemically active material particles; It has a second particle size distribution characterized by a second dispersion degree of 0.5 or less and a second median diameter. an ion-conducting material wherein the second central diameter is at most one-third or less of the first central diameter. A solid electrode for an electrochemical device comprising a second plurality of particles; The solid contains the second particles in a volume fraction of less than 20% of the total particle volume of the electrode. electrode. (Composition 41) An active material characterized by a first particle size distribution having a first median particle size; The invention includes a catholite material characterized by a second particle size distribution having a second median particle size, A solid electrode for an electrochemical device; The volume ratio of the active material to the catholite material is 99:1 to 1:1; and The particle size ratio of the first median particle size to the second median particle size is at least 3:1. , the solid electrode.

Claims

[Claim 1] A first plurality of electrochemically active particles having a first particle size distribution characterized by a first dispersion degree of 0.5 or less and a first median diameter; and A second plurality of ion-conducting particles having a second particle size distribution characterized by a second dispersion degree of 0.5 or less and a second central diameter, wherein the second central diameter is at most one-third or less of the first central diameter. A solid electrode for an electrochemical device, including, The solid electrode includes a permeation network of the ion-conducting material, The electrode contains a volume ratio of the first plurality of particles exceeding 50% of the total particle volume of the electrode, The median diameter is the volume-averaged median particle size measured by SEM; The electrode is characterized by a porosity of less than 10 volume percent as measured by SEM; and The solid electrode wherein the ion-conducting material contains a sulfide-based electrolyte. [Claim 2] The electrode according to claim 1, wherein the first plurality of particles having the first particle size distribution are characterized by a first dispersion degree of 0.25 or less. [Claim 3] The electrode according to claim 1, wherein the second plurality of particles having the second particle size distribution are characterized by a second dispersion degree of 0.25 or less. [Claim 4] The electrode according to claim 1, wherein the electrode contains a volume ratio of a second particle of less than 20% of the total particle volume of the electrode. [Claim 5] The ion-conducting material is Li a X b P c S d O e The electrode according to claim 1, comprising (wherein X is Si, Ge, Al, Sn, or a combination thereof, and 5 ≤ a ≤ 15, 0 < b ≤ 3, 1 ≤ c ≤ 4, 6 ≤ d ≤ 18, and 0 < e ≤ 5). [Claim 6] where the ion conductive material is Li 2 S - SiS 2 , Li 2 S - SiS 2 -LiI, Li 2 S - SiS 2 -Li 3 MO 4 , Li 2 S - SiS 2 -Li 3 MO 3 , Li 2 S - P 2 S 5 -LiI, and an element selected from the group consisting of LATS, wherein M is an element selected from the group consisting of Si, P, Ge, B, Al, Ga, and In. The electrode according to claim 1. [Claim 7] The present invention further comprises an electronically conductive additive, wherein the electronically conductive additive includes acetylene black, carbon black, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotubes, Ketjenblack, or a combination thereof, and / or The electrode according to claim 1, further comprising a binder material, wherein the binder material is a polymer. [Claim 8] The electrode according to claim 1, wherein the second central diameter is at most one-quarter of the first central diameter. [Claim 9] A solid-state battery comprising a solid electrode, a solid electrolyte, and a lithium metal anode as described in claim 1. [Claim 10] An active material characterized by a first particle size distribution having a first median particle size; A solid electrochemical electrode comprising a catholite material characterized by a second particle size distribution having a second median particle size, The catholite material includes a permeation network of ion-conducting materials, The electrode contains more than 50% of the volume of the active material relative to the total particle volume of the electrode, The volume ratio of the active material to the catholite material is 99:1 to 1:1; The particle size ratio of the first median particle size to the second median particle size is at least 3:1; The median diameter is the volume-averaged median particle size measured by SEM; The electrode was characterized by a porosity of less than 10 volume percent as measured by SEM; The catholite material contains a sulfide-based electrolyte, The first particle size distribution has a dispersion degree of 0.5 or less, and / or The solid electrochemical electrode wherein the second particle size distribution has a dispersion degree of 0.5 or less. [Claim 11] The present invention further comprises an electronically conductive additive, wherein the electronically conductive additive includes acetylene black, carbon black, activated carbon, C65, C45, VGCF, carbon fiber, carbon nanotubes, Ketjenblack, or a combination thereof, and / or The electrode according to claim 10, further comprising a binder material, wherein the binder material is a polymer. [Claim 12] Anode current collector; The anode in direct contact with the anode current collector; The electrolyte in direct contact with the anode, wherein the anode is positioned between the anode current collector and the electrolyte, and the electrolyte is characterized by an ionic conductivity of at least 1e-4 S / cm; and The solid positive electrode in direct contact with the electrolyte is the solid electrochemical electrode described in claim 10. An electrochemical cell, including one. [Claim 13] The first particle size distribution of the solid cathode has a dispersion degree of 0.25 or less; and / or The cell according to claim 12, wherein the second particle size distribution of the solid cathode has a dispersion degree of 0.25 or less.

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