Electrode, electrode element, non-aqueous electrolyte storage element

Abstract

To provide an inorganic particle layer in which binding force between inorganic particles can be secured and characteristic of a nonaqueous electrolyte storage element in the case where the inorganic particle layer is used as an electrode of the nonaqueous electrolyte storage element can be improved.SOLUTION: An inorganic particle layer is provided, for use in an electrode of a non-aqueous electrolyte power storage element, and the inorganic particle layer comprises: an insulating inorganic particle 61 having a surface potential; a high polymer molecule 62 having an ion functional group (A) that is charged inversely to surface potential of the inorganic particle and an ion conductive functional group (B); and a binder. The binder of 0.5 mass% or more and 5 mass% or less is contained with respect to the inorganic particle. The high polymer molecule of 40 mass% or more and 100 mass% or less is contained with respect to the binder. The inorganic particle and the high polymer molecule are bonded to each other, the inorganic particle is an alumina particle, and the ion functional group (A) is an anionic functional group.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to an electrode, an electrode element, and a non-aqueous electrolyte storage element. [Background technology]

[0002] In recent years, the energy density of energy storage devices such as batteries and power generation devices such as fuel cells has rapidly increased. However, batteries with high energy density can go into abnormal states such as explosion or fire if foreign matter is mixed in or if they are subjected to external impact, so ensuring the safety of batteries has become an issue.

[0003] The causes of explosion and fire include Joule heat generated by an internal or external short circuit, which causes continuous abnormal reactions in the battery materials, resulting in fire and thermal runaway.

[0004] One example of a technology for suppressing Joule heat generated by an internal short circuit or an external short circuit is a sheet-type electrode for a secondary battery that includes an inorganic particle layer containing inorganic particles and a binder polymer formed on an electrode mixture layer (see, for example, Patent Document 1). Summary of the Invention [Problem to be solved by the invention]

[0005] However, because the inorganic particle layer in the above electrode had to be isolated into a sheet, it was necessary to include about 10% by mass of a binder in the inorganic particle layer. However, when a typical binder was used, although the binding force between the inorganic particles could be ensured, the binder penetrated into the electrode mixture layer and coated the active material, hindering the ionic conductivity of the inorganic particle layer and resulting in a decrease in battery characteristics (input / output characteristics).

[0006] The present invention has been made in view of the above, and aims to provide an inorganic particle layer that can ensure the binding force between inorganic particles and, when used in an electrode of a nonaqueous electrolyte storage element, can improve the characteristics of the nonaqueous electrolyte storage element. [Means for solving the problem]

[0007] The present inorganic particle layer is an inorganic particle layer used in an electrode of a nonaqueous electrolyte storage element, and comprises insulating inorganic particles having a surface potential, a polymer having an ionic functional group (A) and an ion-conductive functional group (B) that are charged oppositely to the surface potential of the inorganic particles, and a binder, wherein the binder accounts for 0.5% by mass or more and 5% by mass or less of the inorganic particles, the polymer accounts for 40% by mass or more and 100% by mass or less of the binder, the inorganic particles and the polymer are bonded to each other, the inorganic particles are alumina particles, and the ionic functional group (A) is an anionic functional group. [Effects of the Invention]

[0008] The disclosed technology can provide an inorganic particle layer that can ensure the binding force between inorganic particles and, when used in an electrode of a nonaqueous electrolyte storage element, can improve the characteristics of the nonaqueous electrolyte storage element. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 2 is a diagram illustrating an example of a negative electrode used in the nonaqueous electrolyte storage element according to the first embodiment. [Figure 2] FIG. 2 is a diagram illustrating a positive electrode used in the nonaqueous electrolyte storage element according to the first embodiment. [Figure 3] 1 is a cross-sectional view illustrating an example of an electrode element used in the nonaqueous electrolyte storage element according to the first embodiment. [Figure 4] 1 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to a first embodiment. [Figure 5] FIG. 2 is a diagram illustrating a core-shell structure of inorganic particles and a polymer according to the first embodiment. [Figure 6] FIG. 2 is a diagram illustrating the zeta potential measurement results of the core-shell structure according to the first embodiment. [Figure 7] FIG. 2 is a diagram illustrating a viscosity measurement result of the core-shell structure according to the first embodiment. [Figure 8] FIG. 4 is a diagram illustrating an example of a negative electrode used in a nonaqueous electrolyte storage element according to a second embodiment. [Figure 9] FIG. 4 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to a second embodiment. [Figure 10] FIG. 10 is a diagram illustrating an example of a negative electrode used in a nonaqueous electrolyte storage element according to a third embodiment. [Figure 11] FIG. 10 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to a third embodiment. [Figure 12] FIG. 10 is a diagram illustrating an example of a negative electrode used in a nonaqueous electrolyte storage element according to a fourth embodiment. [Figure 13] FIG. 10 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to a fourth embodiment. [Figure 14] FIG. 13 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to a first modified example of the fourth embodiment. [Figure 15] FIG. 1 is a diagram showing the results of Examples 1 to 6. [Figure 16] FIG. 1 is a diagram showing the results of Example 1 and Comparative Example 1. [Figure 17] FIG. 1 is a diagram showing the results of Example 3 and Comparative Example 2. [Figure 18] FIG. 1 is a diagram showing the results of Example 6 and Comparative Example 3. [Figure 19] FIG. 1 shows the results of Examples 7 to 10. [Figure 20] FIG. 1 is a diagram showing the results of Example 1, Comparative Example 1, and Comparative Examples 4 to 6. [Figure 21] FIG. 1 shows the results of Example 1 and Examples 11 to 14. [Figure 22] FIG. 1 shows the results of Example 1 and Examples 15 to 21. DETAILED DESCRIPTION OF THE INVENTION

[0010] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following describes the preferred embodiments of the present invention with reference to the accompanying drawings. In the drawings, the same components are designated by the same reference numerals, and redundant explanations may be omitted.

[0011] First Embodiment 1A and 1B are diagrams illustrating a negative electrode used in a nonaqueous electrolyte storage element according to a first embodiment, where FIG. 1A is a plan view and FIG. 1B is a cross-sectional view taken along line AA in FIG. 1A.

[0012] 1, negative electrode 10 has a structure including a negative electrode substrate 11, a negative electrode composite layer 12 formed on negative electrode substrate 11, and an inorganic particle layer 13 formed on negative electrode composite layer 12. The shape of negative electrode 10 is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a flat plate shape.

[0013] 2A and 2B are diagrams illustrating a positive electrode used in the nonaqueous electrolyte storage element according to the first embodiment, with Fig. 2A being a plan view and Fig. 2B being a cross-sectional view taken along line BB in Fig. 2A. Referring to Fig. 2, the positive electrode 20 has a structure including a positive electrode substrate 21 and a positive electrode composite layer 22 formed on the positive electrode substrate 21. The shape of the positive electrode 20 is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a flat plate shape.

[0014] Fig. 3 is a cross-sectional view illustrating an electrode element used in the nonaqueous electrolyte storage element according to the first embodiment. Referring to Fig. 3, the electrode element 40 has a structure in which a negative electrode 17 and a positive electrode 27 are stacked in a state insulated from each other with a separator 30 interposed therebetween. In the electrode element 40, the positive electrodes 27 are stacked on both sides of the negative electrode 17. A negative electrode lead wire 41 is connected to the negative electrode substrate 11. A positive electrode lead wire 42 is connected to the positive electrode substrate 21.

[0015] Negative electrode 17 differs from negative electrode 10 (see FIG. 1) in that a negative electrode composite layer 12 and an inorganic particle layer 13 are formed on both sides of a negative electrode electrode substrate 11, but is otherwise similar to negative electrode 10. Positive electrode 27 differs from positive electrode 20 (see FIG. 2) in that a positive electrode composite layer 22 is formed on both sides of a positive electrode electrode substrate 21, but is otherwise similar to positive electrode 20.

[0016] In the electrode element 40, the number of layers of negative electrodes 17 and positive electrodes 27 can be determined arbitrarily. That is, although Fig. 3 illustrates a total of three layers, one negative electrode 17 and two positive electrodes 27, the present invention is not limited to this, and more negative electrodes 17 and positive electrodes 27 can be stacked. In this case, the number of negative electrodes 17 and the number of positive electrodes 27 may be the same.

[0017] Fig. 4 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to the first embodiment. Referring to Fig. 4, the nonaqueous electrolyte storage element 1 has a structure in which a nonaqueous electrolyte is injected into an electrode element 40 to form an electrolyte layer 51, and the nonaqueous electrolyte storage element 1 is sealed with an exterior casing 52. In the nonaqueous electrolyte storage element 1, a negative electrode lead wire 41 and a positive electrode lead wire 42 are led out of the exterior casing 52. The nonaqueous electrolyte storage element 1 may include other members as necessary. The nonaqueous electrolyte storage element 1 is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a nonaqueous electrolyte secondary battery and a nonaqueous electrolyte capacitor.

[0018] The shape of the nonaqueous electrolyte storage element 1 is not particularly limited and can be appropriately selected from various commonly used shapes depending on the intended use, such as a laminate type, a cylindrical type in which a sheet electrode and a separator are spirally wound, a cylindrical type with an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are stacked.

[0019] The following provides a detailed description of the nonaqueous electrolyte storage element 1. Note that the negative electrode and positive electrode may be collectively referred to as electrodes, the negative electrode electrode substrate and positive electrode substrate may be collectively referred to as electrode substrates, and the negative electrode mixture layer and positive electrode mixture layer may be collectively referred to as electrode mixture layers. <Electrode> <<Electrode base>> The material of the negative electrode substrate 11 is not particularly limited as long as it is made of a conductive material and can be appropriately selected depending on the purpose, and examples thereof include stainless steel, nickel, aluminum, copper, etc. Among these, stainless steel and copper are particularly preferred.

[0020] The shape of the negative electrode substrate 11 is not particularly limited and can be selected appropriately depending on the purpose. The size of the negative electrode substrate 11 is not particularly limited as long as it is a size that can be used in the nonaqueous electrolyte storage element 1 and can be selected appropriately depending on the purpose.

[0021] The material of the positive electrode substrate 21 is not particularly limited as long as it is made of a conductive material and can be appropriately selected depending on the purpose, and examples thereof include stainless steel, nickel, aluminum, copper, titanium, tantalum, etc. Among these, stainless steel and aluminum are particularly preferred.

[0022] The shape of the positive electrode substrate 21 is not particularly limited and can be selected appropriately depending on the purpose. The size of the positive electrode substrate 21 is not particularly limited as long as it is a size that can be used in the nonaqueous electrolyte storage element 1 and can be selected appropriately depending on the purpose. <<Electrode composite layer>> The negative electrode composite layer 12 and the positive electrode composite layer 22 are not particularly limited and can be appropriately selected depending on the purpose. For example, they contain at least an active material (negative electrode active material or positive electrode active material), and may contain a binder (binding agent), a thickener, a conductive agent, etc. as necessary.

[0023] The negative electrode mixture layer 12 can be formed, for example, by preparing a slurry-like negative electrode material composition by adding a binder, a thickener, a conductive agent, a solvent, and the like to a negative electrode active material as needed, and then applying the prepared negative electrode material composition onto the negative electrode substrate 11 and drying it. The positive electrode mixture layer 22 can be formed in the same manner.

[0024] The average thickness of negative electrode mixture layer 12 is not particularly limited and can be appropriately selected depending on the purpose, but the average thickness of negative electrode mixture layer 12 is preferably 10 μm or more and 450 μm or less, and more preferably 20 μm or more and 100 μm or less. If the average thickness of negative electrode mixture layer 12 is less than 10 μm, the energy density may decrease, and if it exceeds 450 μm, the cycle characteristics may deteriorate.

[0025] The negative electrode active material contained in the negative electrode mixture layer 12 is not particularly limited as long as it is a material that can reversibly absorb and release alkali metal ions such as lithium ions. For example, a carbonaceous material can be used as the negative electrode active material contained in the negative electrode mixture layer 12. Examples of carbonaceous materials include graphite such as coke, artificial graphite, and natural graphite, pyrolysis products of organic materials under various pyrolysis conditions, and amorphous carbon. Among these, artificial graphite, natural graphite, and amorphous carbon are particularly preferred.

[0026] The average thickness of positive electrode mixture layer 22 is not particularly limited and can be appropriately selected depending on the purpose, but the average thickness of positive electrode mixture layer 22 is preferably 10 μm or more and 300 μm or less, and more preferably 40 μm or more and 150 μm or less. If the average thickness of positive electrode mixture layer 22 is less than 10 μm, the energy density may decrease, and if it exceeds 300 μm, the load characteristics may deteriorate.

[0027] The positive electrode active material contained in positive electrode mixture layer 22 is not particularly limited as long as it is a material that can reversibly absorb and release alkali metal ions such as lithium ions. For example, an alkali metal-containing transition metal compound can be used as the positive electrode active material contained in positive electrode mixture layer 22.

[0028] Examples of alkali metal-containing transition metal compounds include LiNi X Co Y Mn Z Lithium Ni composite oxide, LiO2(x+y+z=1) X Me Y (PO4) Z A lithium phosphate material having a basic skeleton of (0.5≦x≦4, Me=transition metal, 0.5≦y≦2.5, 0.5≦x≦3.5) can be used.

[0029] LiNi X Co Y Mn Z Examples of lithium Ni composite oxides where O2(x+y+z=1) include LiNi 0.33 Co0.33 Mn 0.33 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.2 Examples include Mn0O2.

[0030] Li X Me Y (PO4) Z Examples of lithium phosphate materials with a basic skeleton of (0.5≦x≦4, Me=transition metal, 0.5≦y≦2.5, 0.5≦x≦3.5) include lithium vanadium phosphate (Li3V2(PO4)3), iron olivine (LiFePO4), manganese olivine (LiMnPO4), cobalt olivine (LiCoPO4), nickel olivine (LiNiPO4), vanadium olivine (LiVOPO4), and similar compounds with these basic skeletons doped with different elements.

[0031] Examples of binders (binding agents) that can be used for the negative electrode or positive electrode include polyvinylidene fluoride (PVDF), PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polyhexyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber (SBR), and carboxymethyl cellulose.

[0032] Alternatively, a copolymer of two or more materials selected from tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene may be used, or a mixture of two or more materials selected from these may be used.

[0033] Examples of the conductive agent contained in the electrode mixture layer include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, conductive fibers such as carbon fiber and metal fiber, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene derivatives and graphene derivatives.

[0034] The active material used in fuel cells is typically a catalyst for the cathode or anode electrode, which is a metal particle such as platinum, ruthenium, or a platinum alloy supported on a catalyst support such as carbon. To support the catalyst particles on the surface of a catalyst support, for example, the catalyst support is suspended in water, and a catalyst particle precursor (e.g., chloroplatinic acid, dinitrodiaminoplatinum, platinic chloride, platinous chloride, bisacetylacetonatoplatinum, dichlorodiammineplatinum, dichlorotetramineplatinum, platinic sulfate chlororuthenic acid, chloroiridic acid, chlororhodium acid, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, iron sulfate, copper chloride, or other alloy components) is added and dissolved in the suspension. An alkali is then added to generate metal hydroxides, resulting in a catalyst support supported on the catalyst support surface. The catalyst support is then applied to an electrode substrate and reduced under a hydrogen atmosphere, yielding an electrode composite layer with catalyst particles (active material) coated on its surface.

[0035] In the case of solar cells and the like, examples of active materials include tungsten oxide powder, titanium oxide powder, and oxide semiconductor layers such as SnO2, ZnO, ZrO2, Nb2O5, CeO2, SiO2, and Al2O3. The semiconductor layers are loaded with dyes, such as ruthenium tris-type transition metal complexes, ruthenium bis-type transition metal complexes, osmium tris-type transition metal complexes, osmium bis-type transition metal complexes, ruthenium cis-diaqua-bipyridyl complexes, phthalocyanines and porphyrins, and organic-inorganic perovskite crystals.

[0036] In the following description, the case where the alkali metal ions are lithium ions will be described as an example. <<Inorganic particle layer>> The inorganic particle layer 13 has a core-shell structure 60 shown in FIG. 5 . The core-shell structure 60 includes insulating inorganic particles 61 having a surface potential and polymers 62 bonded to the inorganic particles 61. The polymers 62 have ionic functional groups that are charged oppositely to the surface potential of the inorganic particles 61 and ion-conductive functional groups that are charged oppositely to the surface potential of the inorganic particles 61. The polymers 62, which are charged oppositely to the surface potential of the inorganic particles 61, bond to the inorganic particles 61 through ionic interaction to form the core-shell structure 60. The core-shell structure 60 has the inorganic particles 61 as the core and the polymers 62 as the shell. Note that in this specification, the core-shell structure 60 may also be referred to as core-shell particles, but the two terms are synonymous.

[0037] Here, the surface potential of the inorganic particles 61 refers to the potential of the surface of the inorganic particles 61 in the solution, and in this specification is synonymous with the potential (zeta potential) of the "slip surface" where liquid flow begins in the electric double layer formed around the inorganic particles 61 in the solution. The surface potential of the inorganic particles 61 is sufficient if it can form the core-shell structure 60 through ionic interaction with the polymer 62.

[0038] In the core-shell structure 60, if the shell film thickness is too thin, sufficient peel strength cannot be obtained. In addition, in the core-shell structure 60, if the shell film thickness is too thick, the spaces between the inorganic particles 61 are filled with the polymer 62, which may hinder the penetration of the electrolyte solution and inhibit ion permeability. Therefore, although there is no limitation on the shell film thickness in the core-shell structure 60, it is preferable to select an appropriate shell film thickness that can obtain sufficient peel strength and does not hinder the penetration of the electrolyte solution.

[0039] Although the shell film thickness can be observed using a transmission electron microscope (TEM), a scanning electron microscope (SEM), or a scanning transmission electron microscope (STEM), the preferred shell film thickness in the core-shell structure 60 is often below the observation limit value. Therefore, it is difficult to strictly define the shell film thickness as a film thickness.

[0040] Therefore, in this specification, the one-layer adsorption amount is defined as follows. First, core-shell particles are prepared with varying ratios of insulating inorganic particles 61 and polymer 62 (polymer), and the zeta potential or viscosity of these core-shell particles is measured. This results in a graph such as that shown in Figure 6 for zeta potential measurements, or in Figure 7 for viscosity measurements. The one-layer adsorption amount is the amount of polymer at the maximum value B of opposite charge to the inorganic particles 61 in Figure 6, or at the minimum value B of viscosity in Figure 7.

[0041] In the core-shell structure 60, the upper limit of the amount of polymer 62 adsorbed on the surface of the inorganic particle 61 is not particularly limited, but is preferably equal to or less than the amount of polymer adsorbed for one layer. That is, in the core-shell structure 60, the upper limit of the amount of polymer 62 adsorbed on the surface of the inorganic particle 61 is not particularly limited, but is preferably equal to or less than the amount of polymer at the maximum value B of opposite charge to that of the inorganic particle 61 in Fig. 6 or the minimum value B of viscosity in Fig. 7.

[0042] The amount of polymer at point A where the zeta potential is 0 mV in Fig. 6 or at maximum viscosity value A in Fig. 7 may result in insufficient surface coverage of inorganic particles 61. Therefore, in the core-shell structure 60, the lower limit of the amount of polymer 62 adsorbed on the surface of inorganic particles 61 (polymer amount) is not particularly limited, but is preferably equal to or greater than the amount of polymer at point A where the zeta potential is 0 mV in Fig. 6 or maximum viscosity value A in Fig. 7.

[0043] That is, in the core-shell structure 60, there are no particular upper or lower limits for the amount of polymer 62 adsorbed on the surface of inorganic particle 61. However, it is preferable that the amount of polymer 62 adsorbed is equal to or greater than the amount of polymer at point A where the zeta potential is 0 mV in Fig. 6 or the amount of polymer at maximum viscosity A in Fig. 7, and equal to or less than the amount of polymer at maximum viscosity B where the charge is opposite to that of inorganic particle 61 in Fig. 6 or the amount of polymer at minimum viscosity B in Fig. 7. This allows the core-shell structure 60 to obtain sufficient peel strength, and sufficient ion permeability without impeding the penetration of the electrolyte.

[0044] Examples of the inorganic particles 61 contained in the inorganic particle layer 13 include metal oxides, metal nitrides, and other metal fine particles. Preferred metal oxides include Al2O3 (alumina), TiO2, BaTiO3, and ZrO2.

[0045] Preferred metal nitrides include aluminum nitride, silicon nitride, etc. Preferred other metal fine particles include poorly soluble ionic crystal fine particles such as aluminum fluoride, calcium fluoride, barium fluoride, and barium sulfate, as well as substances derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, and bentonite, or artificial products thereof.

[0046] Glass ceramic powder can also be used as the inorganic particles 61. The glass ceramic powder is preferably a crystallized glass ceramic using ZnO-MgO-Al2O3-SiO2-based crystallized glass, or a non-glass ceramic using BaO-Al2O3-SiO2-based ceramic powder or Al2O3-CaO-SiO2-MgO-B2O3-based ceramic powder.

[0047] It is more preferable to use an ion-conductive element as the inorganic particles 61. Specifically, the inorganic particles 61 can be made of a material containing at least one element selected from the group consisting of silicon, aluminum, and zirconium, which have ion conductivity.

[0048] It is more preferable to use Al2O3 (alumina) as the inorganic particles 61. If the inorganic particles 61 contained in the inorganic particle layer 13 are alumina particles, the inorganic particle layer 13 can be formed inexpensively with high insulation and heat resistance.

[0049] Use of these inorganic particles 61 can suppress internal short circuits in the nonaqueous electrolyte storage element 1 and improve the safety of the nonaqueous electrolyte storage element 1. In addition, ion conduction occurs on the surface of the inorganic particles 61, which can improve the ion conductivity in the inorganic particle layer 13. This can improve the input / output characteristics of the nonaqueous electrolyte storage element 1.

[0050] The average particle diameter of the inorganic particles 61 contained in the inorganic particle layer 13 is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 3 μm or less. When the average particle diameter of the inorganic particles 61 is 0.1 μm or more and 5 μm or less, the average particle diameter of the inorganic particles 61 is sufficiently small, so that the surface area of ​​the inorganic particles 61 is increased and the lithium ion conductivity effect can be obtained even when the amount of inorganic particles 61 used is small. The average particle diameter of the inorganic particles 61 can be measured by laser diffraction.

[0051] The ionic functional groups and ion-conductive functional groups of the polymer 62 contained in the inorganic particle layer 13 are as follows. -Ionic functional group- In this specification, the ionic functional group means sulfonic acid, sodium sulfonate, potassium sulfonate, lithium sulfonate, ammonium sulfonate, ammonium carboxylate, carboxylic acid, potassium carboxylate, sodium carboxylate, lithium carboxylate, ammonium carboxylate, boronic acid, sodium boronate, potassium boronate, lithium boronate, ammonium boronate, primary, secondary, tertiary amine, and salts thereof.

[0052] Specific repeating units include acrylic acid and salts thereof, methacrylic acid and salts thereof, maleic acid and salts thereof, vinyl sulfonic acid and salts thereof, vinyl phosphonic acid and salts thereof, methyl acrylate having sulfonic acid and salts thereof at the alkyl terminal, methyl acrylate having primary, secondary, or tertiary amine and salts thereof (halogen ions) at the alkyl terminal, aspartic acid, ammonium aspartate, sodium aspartate, lithium aspartate, and potassium aspartate, but the ionic functional group in this specification is not limited to these compounds.

[0053] The ionic functional group may be either an anionic functional group or a cationic functional group. However, when alumina is selected as the inorganic particles 61 in the inorganic particle layer 13, the ionic functional group of the polymer 62 is preferably an anionic functional group because alumina is cationic over a wide pH range.

[0054] In this specification, the anionic functional group refers to a sulfonic acid group, a carboxylic acid group, a phosphate group, or an acid salt via a counter ion. Furthermore, the counter ion is preferably a lithium cation or an ammonium cation, taking into consideration safety when used as an energy storage element. The anionic functional group may have one or more of a sulfonic acid group, a carboxylic acid group, and a phosphate group.

[0055] The ionic functional group in this specification can be located either on a side chain or at both ends of the polymer. However, when the inorganic particle layer 13 is formed by a coating method, it is preferable that multiple ionic functional groups are present on the side chain, taking into consideration the dispersibility of the core-shell particles. -Ion-conductive functional group- In this specification, the ion-conductive functional group specifically refers to a non-ionic functional group having a structure with an inorganicity of 20 or more on the organic-inorganic conceptual diagram. Specific examples include ether groups, oxyalkylene groups, azo groups, nitro groups, imino groups, primary, secondary, and tertiary amino groups, hydroxyl groups, carboxylic anhydride groups, and amide groups.

[0056] It is preferable that the inorganic particle layer 13 has good lithium ion conductivity. From this viewpoint, it is preferable that the ion-conductive functional group is an oxyalkylene group, the alkylene group has 4 or less carbon atoms, and further, is a polyoxyalkylene chain having 3 or more repeating units. Specific examples of the polyoxyalkylene chain are shown in formulas (1) to (5), but the polyoxyalkylene chain in the inorganic particle layer 13 is not limited to these structures.

[0057] [ka] In formulas (1) to (5), A4 represents -OR or -CH2-OR. A5, A6, and A7 represent -OR or -NH-R. R represents a linear or branched hydrocarbon chain or oligoether chain having 1 to 24 carbon atoms. A8 represents a linear or branched hydrocarbon chain or oligoether chain having 1 to 24 carbon atoms.

[0058] The oligoether chain in this specification is a molecule formed by polymerization of ethylene glycol or propylene glycol, and if the molecular weight is too small, dispersibility tends to deteriorate, while if the molecular weight is too large, viscosity tends to increase. Therefore, the molecular weight is preferably 100 to 10,000, and more preferably 100 to 5,000.

[0059] The terminal of the oligoether chain may be a hydroxyl group, or a methyl group, ethyl group, propyl group, etc., as needed. Specific examples of repeating structural units having an oligoether chain are shown below, but the oligoether chain in this specification is not limited to the examples shown below. Furthermore, n, which indicates the degree of polymerization of the oligoether chain in the diagram, can be varied depending on the purpose. Furthermore, by using an oligoether chain, high dispersibility can be maintained even in highly polar solvents. Specific examples of highly polar solvents include methanol, ethanol, propanol, butanol, pentanol, NMP, DMSO, DMF, acetone, and THF.

[0060] Specific examples of repeating structural units having an oligoether chain are shown in formulas (6) to (45), but are not limited to these. In formulas (6) to (45), n represents an integer of 2 or more.

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka] In this specification, the term "polymer" refers to a molecule that not only has the above-mentioned functional group but also has a number-average molecular weight of 500 to 100,000. In order to suppress an increase in the viscosity of the dispersion, the number-average molecular weight is preferably 1,000 to 10,000, and more preferably 1,000 to 5,000. The polymer contained in the inorganic particle layer 13 may have any structure, such as random copolymerization, block polymerization, graft polymer, or dendrimer, but graft polymer is preferred in terms of film-forming properties.

[0066] The inorganic particle layer 13 can be formed by applying ink containing inorganic particles 61 and polymers 62 onto the underlying negative electrode mixture layer 12 by inkjet or other methods and then drying the applied ink. For example, the inorganic particles and polymers are dispersed in a solvent to form an ink. The solvent is selected to be suitable for the inorganic particles to be dispersed. Specifically, water, hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, and ether solvents can be used. When preparing this ink, a homogenizer may be used for dispersion. Examples of homogenizers that can be used include high-speed rotation shear stirring, high-pressure injection dispersion, ultrasonic dispersion, and media stirring mill.

[0067] When preparing the ink, additives such as dispersants and surfactants may be used as needed. Examples of dispersants and surfactants that can be used include Megafac (manufactured by DIC Corporation), Marialim (manufactured by NOF Corporation), Esleem (manufactured by NOF Corporation), Solsperse (manufactured by Lubrizol), and Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.). Other additives that can be used include thickeners such as propylene glycol and carboxymethyl cellulose to adjust viscosity.

[0068] When dispersing inorganic particles in a solvent, a resin may be added. Examples of resins that can be used include acrylic resin, SBR (styrene butadiene rubber) resin, PVdF (polyvinylidene fluoride), and PVP (polyvinylpyrrolidone). A small amount of these resins can be added to firmly bind the inorganic particles together.

[0069] The resin is preferably contained in an amount of 0.5% by mass to 5% by mass relative to the inorganic particles. Furthermore, the polymer is preferably contained in an amount of 40% by mass to 100% by mass relative to the resin. This ensures the adhesive strength between the inorganic particles 61, and improves the input / output characteristics of the nonaqueous electrolyte storage element 1 when the inorganic particle layer 13 is used in an electrode of the nonaqueous electrolyte storage element 1.

[0070] By forming a core-shell structure 60 with inorganic particles 61 having a surface potential and polymers 62, when the ink is prepared, the polymers 62 do not disperse alone in the solution but remain bonded to the inorganic particles 61. This prevents the polymers 62 from penetrating into the negative electrode mixture layer 12 when the inorganic particle layer 13 is formed on the negative electrode mixture layer 12, and does not inhibit ion conduction in the negative electrode mixture layer 12. This prevents a decrease in the input / output characteristics of the nonaqueous electrolyte storage element 1.

[0071] Furthermore, by forming a core-shell structure 60 with the inorganic particles 61 and the polymer 62, the polymer 62 does not completely cover the surfaces of the inorganic particles 61, making it possible to keep the sheet resistance of the inorganic particle layer 13 low. This prevents ion conduction on the surfaces of the inorganic particles 61 from being inhibited, and can prevent a decrease in the input / output characteristics of the nonaqueous electrolyte storage element 1. From the viewpoint of preventing ion conduction from being inhibited and preventing a decrease in the input / output characteristics of the nonaqueous electrolyte storage element 1, the sheet resistance of the inorganic particle layer 13 is set to 0.01 Ω cm. 2 1.0Ω cm or more 2 It is preferable that:

[0072] The polymer 62 having an ion-conductive functional group improves the ion conductivity of the surfaces of the inorganic particles 61 in the inorganic particle layer 13, thereby improving the ion conductivity of the inorganic particle layer 13. This improves the input / output characteristics of the nonaqueous electrolyte storage element 1.

[0073] Furthermore, in the formation of the inorganic particle layer 13, the main chain and side chain of the polymer 62 become entangled, which has the effect of binding together the inorganic particles 61 having the core-shell structure 60. This ensures the bonding strength between the inorganic particles 61, improving the physical strength of the inorganic particle layer 13. Furthermore, shrinkage and breakage of the inorganic particle layer 13 are suppressed, improving the safety of the nonaqueous electrolyte storage element 1.

[0074] The thickness of the inorganic particle layer 13 is preferably 1 μm or more and 30 μm or less, and more preferably 2 μm or more and 20 μm or less. A thick inorganic particle layer 13 enhances the insulating properties of the electrode surface, effectively suppressing internal short circuits even in high-capacity cells, thereby improving the safety of the nonaqueous electrolyte storage element 1. If the inorganic particle layer 13 is too thick, the inter-electrode distance increases, resulting in a deterioration in the input / output characteristics of the nonaqueous electrolyte storage element 1. By setting the thickness of the inorganic particle layer 13 to 20 μm or less, it is possible to effectively suppress internal short circuits while maintaining input / output characteristics. Furthermore, if the thickness of the inorganic particle layer 13 is thinner than 1 μm, the insulating effect is reduced, making it impossible to suppress short circuits and thus failing to improve the safety of the nonaqueous electrolyte storage element 1. By setting the thickness of the inorganic particle layer 13 to 1 μm or more, it is possible to obtain an insulating effect.

[0075] The resistance value per unit area of ​​the inorganic particle layer 13, i.e., the sheet resistance (Ω cm 2 ) can be calculated as follows. First, a first nonaqueous electrolyte storage element is produced using an electrode in which an inorganic particle layer is formed on an electrode mixture layer. Then, the impedance of the first nonaqueous electrolyte storage element after charge and discharge is measured from 100 kΩ to 0.01 kΩ, and the intersection point with the real axis of the Cole-Cole plot obtained is calculated by dividing the intersection point A (Ω) with the total area S (cm ) where the positive and negative electrodes face each other. 2 ) and the sheet resistance Al = A (Ω) × S (cm 2 ) is calculated.

[0076] Next, a second nonaqueous electrolyte storage element is fabricated in the same manner as above, except that the inorganic particle layer 13 is not formed. Then, the intersection point B (Ω) with the real axis of the Cole-Cole plot obtained when the impedance of the second nonaqueous electrolyte storage element after charge and discharge is measured from 100 kΩ to 0.01 kΩ is calculated, and the total area S (cm ) of the opposing positive and negative electrodes is calculated. 2 ) and the sheet resistance REF = B (Ω) × S (cm 2 ) is calculated.

[0077] The sheet resistance Al-sheet resistance REF is the sheet resistance (Ω cm 2 ) <separator> The separator 30 is provided between the negative electrode and the positive electrode to prevent a short circuit between the negative electrode and the positive electrode. The separator 30 is an insulating layer that is ion permeable but not electronically conductive. There are no particular limitations on the material, shape, size, or structure of the separator 30, and they can be appropriately selected depending on the purpose.

[0078] Examples of materials for the separator 30 include paper such as kraft paper, vinylon-mixed paper, and synthetic pulp-mixed paper, cellophane, polyethylene graft membrane, polyolefin nonwoven fabric such as polypropylene melt-flow nonwoven fabric, polyamide nonwoven fabric, glass fiber nonwoven fabric, polyethylene-based microporous membrane, polypropylene-based microporous membrane, etc. Among these, those with a porosity of 50% or more are preferred from the viewpoint of retaining the nonaqueous electrolyte solution.

[0079] The average thickness of the separator 30 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 μm to 50 μm, more preferably 5 μm to 30 μm. If the average thickness of the separator 30 is 3 μm or more, short-circuiting between the negative electrode and the positive electrode can be reliably prevented. Furthermore, if the average thickness of the separator 30 is 50 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be prevented.

[0080] If the average thickness of the separator 30 is 5 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. If the average thickness of the separator 30 is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the electrodes can be further prevented.

[0081] The shape of the separator 30 can be, for example, a sheet. The size of the separator 30 is not particularly limited as long as it is a size that can be used in an energy storage element, and can be appropriately selected depending on the purpose. The structure of the separator 30 may be a single-layer structure or a laminated structure. <Electrolyte layer> The nonaqueous electrolyte that constitutes the electrolyte layer 51 is an electrolyte containing a nonaqueous solvent and an electrolyte salt. There are no particular limitations on the nonaqueous solvent and it can be selected appropriately depending on the purpose, but an aprotic organic solvent is preferred. As the aprotic organic solvent, a carbonate-based organic solvent such as a chain carbonate or a cyclic carbonate is used. Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), and methyl propionate (MP).

[0082] Examples of cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), etc. When using a mixed solvent that combines ethylene carbonate (EC) as the cyclic carbonate and dimethyl carbonate (DMC) as the chain carbonate, the mixing ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) is not particularly limited and can be appropriately selected depending on the purpose.

[0083] As the non-aqueous solvent, an ester-based organic solvent such as a cyclic ester or a chain ester, or an ether-based organic solvent such as a cyclic ether or a chain ether can be used as needed.

[0084] Examples of cyclic esters include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone.

[0085] Examples of chain esters include alkyl propionates, dialkyl malonates, alkyl acetates (methyl acetate (MA), ethyl acetate, etc.), and alkyl formates (methyl formate (MF), ethyl formate, etc.).

[0086] Examples of cyclic ethers include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and 1,4-dioxolane.

[0087] Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and tetraethylene glycol dialkyl ether.

[0088] Lithium salts can be used as the electrolyte salt. The lithium salt is not particularly limited and can be appropriately selected depending on the purpose. Examples include lithium hexafluorophosphate (LiPF), lithium perchlorate (LiClO), lithium chloride (LiCl), lithium borofluoride (LiBF), lithium arsenic hexafluoride (LiAsF), lithium trifluoromethansulfonate (LiCFSO), lithium bistrifluoromethylsulfonylimide (LiN(CFSO)), and lithium bistrifluoroethylsulfonylimide (LiN(CFSO)). These may be used alone or in combination of two or more. Among these, LiPF is particularly preferred from the viewpoint of the amount of anions absorbed into the carbon electrode.

[0089] The content of the electrolyte salt is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.7 mol / L or more and 4 mol / L or less, more preferably 1.0 mol / L or more and 3 mol / L or less, in the non-aqueous solvent, and more preferably 1.0 mol / L or more and 2.5 mol / L or less from the viewpoint of achieving both the capacity and output of the energy storage element. <Method of manufacturing a nonaqueous electrolyte capacitor element> - Preparation of negative electrode - To fabricate the negative electrode 17 shown in FIG. 3, first, a negative electrode substrate 11 made of stainless steel, copper, or the like is prepared. Then, a negative electrode material composition for the negative electrode composite layer 12 is prepared as a slurry by adding a binder, a conductive agent, a solvent, or the like to the negative electrode active material as needed, and the slurry is applied to one surface of the negative electrode substrate 11 and dried to form the negative electrode composite layer 12. Similarly, a negative electrode composite layer 12 is formed on the other surface of the negative electrode substrate 11. The negative electrode substrate 11 and each negative electrode composite layer 12 are bonded to each other.

[0090] Next, a composition for inorganic particle layer 13 is prepared as an ink by mixing ceramic particles such as alumina with a polymer and a solvent, and this ink is applied to one of the negative electrode mixture layers 12 and dried to form inorganic particle layer 13. In the same manner, an inorganic particle layer 13 is also formed on the other negative electrode mixture layer 12. In this manner, negative electrode 17 is completed.

[0091] For example, an inkjet method can be used to apply the negative electrode material composition or the composition for the inorganic particle layer 13. However, the application method is not particularly limited and can be appropriately selected depending on the purpose, and for example, a die coater, a comma coater, a gravure coater, screen printing, dry press coating, a dispenser method, or the like may be used.

[0092] The inkjet method is advantageous in that it can apply a target material to a targeted location in the lower layer. The inkjet method is also advantageous in that it can bond the upper and lower contacting surfaces of the negative electrode substrate 11, the negative electrode composite layer 12, and the inorganic particle layer 13. The inkjet method is also advantageous in that it can achieve a uniform film thickness for each layer.

[0093] The solvent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aqueous solvents, organic solvents, etc. Examples of aqueous solvents include water, alcohol, etc. Examples of organic solvents include N-methyl-2-pyrrolidone (NMP), toluene, etc.

[0094] Furthermore, the negative electrode active material to which a binder, a conductive agent, etc. have been added can be roll-formed as is to form a sheet electrode, or can be compression-molded to form a pellet electrode, or a thin film of the negative electrode active material can be formed on the negative electrode substrate 11 by a method such as vapor deposition, sputtering, or plating. -Preparation of positive electrode- To fabricate the positive electrode 27 shown in FIG. 3, first, a positive electrode substrate 21 made of stainless steel, aluminum, or the like is prepared. Then, a positive electrode material composition for the positive electrode mixture layer 22 is prepared as a slurry by adding a binder, a thickener, a conductive agent, a solvent, or the like to the positive electrode active material as needed, and the slurry is applied to the positive electrode substrate 21 and dried to form the positive electrode mixture layer 22. In a similar manner, a positive electrode mixture layer 22 is also formed on the other surface of the positive electrode substrate 21. The positive electrode substrate 21 and each positive electrode mixture layer 22 are bonded to each other.

[0095] The cathode material composition can be applied, for example, by an inkjet method, but is not particularly limited and can be appropriately selected depending on the purpose. However, the application method is not particularly limited and can be appropriately selected depending on the purpose, and for example, a die coater, a comma coater, a gravure coater, screen printing, dry press coating, a dispenser method, etc. may be used.

[0096] The solvent can be the same as that used in the method for producing the negative electrode 17. The positive electrode active material can also be roll-formed as it is to form a sheet electrode, or can be compression-molded to form a pellet electrode. - Fabrication of electrode elements and non-aqueous electrolyte storage elements - To fabricate the electrode element 40 and the nonaqueous electrolyte storage element 1, first, the positive electrode 27 is placed on one side of the negative electrode 17 so that the inorganic particle layer 13 on one side of the negative electrode 17 and the positive electrode mixture layer 22 of the positive electrode 27 face each other with the separator 30 interposed therebetween. Similarly, the positive electrode 27 is placed on the other side of the negative electrode 17 so that the inorganic particle layer 13 on the other side of the negative electrode 17 and the positive electrode mixture layer 22 of the positive electrode 27 face each other with the separator 30 interposed therebetween.

[0097] Next, a negative electrode lead wire 41 is joined to the negative electrode substrate 11 by welding or the like, and a positive electrode lead wire 42 is joined to the positive electrode substrate 21 by welding or the like, thereby producing the electrode element 40 shown in Fig. 3. Next, a nonaqueous electrolyte is injected into the electrode element 40 to form an electrolyte layer 51, and the electrode element 40 is sealed with an exterior casing 52, thereby producing the nonaqueous electrolyte storage element 1 shown in Fig. 4.

[0098] As described above, the number of layers of negative electrodes 17 and positive electrodes 27 can be determined arbitrarily in the electrode element 40. That is, although a total of three layers, one negative electrode 17 and two positive electrodes 27, are illustrated in Fig. 3 and Fig. 4, the number is not limited to this, and more negative electrodes 17 and positive electrodes 27 can be stacked.

[0099] As described above, the negative electrode 17 used in the nonaqueous electrolyte storage element 1 according to this embodiment has a negative electrode mixture layer 12 and an inorganic particle layer 13. The inorganic particle layer 13 contains insulating inorganic particles 61 having a surface potential and a polymer 62 having an ionic functional group (A) and an ion-conductive functional group (B) that are oppositely charged to the surface potential of the inorganic particles 61, and the inorganic particles 61 and the polymer 62 are bonded to each other through ionic interaction.

[0100] This makes it possible to suppress the penetration of the polymer into negative electrode mixture layer 12 and effectively suppress the decrease in lithium ion conductivity in negative electrode mixture layer 12.

[0101] Furthermore, because the inorganic particles 61 and the polymer 62 are bonded by ionic interaction, the polymer 62 does not cover the surfaces of the inorganic particles 61. This allows lithium ions to diffuse on the surfaces of the inorganic particles 61, thereby improving the input / output characteristics of the nonaqueous electrolyte storage element 1.

[0102] Furthermore, since the polymer 62 has an ionic functional group, the main chain and side chain of the polymer 62 are entangled, which has the effect of binding together the inorganic particles 61 having the core-shell structure 60. This improves the physical strength of the inorganic particle layer 13, and can improve the safety of the nonaqueous electrolyte storage element 1.

[0103] In the first embodiment, an example in which an inorganic particle layer is provided on the negative electrode in the nonaqueous electrolyte storage element 1 has been described. However, the present invention is not limited to this, and an inorganic particle layer may be provided on the positive electrode composite layer of the positive electrode. In this case, an inorganic particle layer does not need to be provided on the negative electrode. Alternatively, an inorganic particle layer may be provided on the positive electrode, and an inorganic particle layer may also be provided on the negative electrode. In either case, the same effects as those of the first embodiment are achieved.

[0104] When an inorganic particle layer is provided on the positive electrode, the thickness of the inorganic particle layer can be set to the same as that of the negative electrode, thereby obtaining the same effect as that of the negative electrode.

[0105] The above is just an example, and the battery can be designed appropriately depending on the desired battery characteristics.

[0106] Second Embodiment In the second embodiment, an example in which a mixed layer is disposed between an electrode mixture layer and an inorganic particle layer is shown. Note that in the second embodiment, the description of the same components as those in the already described embodiments may be omitted.

[0107] 8A and 8B are diagrams illustrating a negative electrode used in a nonaqueous electrolyte storage element according to a second embodiment, where FIG. 8A is a plan view and FIG. 8B is a cross-sectional view taken along line CC in FIG. 8A.

[0108] Referring to FIG. 8, negative electrode 10A differs from negative electrode 10 (see FIG. 1) in that mixed layer 14 is formed on negative electrode mixture layer 12.

[0109] The mixed layer 14 is a layer containing a negative electrode mixture, inorganic particles, and a polymer. The negative electrode mixture contained in the mixed layer 14 is as described above. That is, the mixed layer 14 contains at least a negative electrode active material, and may also contain a binder, a thickener, a conductive agent, and the like as necessary.

[0110] The inorganic particles contained in the mixed layer 14 can be the same as the insulating inorganic particles described for the inorganic particle layer 13. That is, metal oxides, metal nitrides, and other metal fine particles can be used. Preferred metal oxides include Al2O3 (alumina), TiO2, BaTiO3, and ZrO2.

[0111] Preferred metal nitrides include aluminum nitride, silicon nitride, etc. Preferred other metal fine particles include poorly soluble ionic crystal fine particles such as aluminum fluoride, calcium fluoride, barium fluoride, and barium sulfate, as well as substances derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, and bentonite, or artificial products thereof.

[0112] The inorganic particles may also include glass ceramic powders, such as crystallized glass ceramics using ZnO-MgO-Al2O3-SiO2-based crystallized glass, and non-glass ceramics using BaO-Al2O3-SiO2-based ceramic powders or Al2O3-CaO-SiO2-MgO-B2O3-based ceramic powders.

[0113] It is more desirable to use an ion-conductive element as the inorganic particles. Specifically, for example, a material containing at least one element selected from the group consisting of silicon, aluminum, and zirconium, which have ion conductivity, can be used as the inorganic particles. More preferably, Al2O3 (alumina) can be used.

[0114] By providing mixed layer 14 on negative electrode mixture layer 12, it is possible to promote the diffusion of lithium near the surface of negative electrode mixture layer 12 and suppress the deposition of lithium near the surface of negative electrode mixture layer 12. As a result, it is possible to suppress the deterioration of nonaqueous electrolyte storage element 1 due to the deposition of lithium near the negative electrode surface, and the life characteristics of nonaqueous electrolyte storage element 1 can be improved.

[0115] The average particle size of the inorganic particles contained in the mixed layer 14 is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 3 μm or less. When the average particle size of the inorganic particles is 0.1 μm or more and 5 μm or less, the average particle size of the inorganic particles is sufficiently small, so that the surface area of ​​the inorganic particles is increased and the lithium diffusion effect can be obtained even when the amount of inorganic particles used is small. The average particle size of the inorganic particles can be measured by laser diffraction.

[0116] The polymer contained in the mixed layer 14 can be the same as the polymer having an ionic functional group and an ion-conductive functional group that are oppositely charged to the surface potential of the inorganic particles, as described in the inorganic particle layer 13. The ionic functional group and the ion-conductive functional group are as described in the first embodiment. As in the first embodiment, the polymer that is oppositely charged to the surface potential of the inorganic particles bonds to the inorganic particles through ionic interaction to form a core-shell structure.

[0117] The thickness of the mixed layer 14 is preferably in the range of 1% to 20% of the thickness of the negative electrode composite layer 12. By providing the mixed layer 14 on the negative electrode composite layer 12, lithium conduction is achieved on the surface of the inorganic particles, and lithium deposition, which tends to occur near the surface of the negative electrode composite layer 12, can be more effectively suppressed, thereby improving the life characteristics of the nonaqueous electrolyte storage element 1. If the mixed layer 14 is too thick relative to the negative electrode composite layer 12, the interelectrode distance between the positive and negative electrodes increases, thereby degrading the input / output characteristics of the nonaqueous electrolyte storage element 1. If the mixed layer 14 is too thin relative to the negative electrode composite layer 12, the desired effect cannot be achieved. Furthermore, mixing the negative electrode composite with the inorganic particles improves lithium diffusibility on the inorganic particle surfaces, thereby improving lithium diffusibility in the mixed layer 14. This improves the input / output characteristics of the nonaqueous electrolyte storage element 1.

[0118] The film thickness of negative electrode mixture layer 12 and mixed layer 14 can be measured as follows: That is, a cross section of each layer is cut out and observed with an SEM, and the film thickness can be measured from the results.

[0119] The mixed layer 14 can be formed by applying an ink containing a negative electrode active material, a conductive additive, inorganic particles 61, and a polymer 62 onto the underlying negative electrode composite layer 12 by inkjet printing or the like, and then drying the applied ink. For example, the negative electrode active material, the conductive additive, the dispersant, the surfactant, the inorganic particles, and the polymer are dispersed in a solvent to form an ink. The solvent is selected to be suitable for the negative electrode active material and inorganic particles to be dispersed. Specifically, water, hydrocarbon solvents, alcohol solvents, ketone solvents, ester solvents, and ether solvents can be used. When preparing this ink, a homogenizer may be used for dispersion. Examples of homogenizers that can be used include high-speed rotation shear stirring, high-pressure injection dispersion, ultrasonic dispersion, and media stirring mill.

[0120] When preparing the ink, additives such as dispersants and surfactants may be used as needed. Examples of dispersants and surfactants that can be used include Megafac (manufactured by DIC Corporation), Marialim (manufactured by NOF Corporation), Esreem (manufactured by NOF Corporation), Solsperse (manufactured by Lubrizol), and Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.). Other additives that can be used include thickeners such as propylene glycol and carboxymethyl cellulose to adjust viscosity. Resins may be added when dispersing inorganic particles in a solvent. Examples of resins that can be used include acrylic resin, SBR (styrene butadiene rubber), PVdF (polyvinylidene fluoride), and PVP (polyvinylpyrrolidone). A small amount of these resins effectively binds inorganic particles together. The amount of the polymer and resin added is preferably 0.5% by mass or more and 5% by mass or less relative to the inorganic particles. The mixed layer 14 can be formed to any desired thickness by adjusting the amount of ink applied.

[0121] Fig. 9 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to embodiment 2. Referring to Fig. 9, nonaqueous electrolyte storage element 1A differs from nonaqueous electrolyte storage element 1 (see Fig. 4) in that electrode element 40 is replaced with electrode element 40A.

[0122] Electrode element 40A has a structure in which positive electrodes 27 are stacked on both sides of negative electrode 17A with separators 30 interposed therebetween. Negative electrode 17A differs from negative electrode 10A (see FIG. 8) in that negative electrode mixture layer 12, mixed layer 14, and inorganic particle layer 13 are formed on both sides of negative electrode substrate 11, but is otherwise similar to negative electrode 10A.

[0123] In the electrode element 40A, the number of layers of negative electrodes 17A and positive electrodes 27 can be determined arbitrarily. That is, although Fig. 9 illustrates a total of three layers, one negative electrode 17A and two positive electrodes 27, the present invention is not limited to this, and more negative electrodes 17A and positive electrodes 27 can be layered. In this case, the number of negative electrodes 17A and the number of positive electrodes 27 may be the same.

[0124] In this way, in nonaqueous electrolyte storage element 1A, disposing mixed layer 14 on negative electrode mixture layer 12 of negative electrode 17A provides the following effect in addition to the effects provided by nonaqueous electrolyte storage element 1. That is, it is possible to suppress lithium deposition near the surface of negative electrode mixture layer 12, thereby improving the life characteristics of nonaqueous electrolyte storage element 1A.

[0125] Furthermore, by providing the mixed layer 14, lithium diffusibility is improved on the surface of the inorganic particles, thereby improving lithium diffusibility in the mixed layer 14. This allows the input / output characteristics of the nonaqueous electrolyte storage element 1 to be improved.

[0126] Furthermore, by providing inorganic particle layer 13 on mixed layer 14, it is possible to prevent foreign matter from being mixed into negative electrode 17 and also to prevent a short circuit between the negative electrode and the positive electrode, thereby improving the safety of nonaqueous electrolyte storage element 1. Furthermore, although it is not essential to provide a separator between the negative electrode and the positive electrode, providing a separator between the negative electrode and the positive electrode can prevent a short circuit between the negative electrode and the positive electrode when the separator melts.

[0127] That is, in negative electrode 17A, by providing mixed layer 14 on negative electrode composite layer 12 and providing inorganic particle layer 13 on mixed layer 14, it is possible to improve the life characteristics of nonaqueous electrolyte storage element 1A and simultaneously satisfy input / output characteristics and safety.

[0128] In the second embodiment, an example was shown in which the mixed layer 14 and the inorganic particle layer 13 were provided on the negative electrode in the nonaqueous electrolyte storage element 1A. However, the present invention is not limited to this. A mixed layer of a positive electrode composite and inorganic particles may be provided on a positive electrode composite layer of the positive electrode, and an inorganic particle layer may be provided on the mixed layer. In this case, the mixed layer 14 and the inorganic particle layer 13 may not be provided on the negative electrode. Alternatively, a mixed layer of a positive electrode composite and inorganic particles and an inorganic particle layer may be provided on the positive electrode, and the mixed layer 14 and the inorganic particle layer 13 may further be provided on the negative electrode. In either case, the same effects as those of the second embodiment are achieved.

[0129] Furthermore, when a mixed layer of a positive electrode composite and inorganic particles is provided on the positive electrode, the film thickness of the mixed layer of a positive electrode composite and inorganic particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 μm or more and 30 μm or less, more preferably 0.1 μm or more and 10 μm or less, and even more preferably 0.1 μm or more and 5 μm or less.

[0130] When the thickness of the mixed layer of the positive electrode composite and inorganic particles is 0.1 μm to 30 μm, the ion-conductive inorganic particles can diffuse lithium near the positive electrode surface, thereby supplying lithium ions to the low-electrical-conductivity positive electrode material (metal oxide), thereby improving the performance (input / output characteristics) of the nonaqueous electrolyte storage element 1.

[0131] If the thickness of the mixed layer of the positive electrode mixture and inorganic particles is 0.1 μm or more and 10 μm or less, it is possible to supply more lithium ions to the positive electrode material (metal oxide) having low electrical conductivity, thereby further improving the performance (input / output characteristics) of the nonaqueous electrolyte storage element 1. If the thickness of the mixed layer of the positive electrode mixture and inorganic particles is 0.1 μm or more and 5 μm or less, it is possible to supply more lithium ions to the positive electrode material (metal oxide) having low electrical conductivity, thereby further improving the performance (input / output characteristics) of the nonaqueous electrolyte storage element 1.

[0132] When an inorganic particle layer is provided on the positive electrode, the thickness of the inorganic particle layer can be set to the same as that of the negative electrode, thereby obtaining the same effect as that of the negative electrode.

[0133] The above is just an example, and the battery can be designed appropriately depending on the desired battery performance.

[0134] Third Embodiment In the third embodiment, an example is shown in which a mixed layer of inorganic particles and a porous resin is disposed on an inorganic particle layer. Note that in the third embodiment, the description of the same components as those in the previously described embodiments may be omitted.

[0135] 10A and 10B are diagrams illustrating a negative electrode used in a nonaqueous electrolyte storage element according to a third embodiment, where FIG. 10A is a plan view and FIG. 10B is a cross-sectional view taken along line DD in FIG. 10A.

[0136] Referring to FIG. 10, negative electrode 10B differs from negative electrode 10 (see FIG. 8) in that mixed layer 15 is formed on inorganic particle layer 13.

[0137] The mixed layer 15 is a layer containing inorganic particles and a porous resin. The inorganic particles contained in the mixed layer 15 can be the same as the insulating inorganic particles described for the mixed layer 14. That is, metal oxides, metal nitrides, and other metal fine particles can be used. Preferred metal oxides include Al2O3 (alumina), TiO2, BaTiO3, and ZrO2.

[0138] Preferred metal nitrides include aluminum nitride, silicon nitride, etc. Preferred other metal fine particles include poorly soluble ionic crystal fine particles such as aluminum fluoride, calcium fluoride, barium fluoride, and barium sulfate, as well as substances derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, and bentonite, or artificial products thereof.

[0139] The inorganic particles may be glass ceramic powder. The glass ceramic powder may be a crystallized glass ceramic using ZnO-MgO-Al2O3-SiO2-based crystallized glass, or a non-glass ceramic using BaO-Al2O3-SiO2-based ceramic powder or Al2O3-CaO-SiO2-MgO-B2O3-based ceramic powder. The inorganic particles contained in the mixed layer 15 preferably have an average particle size of 0.1 μm or more and 5 μm or less, more preferably 0.1 μm or more and 3 μm or less.

[0140] Examples of resins for forming the resin pores contained in the mixed layer 15 include acrylate resins, methacrylate resins, urethane acrylate resins, vinyl ester resins, unsaturated polyesters, epoxy resins, oxetane resins, vinyl ethers, and resins utilizing an ene-thiol reaction. Among these, acrylate resins, methacrylate resins, urethane acrylate resins, and vinyl ester resins are particularly preferred from the viewpoint of productivity, as they have high reactivity and can easily form structures using radical polymerization.

[0141] The thickness of the mixed layer 15 is preferably 0.1 μm or more and 100 μm or less. By making the thickness of the mixed layer 15 0.1 μm or more and 100 μm or less, the diffusibility of lithium on the inorganic particle surface improves, thereby improving the diffusibility of lithium in the mixed layer 15. This improves the input / output characteristics of the nonaqueous electrolyte storage element 1.

[0142] The thickness of the mixed layer 15 is more preferably 3 μm or more and 50 μm or less, and even more preferably 5 μm or more and 30 μm or less. The mixed layer 15 has a function of suppressing short circuits between the positive electrode and the negative electrode. If the thickness of the mixed layer 15 is 3 μm or more, short circuits between the negative electrode and the positive electrode can be reliably prevented. If the thickness of the mixed layer 15 is 5 μm or more, short circuits between the negative electrode and the positive electrode can be more reliably prevented.

[0143] If the thickness of mixed layer 15 is 50 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be prevented. If the thickness of mixed layer 15 is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be further prevented.

[0144] The porosity of the mixed layer 15 is preferably 30% to 80%, more preferably 40% to 75%. If the porosity is low, the electrolyte retention capacity will be low, so the film thickness must be increased. If the film thickness is too thick, the distance between the electrodes will increase, resulting in reduced input / output characteristics. If the porosity is high, the resistance to electrolyte movement will be reduced, improving input / output characteristics, but if the porosity is too high, the structure will become brittle and vulnerable to vibration and impact. By setting the porosity of the mixed layer 15 to 30% to 80%, the electrolyte retention capacity can be secured without increasing the film thickness, and the desired input / output characteristics can be achieved while preventing the structure from becoming brittle.

[0145] The porosity can be determined from the area ratio of voids to structures from an image of a cross section of the mixed layer observed by SEM.

[0146] The total thickness of the inorganic particle layer 13 and the mixed layer 15 is preferably 1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[0147] If the total thickness of the inorganic particle layer 13 and the mixed layer 15 is 1 μm or more, it is possible to reliably prevent a short circuit between the negative electrode and the positive electrode. If the total thickness of the inorganic particle layer 13 and the mixed layer 15 is 100 μm or less, it is possible to prevent an increase in electrical resistance between the negative electrode and the positive electrode due to the negative electrode and the positive electrode being too far apart.

[0148] Furthermore, if the total thickness of the inorganic particle layer 13 and the mixed layer 15 is 3 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. Furthermore, if the total thickness of the inorganic particle layer 13 and the mixed layer 15 is 50 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be more reliably prevented.

[0149] Furthermore, if the total thickness of the inorganic particle layer 13 and the mixed layer 15 is 5 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. Furthermore, if the total thickness of the inorganic particle layer 13 and the mixed layer 15 is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be further prevented.

[0150] The mixed layer 15 can be formed using an ink for producing a mixed layer of inorganic particles and resin porous material, which is a mixture of the insulating inorganic particles described for the mixed layer 14 and a stock solution (described below) for forming a resin porous material.

[0151] There are no particular limitations on the printing apparatus as long as it can be used to form a coating, and any printing apparatus can be used that is suitable for various printing methods, such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing.

[0152] The stock solution for forming the resin porous material is composed of, for example, a polymerizable compound, a photoinitiator, and a solvent. The polymerizable compound corresponds to a precursor of the resin for forming the porous material, and any resin capable of forming a crosslinkable material by irradiation with light may be used. However, from the viewpoint of productivity, for example, the above-mentioned acrylate resin, methacrylate resin, urethane acrylate resin, vinyl ester resin, unsaturated polyester, epoxy resin, oxetane resin, vinyl ether, and resins utilizing an ene-thiol reaction are preferred. Among these, acrylate resin, methacrylate resin, urethane acrylate resin, and vinyl ester resin are particularly preferred, as they are highly reactive and can easily form a material by radical polymerization.

[0153] The resin compound can be cured by light by preparing a mixture of a polymerizable compound and a compound that generates radicals or acids when exposed to light. The polymerizable compound has at least one radically polymerizable functional group. Examples of such a radically polymerizable compound include monofunctional, difunctional, trifunctional or higher functional radically polymerizable compounds, functional monomers, and radically polymerizable oligomers. Among these, difunctional or higher functional radically polymerizable compounds are particularly preferred.

[0154] Examples of monofunctional radically polymerizable compounds include 2-(2-ethoxyethoxy)ethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, cyclohexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, etc. These may be used alone or in combination of two or more.

[0155] Examples of bifunctional radically polymerizable compounds include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, etc. These may be used alone or in combination of two or more.

[0156] Examples of the trifunctional or higher radical polymerizable compound include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, and trimethylolpropane trimethacrylate. Examples of such acrylates include tris(acryloxyethyl)isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxy tetraacrylate, EO-modified phosphate triacrylate, and 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate. These may be used alone or in combination of two or more.

[0157] As the photopolymerization initiator, a photoradical generator can be used. For example, photoradical polymerization initiators such as Michler's ketone and benzophenone, known under the trade names Irgacure and Darocure, more specific compounds include benzophenone, acetophenone derivatives, such as α-hydroxy- or α-aminocetophenone, 4-aroyl-1,3-dioxolane, benzil ketal, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzophenone, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzil, benzoin, benzil dimethyl ketal, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, azobisisobutyronitrile, benzoin peroxide, etc. oxide, di-tert-butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoyl formate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin n-propyl and other benzoin alkyl ethers and esters, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173), bis(2,6-dimethoxybenzoyl)-2, 4,4-trimethyl-pentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one monoacylphosphine oxide, bisacylphosphine oxide or titanocene, fluorescein, anthraquinone, thioxanthone or xanthone, lophine dimer, trihalomethyl compounds or dihalomethyl compounds, active ester compounds, organoboron compounds, and the like are preferably used.

[0158] Furthermore, a photocrosslinking radical generator such as a bisazide compound may be simultaneously contained. When the polymerization is accelerated by heat, a conventional thermal polymerization initiator such as A(AIBN), which is a conventional photoradical generator, may be mixed and used.

[0159] On the other hand, a similar function can be achieved by preparing a mixture of a photoacid generator that generates acid upon exposure to light and at least one monomer that polymerizes in the presence of acid. When such a liquid ink is irradiated with light, the photoacid generator generates acid, which functions as a catalyst for the crosslinking reaction of the polymerizable compound. The generated acid also diffuses within the ink layer. Moreover, the diffusion of the acid and the crosslinking reaction catalyzed by the acid can be accelerated by heating, and unlike radical polymerization, this crosslinking reaction is not inhibited by the presence of oxygen. The resulting resin layer also has superior adhesion compared to radical polymerization systems.

[0160] Examples of polymerizable compounds that crosslink in the presence of an acid include compounds having a cyclic ether group such as an epoxy group, an oxetane group, or an oxolane group, acrylic or vinyl compounds having the above-mentioned substituents on their side chains, carbonate compounds, low-molecular-weight melamine compounds, vinyl ethers, vinyl carbazoles, styrene derivatives, alpha-methylstyrene derivatives, vinyl alcohol esters including ester compounds of vinyl alcohol with acrylic or methacrylic, and the like, which are used in combination with monomers having a vinyl bond that can be polymerized cationically.

[0161] Examples of photoacid generators that generate acid upon irradiation with light include onium salts, diazonium salts, quinone diazide compounds, organic halides, aromatic sulfonate compounds, bisulfone compounds, sulfonyl compounds, sulfonate compounds, sulfonium compounds, sulfamide compounds, iodonium compounds, sulfonyldiazomethane compounds, and mixtures thereof.

[0162] Among them, it is desirable to use an onium salt as the photoacid generator. Examples of usable onium salts include diazonium salts, phosphonium salts, and sulfonium salts having a fluoroborate anion, a hexafluoroantimonate anion, a hexafluoroarsenate anion, a trifluoromethanesulfonate anion, a paratoluenesulfonate anion, and a paranitrotoluenesulfonate anion as a counter ion. Furthermore, a halogenated triazine compound can also be used as the photoacid generator.

[0163] The photoacid generator may further contain a sensitizing dye in some cases, such as an acridine compound, benzoflavins, perylene, anthracene, and laser dyes.

[0164] Next, the solvent used will be described. Formation of a porous body by polymerization-induced phase separation can be achieved by preparing a mixed solution in which a solvent is mixed in advance with the polymerizable compound and a compound that generates radicals or acids when exposed to light. The solvent functions as a porogen that forms porous pore regions during the progress of polymerization due to light.

[0165] The porogen can be arbitrarily selected from liquid substances that can dissolve the polymerizable compound and the compound that generates radicals or an acid when exposed to light, and that can cause phase separation during the polymerization process of the polymerizable compound and the compound that generates radicals or an acid when exposed to light.

[0166] Examples of porogens include ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; esters such as gamma-butyrolactone and propylene carbonate; and amides such as NN-dimethylacetamide. Liquid substances with relatively high molecular weights, such as methyl tetradecanoate, methyl decanoate, methyl myristate, and tetradecane, also tend to function as porogens. Among these, many ethylene glycols have high boiling points. The structure formed by the phase separation mechanism is highly dependent on the porogen concentration. Therefore, the use of the above liquid substances enables the formation of a stable porous body. Porogens may be used alone or in combination of two or more.

[0167] The viscosity of the resulting film-forming solution is preferably 1 to 1000 Pa·s, more preferably 5 to 200 mPa·s at 25° C., taking into consideration handling properties and leveling performance, ensuring print quality.

[0168] The solids concentration of the polymerizable compound in the film-forming solution is preferably 5 to 70% by mass, more preferably 10 to 50% by mass. If the polymerizable compound concentration is higher than the above range, the pore size tends to be small, at several tens of nanometers or less, making it difficult for liquids or gases to penetrate. If the polymerizable compound concentration is lower than the above range, the three-dimensional network structure of the resin is not sufficiently formed, and the strength of the resulting porous body tends to be significantly reduced.

[0169] Fig. 11 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to Embodiment 3. Referring to Fig. 11, nonaqueous electrolyte storage element 1B differs from nonaqueous electrolyte storage element 1A (see Fig. 9) in that electrode element 40A is replaced with electrode element 40B.

[0170] Electrode element 40B has a structure in which a positive electrode 27 is laminated on both sides of a negative electrode 17B. Negative electrode 17B differs from negative electrode 10B (see FIG. 10 ) in that a negative electrode composite layer 12, a mixed layer 14 of a negative electrode composite and inorganic particles, an inorganic particle layer 13, and a mixed layer 15 of inorganic particles and porous resin are formed on both sides of a negative electrode electrode substrate 11, but is otherwise similar to negative electrode 10B.

[0171] In the electrode element 40B, the number of layers of negative electrodes 17B and positive electrodes 27 can be determined arbitrarily. That is, although Fig. 11 illustrates a total of three layers, one negative electrode 17B and two positive electrodes 27, the present invention is not limited to this, and more negative electrodes 17B and positive electrodes 27 can be stacked. In this case, the number of negative electrodes 17B and the number of positive electrodes 27 may be the same.

[0172] In this way, in nonaqueous electrolyte storage element 1B, by arranging mixed layer 15 of inorganic particles and porous resin on inorganic particle layer 13 of negative electrode 17B, in addition to the effects achieved by nonaqueous electrolyte storage element 1A, the effect of improving ionic conduction is obtained.

[0173] In the third embodiment, an example in which the mixed layer 14, the inorganic particle layer 13, and the mixed layer 15 are provided on the negative electrode has been described. However, the present invention is not limited to this. The positive electrode may be provided with a mixed layer of the positive electrode composite and inorganic particles, an inorganic particle layer, and a mixed layer of inorganic particles and a porous resin. In this case, the mixed layer 14, the inorganic particle layer 13, and the mixed layer 15 may not be provided on the negative electrode. Alternatively, the positive electrode may be provided with a mixed layer of the positive electrode composite and inorganic particles, an inorganic particle layer, and a mixed layer of inorganic particles and a porous resin, and the negative electrode may further be provided with the mixed layer 14, the inorganic particle layer 13, and the mixed layer 15. In either case, the same effects as those of the third embodiment are achieved.

[0174] When a mixed layer of inorganic particles and porous resin is provided on the positive electrode, the same effect as in the case of the negative electrode can be obtained by setting the thickness of the mixed layer of inorganic particles and porous resin to the same as in the case of the negative electrode.

[0175] The total thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm.

[0176] When the combined thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is 1 μm or more, a short circuit between the negative electrode and the positive electrode can be reliably prevented. When the combined thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is 100 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be prevented.

[0177] Furthermore, if the combined thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is 3 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. Furthermore, if the combined thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is 50 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be more reliably prevented.

[0178] Furthermore, if the combined thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is 5 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. Furthermore, if the combined thickness of the inorganic particle layer and the mixed layer of inorganic particles and porous resin is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be further prevented.

[0179] Fourth Embodiment In the fourth embodiment, an example is shown in which a porous resin layer is disposed on a mixed layer of inorganic particles and porous resin. Note that in the fourth embodiment, the description of the same components as those in the previously described embodiments may be omitted.

[0180] 12A and 12B are diagrams illustrating a negative electrode used in a nonaqueous electrolyte storage element according to a fourth embodiment, where FIG. 12A is a plan view and FIG. 12B is a cross-sectional view taken along line EE in FIG. 12A.

[0181] 12, negative electrode 10C differs from negative electrode 10B (see FIG. 10) in that a resin porous layer 16 is formed on mixed layer 15.

[0182] The thickness of the resin porous layer 16 is preferably 0.1 μm or more and 100 μm or less, more preferably 3 μm or more and 50 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[0183] If the thickness of the resin porous layer 16 is 0.1 μm or more, it is possible to reliably prevent a short circuit between the negative electrode and the positive electrode. If the thickness of the resin porous layer 16 is 100 μm or less, it is possible to prevent an increase in electrical resistance between the negative electrode and the positive electrode due to the negative electrode and the positive electrode being too far apart.

[0184] Furthermore, if the thickness of the resin porous layer 16 is 3 μm or more, it is possible to more reliably prevent a short circuit between the negative electrode and the positive electrode. If the thickness of the resin porous layer 16 is 50 μm or less, it is possible to more reliably prevent an increase in electrical resistance between the negative electrode and the positive electrode due to the negative electrode and the positive electrode being too far apart.

[0185] Furthermore, if the thickness of the resin porous layer 16 is 5 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. If the thickness of the resin porous layer 16 is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the electrodes can be further prevented.

[0186] The porosity of the resin porous layer 16 is preferably 40% to 90%, and more preferably 45% to 85%. A small porosity reduces the amount of electrolyte solution retained, so the film thickness must be increased. A thick film increases the distance between the electrodes, resulting in reduced input / output characteristics. A large porosity reduces the resistance to electrolyte solution movement and improves input / output characteristics, but if the porosity is too high, the structure becomes brittle and vulnerable to vibration and impact. By setting the porosity of the resin porous layer 16 to 40% to 90%, it is possible to ensure the amount of electrolyte solution retained without increasing the film thickness, achieve the desired input / output characteristics, and prevent the structure from becoming brittle.

[0187] The total thickness of the inorganic particle layer 13, the mixed layer 15 and the resin porous layer 16 is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm.

[0188] When the total thickness of the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 is 1 μm or more, it is possible to reliably prevent a short circuit between the negative electrode and the positive electrode. When the total thickness of the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 is 100 μm or less, it is possible to prevent an increase in electrical resistance between the negative electrode and the positive electrode due to the negative electrode and the positive electrode being too far apart.

[0189] Furthermore, if the total thickness of the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 is 3 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. If the total thickness of the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 is 50 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be more reliably prevented.

[0190] Furthermore, if the total thickness of the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 is 5 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. If the total thickness of the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be further prevented.

[0191] The porous resin layer 16 can be formed using an ink for producing a porous resin layer, which is made from the stock solution for forming the porous resin described for the mixed layer 15 of inorganic particles and porous resin. There are no particular limitations on the printing apparatus used as long as it can be applied. Any printing apparatus suitable for various printing methods, such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexographic printing, offset printing, reverse printing, and inkjet printing, can be used. The stock solution for forming the porous resin layer can be, for example, a polymerizable compound, a photoinitiator, and a solvent. The porous resin described for the mixed layer 15 of inorganic particles and porous resin can be used as the material.

[0192] Fig. 13 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to embodiment 4. Referring to Fig. 13, nonaqueous electrolyte storage element 1C differs from nonaqueous electrolyte storage element 1B (see Fig. 11) in that electrode element 40B is replaced with electrode element 40C.

[0193] Electrode element 40C has a structure in which a positive electrode 27 is laminated on both sides of a negative electrode 17C. Negative electrode 17C differs from negative electrode 10C (see FIG. 12 ) in that a negative electrode composite layer 12, a mixed layer 14 of a negative electrode composite and inorganic particles, an inorganic particle layer 13, a mixed layer 15 of inorganic particles and porous resin, and a porous resin layer 16 are formed on both sides of a negative electrode electrode substrate 11, but is otherwise similar to negative electrode 10C.

[0194] In the electrode element 40C, the number of layers of negative electrodes 17C and positive electrodes 27 can be determined arbitrarily. That is, although Fig. 13 illustrates a total of three layers, one negative electrode 17C and two positive electrodes 27, the present invention is not limited to this, and more negative electrodes 17C and positive electrodes 27 can be stacked. In this case, the number of negative electrodes 17C and the number of positive electrodes 27 may be the same.

[0195] In this way, in the non-aqueous electrolyte storage element 1C, by disposing the resin porous layer 16 on the mixed layer 15 of inorganic particles and resin porous material of the negative electrode 17C, in addition to the effects achieved by the non-aqueous electrolyte storage element 1B, the effect of more reliably preventing a short circuit between the negative electrode 17C and the positive electrode 27 can be obtained.

[0196] In the fourth embodiment, an example in which the mixed layer 14, the inorganic particle layer 13, the mixed layer 15, and the resin porous layer 16 are provided on the negative electrode has been described. However, the present invention is not limited to this. The positive electrode may be provided with a mixed layer of a positive electrode composite and inorganic particles, an inorganic particle layer, a mixed layer of inorganic particles and a porous resin, and a porous resin layer. In this case, the mixed layer 14, the inorganic particle layer 13, the mixed layer 15, and the porous resin layer 16 may not be provided on the negative electrode. Alternatively, the positive electrode may be provided with a mixed layer of a positive electrode composite and inorganic particles, an inorganic particle layer, a mixed layer of inorganic particles and a porous resin, and a porous resin layer, and the negative electrode may further be provided with the mixed layer 14, the inorganic particle layer 13, the mixed layer 15, and the porous resin layer 16. In either case, the same effects as those of the third embodiment are achieved.

[0197] When the resin porous layer is provided on the positive electrode, the thickness of the layer is set to the same as that of the negative electrode, and the same effect as that of the negative electrode can be obtained.

[0198] The total thickness of the inorganic particle layer, the mixed layer of inorganic particles and porous resin, and porous resin layer is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm.

[0199] When the total thickness of the inorganic particle layer, the mixed layer of inorganic particles and porous resin, and the porous resin layer is 1 μm or more, short-circuiting between the negative electrode and the positive electrode can be reliably prevented. When the total thickness of the mixed layer of inorganic particles and porous resin, and the porous resin layer is 100 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be prevented.

[0200] Furthermore, if the total thickness of the inorganic particle layer, the mixed layer of inorganic particles and porous resin, and the porous resin layer is 3 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented. Furthermore, if the total thickness of the inorganic particle layer, the mixed layer of inorganic particles and porous resin, and the porous resin layer is 50 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be more reliably prevented.

[0201] Furthermore, if the total thickness of the inorganic particle layer, the mixed layer of inorganic particles and porous resin, and the porous resin layer is 5 μm or more, short-circuiting between the negative electrode and the positive electrode can be more reliably prevented.If the total thickness of the inorganic particle layer, the mixed layer of inorganic particles and porous resin, and the porous resin layer is 30 μm or less, an increase in electrical resistance between the negative electrode and the positive electrode due to excessive separation between the negative electrode and the positive electrode can be further prevented.

[0202] <Modification 1 of the Fourth Embodiment> In Modification 1 of the fourth embodiment, an example is shown in which a separator is disposed between the positive electrode and the negative electrode. Note that in Modification 1 of the fourth embodiment, the description of the same components as those in the already described embodiments may be omitted.

[0203] Fig. 14 is a cross-sectional view illustrating a nonaqueous electrolyte storage element according to Modification 1 of Embodiment 4. Referring to Fig. 14, nonaqueous electrolyte storage element 1D differs from nonaqueous electrolyte storage element 1C (see Fig. 13) in that electrode element 40C is replaced with electrode element 40D.

[0204] The electrode element 40D has a structure in which a positive electrode 27 is laminated on both sides of a negative electrode 17C with a separator 30 interposed therebetween.

[0205] 13, an electrode element 40C of a nonaqueous electrolyte storage element 1C does not require a separator because the inorganic particle layer 13, the mixed layer 14, and the resin porous layer 16 of the negative electrode 17C prevent a short circuit between the negative electrode 17C and the positive electrode 27. However, as in an electrode element 40D of a nonaqueous electrolyte storage element 1D shown in FIG. 14, a separator 30 may be provided between the negative electrode 17C and the positive electrode 27 as needed to more reliably prevent a short circuit between the negative electrode 17C and the positive electrode 27.

[0206] In the electrode element 40D, the number of negative electrodes 17C and positive electrodes 27 stacked with separators 30 interposed therebetween can be determined arbitrarily. That is, although Fig. 14 illustrates a total of three layers, one negative electrode 17C and two positive electrodes 27, the present invention is not limited to this, and more negative electrodes 17C and positive electrodes 27 can be stacked. In this case, the number of negative electrodes 17C and the number of positive electrodes 27 may be the same.

[0207] The nonaqueous electrolyte storage element and the like will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "parts" and "%" are by mass unless otherwise specified.

[0208] First, the synthesis methods of polymer dispersants 1 to 7 containing polymers used in some of the examples will be described.

[0209] <Synthesis of polymer dispersant 1> 100 parts of 2-[2-(2-Methoxyethoxy)ethoxy]ethyl Acrylate (Tokyo Chemical Industry Co., Ltd.) and 5 parts of acrylic acid (Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 parts of dioxane. Then, 0.1 parts of 2,2'-Azobis(2-methylpropionitrile) was added, and the mixture was stirred at 75°C for 8 hours under a nitrogen atmosphere to polymerize. After polymerization was completed, the mixture was dried under reduced pressure to obtain polymer dispersant 1 with a number average molecular weight of 5,000.

[0210] <Synthesis of polymer dispersant 2> 105 parts of polymer dispersant 1 was dissolved in 100 parts of dioxane. Then, an aqueous solution containing 1.3 parts of ammonia was added, and the mixture was stirred at 100°C for 2 hours to react. After the reaction was completed, the mixture was dried under reduced pressure to obtain polymer dispersant 2.

[0211] <Synthesis of polymer dispersant 3> 105 parts of polymer dispersant 1 was dissolved in 100 parts of dioxane. Then, an aqueous solution containing 3.1 parts of sodium hydroxide was added, and the mixture was stirred at 100°C for 2 hours to react. After the reaction was completed, the mixture was dried under reduced pressure to obtain polymer dispersant 3.

[0212] <Synthesis of polymer dispersant 4> 100 parts of stearyl acrylate (Tokyo Chemical Industry Co., Ltd.) and 5 parts of acrylic acid (Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 parts of dioxane. Then, 0.1 parts of 2,2'-Azobis(2-methylpropionitrile) was added, and the mixture was stirred at 75°C for 8 hours under a nitrogen atmosphere to polymerize. After polymerization was completed, the mixture was dried under reduced pressure to obtain polymer dispersant 4 with a number average molecular weight of 5,000. <Synthesis of polymer dispersant 5> Under a nitrogen atmosphere, 40 parts by weight of L-aspartic acid (Tokyo Chemical Industry Co., Ltd.) was added to 400 parts by weight of sulfolane (Tokyo Chemical Industry Co., Ltd.) and stirred for 12 hours. After stirring, 1.5 parts by weight of phosphoric acid (Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 180°C for 12 hours. Then, 1,000 parts by weight of methanol was added to obtain a precipitate. The precipitate was filtered under reduced pressure, and the resulting solid was washed with ion-exchanged water until the supernatant became neutral. The precipitate was then filtered under reduced pressure and vacuum dried to obtain a precursor of polymer dispersant 5.

[0213] Under a nitrogen atmosphere, 10 parts by mass of the obtained precursor was mixed with 6 parts by mass of 3,6,9,12-tetraoxadecanamine (Tokyo Chemical Industry Co., Ltd.) and 250 parts by mass of dimethylformamide (Tokyo Chemical Industry Co., Ltd.), and the mixture was heated and stirred at 70°C for 24 hours. After heating and stirring, the reaction solution was cooled to 30°C and added dropwise to 500 parts by mass of 1N aqueous ammonia. After addition, the mixture was stirred for 12 hours and then dried under reduced pressure to obtain polymer dispersant 5 with a number average molecular weight of 10,000.

[0214] <Synthesis of polymer dispersant 6> 100 parts of 2-[2-(2-Methoxyethoxy)ethoxy]ethyl Acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of vinyl sulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 parts of dioxane. Then, 0.1 parts of 2,2'-Azobis(2-methylpropionitrile) was added, and the mixture was stirred at 75°C for 8 hours under a nitrogen atmosphere to polymerize. After polymerization was completed, the mixture was dried under reduced pressure to obtain polymer dispersant 6 with a number average molecular weight of 5,000.

[0215] <Synthesis of polymer dispersant 7> 100 parts of 2-[2-(2-Methoxyethoxy)ethoxy]ethyl Acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of vinylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100 parts of dioxane. Then, 0.1 parts of 2,2'-Azobis(2-methylpropionitrile) was added, and the mixture was stirred at 75°C for 8 hours under a nitrogen atmosphere to polymerize. After polymerization was completed, the mixture was dried under reduced pressure to obtain polymer dispersant 7 with a number average molecular weight of 5,000.

[0216] [Example 1] An electrode paint was prepared by mixing 97 parts by mass of graphite, 1 part by mass of a thickener (carboxymethyl cellulose), 2 parts by mass of a binder (styrene butadiene rubber), and 100 parts by mass of water as a solvent for forming a negative electrode composite layer. The electrode paint was applied to a copper negative electrode substrate and dried to a coating amount per unit area (area density) of 9 mg / cm on one side. 2 The negative electrode mixture layers were formed on both sides of the negative electrode substrate.

[0217] Next, for forming the inorganic particle layer, 30 parts by mass of alumina particles AKP-3000 (manufactured by Sumitomo Chemical Co., Ltd.), 0.675 parts by mass of Marialim HKM-50A (manufactured by NOF Corporation): a copolymer of ammonium fumarate and a monomer having a side chain with an oxyalkylene group or a polyoxyalkylene group as a polymer, 50 parts by mass of propylene glycol as an organic solvent, and 19.7 parts by mass of water were added to prepare a coating ink.

[0218] <Median diameter of core-shell particles (D50)> The ink was ultrasonically treated for 3 minutes using an ultrasonic homogenizer US-300T (manufactured by Nippon Seiki Seisakusho Co., Ltd.) and then diluted with ion-exchanged water to an optically measurable concentration.The median diameter (D50) of the particles contained in the ink (mixture) was then measured using a laser diffraction particle size analyzer Mastersizer 3000 (manufactured by Malvern Instruments).

[0219] <Zeta potential measurement of core-shell particles> The zeta potential of the prepared dispersion was measured by diluting the dispersion to the optically measurable concentration range using ELS-Z (manufactured by Otsuka Electronics Co., Ltd.).

[0220] In this example, the shell thickness of the core-shell particles was so thin that quantitative measurement was difficult. Therefore, in this example, the formation of core-shell particles was confirmed by measuring the change in zeta potential (the state of being charged opposite to the surface potential of insulating inorganic particles) with reference to the description in Macromolecules 1999, 32, 2317-2328 (J. Am. Ceram. Soc. 1998, 81, 140.).

[0221] Specifically, insulating inorganic particles and polymers are mixed in ion-exchange water, and dispersion treatment is performed as necessary to obtain a dispersion. The zeta potential of the appropriately diluted dispersion is then measured. This shows that the zeta potential decreases up to the amount added that reaches a neutral point relative to the surface potential of the insulating inorganic particles (for example, alumina particles are positively charged near the neutral region), and beyond that point, the charge increases in the opposite direction, and the formation of core-shell particles is observed.

[0222] For example, the zeta potential of alumina (AKP3000, manufactured by Sumitomo Chemical Co., Ltd.) is +50 mV under neutral conditions. Therefore, if the zeta potential of a core-shell particle made with alumina as the core is in the range of +50 mV to 0 or a negative value, it can be said to have a core-shell structure in which the shell is made of a polymer with an opposite charge to the surface potential of the alumina.

[0223] The coating ink was applied to one of the negative electrode mixture layers using an inkjet device and dried to give a coating weight of 1.3 mg / cm 2 Similarly, an inorganic particle layer was formed on the other negative electrode mixture layer under the same coating conditions (basis weight 1.3 mg / cm). 2 The thickness was approximately 6.5 μm.

[0224] As a result, an electrode was obtained in which a negative electrode composite layer and an inorganic particle layer were sequentially laminated on both sides of the negative electrode substrate. The obtained electrode was punched out to a predetermined size (coated side 30 mm × 50 mm, uncoated side 10 mm × 11 mm) to prepare a negative electrode.

[0225] An electrode paint was prepared by adding 93 parts by mass of lithium-nickel-cobalt aluminum composite oxide (NCA), 3 parts by mass of a conductive additive, 4 parts by mass of a binder (polyvinylidene fluoride), and 100 parts by mass of N-methylpyrrolidone as a solvent to form a positive electrode composite layer. The electrode paint was applied to an aluminum positive electrode substrate and dried to a coating amount per unit area (area density) of 15.0 mg / cm on one side. 2 Thus, an electrode was obtained in which the positive electrode mixture layer was formed on both sides.

[0226] The obtained electrode was punched out to a predetermined size (coated surface 28 mm x 48 mm, uncoated surface 10 mm x 13 mm) to prepare a positive electrode. Note that no inorganic particle layer was provided on the positive electrode.

[0227] The positive and negative electrodes prepared as described above were alternately stacked with film separators between them to form an electrode element with a stacking thickness of approximately 10 mm, and the uncoated portions of the electrodes were joined together, with a nickel tab welded to the negative electrode as a negative electrode lead wire and an aluminum tab welded to the positive electrode as a positive electrode lead wire. This electrode element was then impregnated with a 1.5M LiPF6EC:DMC:EMC=1:1:1 nonaqueous electrolyte solution and sealed in an aluminum laminate film to produce a nonaqueous electrolyte storage element.

[0228] (First charge and initial capacity measurement) The positive electrode lead wire and negative electrode lead wire of the nonaqueous electrolyte storage element prepared as described above were connected to a charge / discharge tester, and the element was charged at a constant current and constant voltage of 4.2 V at a current rate of 0.2 C for 5 hours. After charging was completed, the element was left standing in a thermostatic chamber at 40°C for 5 days. The element was then discharged at a constant current and constant voltage of 0.2 C to 2.5 V. The element was then charged at a constant current and constant voltage of 4.2 V at a current rate of 0.2 C for 5 hours, and after a 10-minute break, was discharged at a constant current and constant voltage of 0.2 C to 2.5 V. The discharge capacity at this time was recorded as the initial capacity.

[0229] (Power density evaluation test): Rating 1 The positive and negative electrode leads of the nonaqueous electrolyte storage element, whose initial capacity had been measured as described above, were connected to a charge / discharge tester and charged at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours. After a 10-minute break, the element was discharged at a constant current of 0.2 C for 2.5 hours, bringing the charge depth of the nonaqueous electrolyte storage element to 50%. Pulses of current rates of 1 C to 10 C were then applied for 10 seconds. The power required to reach a 2.5 V cutoff voltage was calculated from the correlation line between the post-pulse voltage and the current value, and the power density (Wh / kg) was calculated by dividing this by the cell weight. The resulting power density was 3150 Wh / kg. [Evaluation criteria] ◯: The output density value of Example 1 is taken as 100%, and the relative value is 70% or more ×: Less than 70% in relative value, with the output density value of Example 1 taken as 100% (Peel strength test): Rating 2 The peel strength of the electrode on which the inorganic particle layer was formed was measured. The measurement method was to attach cellophane tape to the electrode surface, and measure the peel strength (N) when peeling the cellophane tape at a 90° peel angle. The result was 0.45N. [Evaluation criteria] Good: The peel strength value of Example 1 is taken as 100%, and the relative value is 70% or more ×: Less than 70% as a relative value, with the peel strength value of Example 1 taken as 100% (Calculation of sheet resistance of inorganic particle layer) The nonaqueous electrolyte storage element of Example 1 was charged at a constant current and constant voltage at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours, and after charging was completed, it was left to stand in a thermostatic chamber at 40°C for 5 days. Thereafter, it was discharged at a constant current and constant voltage to 2.5 V at a current rate of 0.2 C. Thereafter, it was charged at a constant current and constant voltage at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours, and after a 10-minute break, it was discharged at a constant current and constant voltage to 2.5 V at a current rate of 0.2 C. Next, the intersection of the real axis of the Cole-Cole plot obtained when the impedance was measured from 100 kΩ to 0.01 kΩ: A (Ω) was calculated, and the total area S (cm) of the opposing positive and negative electrodes was calculated. 2 ) and the sheet resistance Al = A (Ω) × S (cm 2 ) was calculated.

[0230] Next, a nonaqueous electrolyte storage element was prepared in the same manner as above, except that the inorganic particle layer was not formed. This nonaqueous electrolyte storage element was charged at a constant current and constant voltage at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours. After charging was completed, the element was left to stand in a thermostatic chamber at 40°C for 5 days. It was then discharged at a constant current and constant voltage to 2.5 V at a current rate of 0.2 C. It was then charged at a constant current and constant voltage at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours, followed by a 10-minute break and then discharged at a constant current and constant voltage to 2.5 V at a current rate of 0.2 C. Next, the intersection of the real axis of the Cole-Cole plot obtained when the impedance was measured from 100 kΩ to 0.01 kΩ: B (Ω) was calculated, and the total area S (cm) of the opposing positive and negative electrodes was calculated. 2 ) and the sheet resistance REF = B (Ω) × S (cm 2 ) was calculated.

[0231] Furthermore, the sheet resistance (Ω cm 2 The sheet resistance (A1) was calculated as follows: A1 = sheet resistance A1 - sheet resistance REF. As a result, the sheet resistance of the inorganic particle layer of Example 1 was 0.22 Ω cm 2 It was.

[0232] [Example 2] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 0.3 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0233] [Example 3] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 0.15 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0234] [Example 4] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 0.9 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0235] [Example 5] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 1.2 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0236] [Example 6] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 1.5 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0237] [Explanation of Examples 1 to 6] Examples 1 to 6 are examples in which a polymer was used to form the inorganic particle layer. As shown in Fig. 15, good results were obtained in terms of output characteristics and peel strength when the amount of polymer added to the inorganic particle layer was in the range of 0.5% by mass to 5% by mass relative to the inorganic particles. When the amount of polymer added was more than 3% by mass, a slight decrease in output characteristics was observed.

[0238] [Comparative Example 1] A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that 0.3 parts by mass of an acrylic binder (manufactured by Zeon Corporation) was used instead of a polymer as the coating ink for forming the inorganic particle layer. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and Evaluations 1 and 2 were carried out. The results are shown in FIG. 16 together with the results of Example 1. The sheet resistance of the inorganic particle layer of Comparative Example 1 was measured in the same manner as in Example 1, and was found to be 5.2 Ω cm 2 It was.

[0239] [Comparison of Example 1 and Comparative Example 1] Comparative Example 1 is an example in which an acrylic binder was used instead of a polymer. As shown in Figure 16, a small amount of acrylic binder was enough to firmly bind the inorganic particles together. However, the output characteristics decreased. This is thought to be because the acrylic binder inhibited the ionic conductivity in the inorganic particle layer. Furthermore, the sheet resistance value was larger than that of Example 1, and impedance measurements revealed that the sheet resistance of the inorganic particle layer in Comparative Example 1 was high.

[0240] Comparative Example 2 A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 0.12 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results of Comparative Example 2 are shown in FIG. 17 together with the results of Example 3.

[0241] [Comparison of Example 3 and Comparative Example 2] Comparative Example 2 is an example in which the amount of polymer added to the inorganic particles was 0.4% by mass. In this case, as shown in Figure 17, the electrode peel strength value was small and below the evaluation standard. This is thought to be because the amount of polymer binding the inorganic particles to the inorganic particles was small.

[0242] Comparative Example 3 A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of polymer used in forming the inorganic particle layer was 1.8 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results of Comparative Example 3 are shown in FIG. 18 together with the results of Example 6.

[0243] [Comparison of Example 6 and Comparative Example 3] Comparative Example 3 is an example in which the amount of polymer added to the inorganic particles was 6.0% by mass. In this case, as shown in Fig. 18, the output characteristics were small and below the evaluation standard. This is thought to be because some polymer was not adsorbed onto the inorganic particle surface, and the polymer penetrated into the electrode mixture layer, coating the active material, thereby reducing ion diffusibility.

[0244] [Example 7] A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the amount of polymer was 0.45 parts by mass and the amount of acrylic binder was 0.03 parts by mass in forming the inorganic particle layer. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0245] [Example 8] A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the amount of polymer was 0.3 parts by mass and the amount of acrylic binder was 0.06 parts by mass in forming the inorganic particle layer. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0246] [Example 9] A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the amount of polymer was 0.15 parts by mass and the amount of acrylic binder was 0.075 parts by mass in forming the inorganic particle layer. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0247] [Example 10] A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the amount of polymer was 0.06 parts by mass and the amount of acrylic binder was 0.09 parts by mass in forming the inorganic particle layer. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG.

[0248] [Explanation of Examples 7 to 10] Examples 7 to 10 are examples in which a polymer and a binder were used in combination to form the inorganic particle layer, and as shown in Fig. 19, good results were obtained in terms of output characteristics and peel strength.

[0249] Comparative Example 4 A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of acrylic binder used in forming the inorganic particle layer was 0.45 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 20 together with the results of Example 1 and Comparative Example 1.

[0250] Comparative Example 5 A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of acrylic binder used in forming the inorganic particle layer was 0.15 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 20 together with the results of Example 1 and Comparative Example 1.

[0251] Comparative Example 6 A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that the amount of acrylic binder used in forming the inorganic particle layer was 0.12 parts by mass. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 20 together with the results of Example 1 and Comparative Example 1.

[0252] [Comparison of Example 1 and Comparative Examples 1, 4, and 5] Comparative Examples 1, 4, and 5 are examples in which an acrylic binder was used instead of a polymer. As shown in Figure 20, the peel strength of the electrode increased with increasing amount of acrylic binder added, and the standard was met. However, the output characteristics decreased under all conditions, and the standard for output characteristics was not met.

[0253] [Comparison of Example 1 and Comparative Example 6] Comparative Example 6 is an example in which an acrylic binder was used instead of a polymer. As shown in Figure 20, the output characteristics met the standard, but the electrode strength did not. This is thought to be because the amount of acrylic binder added was too small.

[0254] [Example 11] In forming the inorganic particle layer, the basis weight of the inorganic particle layer is 0.8 mg / cm 2 A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the thickness of the inorganic particle layer in Example 11 was 3.5 μm. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 21 together with the results of Example 1. The sheet resistance of the inorganic particle layer in Example 11 was measured in the same manner as in Example 1, and was found to be 0.11 Ω cm 2 It was.

[0255] [Example 12] In forming the inorganic particle layer, the basis weight of the inorganic particle layer is 0.6 mg / cm 2A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the thickness of the inorganic particle layer in Example 12 was 2.6 μm. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 21 together with the results of Example 1. The sheet resistance of the inorganic particle layer in Example 12 was measured in the same manner as in Example 1, and was found to be 0.05 Ω cm 2 It was.

[0256] [Example 13] In forming the inorganic particle layer, the basis weight of the inorganic particle layer is 2.6 mg / cm 2 A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the thickness of the inorganic particle layer in Example 13 was 15 μm. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 21 together with the results of Example 1. The sheet resistance of the inorganic particle layer in Example 13 was measured in the same manner as in Example 1, and was found to be 0.43 Ω cm 2 It was.

[0257] [Example 14] In forming the inorganic particle layer, the basis weight of the inorganic particle layer is 5.0 mg / cm 2 A negative electrode and a positive electrode were fabricated under the same conditions as in Example 1, except that the inorganic particle layer of Example 14 had a thickness of 30 μm. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 21 together with the results of Example 1. The sheet resistance of the inorganic particle layer of Example 14 was measured in the same manner as in Example 1, and was found to be 0.81 Ω cm 2 It was.

[0258] [Explanation of Examples 1, 11 to 14] In Examples 1 and 11 to 14, Evaluations 1 and 2 were carried out by changing the basis weight (film thickness) of the inorganic particle layer. As shown in Figure 21, the output characteristics were almost unchanged. Normally, increasing the film thickness increases the distance between the positive and negative electrodes, resulting in a significant decrease in output characteristics, but this did not occur in the results of this Example. This is thought to be because the polymer did not hinder lithium ion conduction in the inorganic particle layer, allowing the lithium ion conduction function to be exerted on the inorganic particle surface. This makes it possible to minimize the increase in resistance due to an increase in the thickness of the inorganic particle layer. Although the sheet resistance of the inorganic particle layer tends to increase as the inorganic particle layer becomes thicker, it was 1.0 Ω cm under all conditions. 2 The following was confirmed:

[0259] [Example 15] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to polymer dispersant 1. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0260] [Example 16] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to polymer dispersant 2. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0261] [Example 17] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to polymer dispersant 3. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0262] [Example 18] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to polymer dispersant 4. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0263] [Example 19] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to Polymer Dispersant 5. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and Evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0264] [Example 20] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to polymer dispersant 6. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0265] [Example 21] A negative electrode and a positive electrode were prepared under the same conditions as in Example 1, except that in forming the inorganic particle layer, the type of polymer was changed to polymer dispersant 7. A nonaqueous electrolyte storage element was then prepared in the same manner as in Example 1, and evaluations 1 and 2 were carried out. The results are shown in FIG. 22 together with the results of Example 1.

[0266] [Explanation of Examples 15 to 21] In Examples 15 to 21, evaluations 1 and 2 were performed by changing the type of polymer in the inorganic particle layer. As shown in Fig. 22, both the output characteristics and electrode strength met the evaluation criteria. It was confirmed that the same effects as in Example 1 were achieved when polymer dispersants 1 to 7 were used.

[0267] [Example 22] An electrode paint was prepared by mixing 97 parts by mass of graphite, 1 part by mass of a thickener (carboxymethyl cellulose), 2 parts by mass of a binder (styrene butadiene rubber), and 100 parts by mass of water as a solvent for forming a negative electrode composite layer. The electrode paint was applied to a copper negative electrode substrate and dried to a coating amount per unit area (area density) of 9 mg / cm on one side. 2 The negative electrode mixture layers were formed on both sides of the negative electrode substrate.

[0268] Next, to form a first mixed layer of negative electrode composite and inorganic particles, 40 parts by mass of the above electrode paint was added, and 20 parts by mass of alumina particles AKP-3000 (manufactured by Sumitomo Chemical Co., Ltd.) as inorganic particles, 30 parts by mass of propylene glycol as organic solvent, and 10 parts by mass of water were added to prepare a coating ink. This coating ink was applied to one negative electrode composite layer using an inkjet device and dried to form a first mixed layer (approximately 10 μm thick) of negative electrode composite and inorganic particles. Similarly, a first mixed layer (approximately 10 μm thick) of negative electrode composite and inorganic particles was formed on the other negative electrode composite layer.

[0269] Next, a coating ink was prepared for forming an inorganic particle layer by adding 30 parts by weight of alumina particles AKP-3000 (manufactured by Sumitomo Chemical Co., Ltd.), 0.3 parts by weight of Marialim HKM-50A (manufactured by NOF Corporation) as a dispersant, 50 parts by weight of propylene glycol as an organic solvent, and 19.7 parts by weight of water. This coating ink was applied to one of the first mixed layers using an inkjet device and dried to form an inorganic particle layer (approximately 5 μm thick). Similarly, an inorganic particle layer (approximately 5 μm thick) was formed on the other first mixed layer.

[0270] Next, a coating ink was prepared for the formation of a second mixed layer of inorganic particles and porous resin. The ink was prepared by mixing 20 parts by weight of alumina particles AKP-3000 (Sumitomo Chemical Co., Ltd.) as inorganic particles, 23.2 parts by weight of tricyclodecane dimethanol acrylate (Daicel-Allnex Corporation) as resin, 56 parts by weight of tetradecane (Kanto Chemical Industry Co., Ltd.) as solvent, and 0.8 parts by weight of Irgacure 184 (BASF) as polymerization initiator. This coating ink was applied to one of the inorganic particle layers using an inkjet device, irradiated with UV light in an environment purged with N2 (polymerizable inert gas), and then placed in a thermostatic chamber set at 80 °C to remove the solvent and promote the polymerization reaction, forming a second mixed layer (approximately 5 μm thick) of inorganic particles and porous resin. Similarly, a second mixed layer (approximately 5 μm thick) of inorganic particles and porous resin was formed on the other inorganic particle layer.

[0271] Next, a coating ink was prepared for forming a resin porous layer by mixing 29 parts by weight of tricyclodecane dimethanol acrylate (Daicel-Allnex Corporation) as the resin, 70 parts by weight of tetradecane (Kanto Chemical Industry Co., Ltd.) as the solvent, and 1 part by weight of Irgacure 184 (BASF) as the polymerization initiator. This coating ink was applied to one of the second mixed layers using an inkjet device, irradiated with UV light in an environment purged with N2, an inert polymerizable gas, and then placed in a thermostatic chamber set at 80°C to remove the solvent and promote the polymerization reaction, forming a resin porous layer (approximately 10 μm thick). Similarly, a resin porous layer (approximately 10 μm thick) was formed on the other second mixed layer.

[0272] As a result, an electrode was obtained in which a negative electrode composite layer, a first mixed layer of the negative electrode composite and inorganic particles, an inorganic particle layer, a second mixed layer of inorganic particles and a porous resin, and a porous resin layer were sequentially laminated on both sides of the negative electrode substrate. The obtained electrode was punched out to a predetermined size (coated side 30 mm × 50 mm, uncoated side 10 mm × 11 mm) to prepare a negative electrode.

[0273] An electrode paint was prepared by adding 93 parts by mass of lithium-nickel-cobalt aluminum composite oxide (NCA), 3 parts by mass of a conductive additive, 4 parts by mass of a binder (polyvinylidene fluoride), and 100 parts by mass of N-methylpyrrolidone as a solvent to form a positive electrode composite layer. The electrode paint was applied to an aluminum positive electrode substrate and dried to a coating amount per unit area (area density) of 15.0 mg / cm on one side. 2 Thus, an electrode was obtained in which the positive electrode mixture layer was formed on both sides.

[0274] The obtained electrode was punched out to a predetermined size (coated surface 28 mm×48 mm, uncoated surface 10 mm×13 mm) to prepare a positive electrode.

[0275] The positive electrode was not provided with a first mixed layer of the positive electrode mixture and inorganic particles, an inorganic particle layer, a second mixed layer of inorganic particles and a porous resin, or a porous resin layer.

[0276] The positive and negative electrodes prepared as described above were alternately stacked to a thickness of about 10 mm to form an electrode element, and the uncoated portions of the electrodes were joined together, with a nickel tab welded to the negative electrode to serve as a negative electrode lead wire and an aluminum tab welded to the positive electrode to serve as a positive electrode lead wire. This electrode element was then impregnated with a nonaqueous electrolyte solution of 1.5M LiPF6 EC:DMC:EMC=1:1:1 and sealed in an aluminum laminate film to produce a nonaqueous electrolyte storage element. (First charge and initial capacity measurement) The positive electrode lead wire and negative electrode lead wire of the nonaqueous electrolyte storage element prepared as described above were connected to a charge / discharge tester, and the element was charged at a constant current and constant voltage of 4.2 V at a current rate of 0.2 C for 5 hours. After charging was completed, the element was left standing in a thermostatic chamber at 40°C for 5 days. The element was then discharged at a constant current and constant voltage of 0.2 C to 2.5 V. The element was then charged at a constant current and constant voltage of 4.2 V at a current rate of 0.2 C for 5 hours, and after a 10-minute break, was discharged at a constant current and constant voltage of 0.2 C to 2.5 V. The discharge capacity at this time was recorded as the initial capacity.

[0277] (Power density evaluation test): Rating 3 The positive and negative electrode leads of the nonaqueous electrolyte storage element, whose initial capacity had been measured as described above, were connected to a charge / discharge tester and charged at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours. After a 10-minute break, the element was discharged at a constant current of 0.2 C for 2.5 hours, bringing the charge depth of the nonaqueous electrolyte storage element to 50%. Pulses of current rates of 1 C to 10 C were then applied for 10 seconds. The power required to reach a 2.5 V cutoff voltage was calculated from the correlation line between the post-pulse voltage and the current value, and the power density (Wh / kg) was calculated by dividing this by the cell weight. The resulting power density was 3150 Wh / kg.

[0278] (Life evaluation test): Rating 4 The positive and negative electrode leads of the nonaqueous electrolyte storage element, whose initial capacity had been measured as described above, were connected to a charge / discharge tester and subjected to constant-current / constant-voltage charging at a maximum voltage of 4.2 V and a current rate of 1 C for 3 hours. After charging was completed, the element was discharged at a constant current rate of 1 C to 2.5 V. This cycle was repeated 1,000 times with a 10-minute pause between cycles. After cycling, the element was charged at a maximum voltage of 4.2 V and a current rate of 0.2 C for 5 hours. After charging was completed, the element was discharged at a constant current rate of 0.2 C to 2.5 V with a 10-minute pause between cycles. The discharge capacity at this time was taken as the post-cycle discharge capacity, and the cycle capacity retention rate (post-cycle discharge capacity / initial discharge capacity × 100) was calculated. The results were evaluated according to the following criteria. [Evaluation criteria] ○: 0.2C discharge capacity after 1000 cycles is 80% or more of the initial 0.2C discharge capacity ×: 0.2C discharge capacity after 1000 cycles is less than 80% of the initial 0.2C discharge capacity (Safety evaluation test): Rating 5 The positive electrode lead wire and negative electrode lead wire of the nonaqueous electrolyte storage element whose initial capacity had been measured as described above were connected to a charge / discharge tester, and the element was charged at a constant current and constant voltage of 4.2 V at a current rate of 1 C for 3 hours until the charge depth reached 100% (fully charged). Next, a 4.5 mm diameter iron nail was inserted parallel to the direction in which the electrodes were stacked, intentionally short-circuiting the element, and the state of the element was observed. The observation results were evaluated according to the following criteria. [Evaluation criteria] ○: No ignition ×: Ignition occurred [Example 23] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the thickness of the second mixed layer of inorganic particles and porous resin on the negative electrode was 15 μm and no porous resin layer was provided. A nonaqueous electrolyte storage element was then produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0279] [Example 24] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the thickness of the first mixed layer of the negative electrode mixture and inorganic particles on the negative electrode was set to 5 μm. A nonaqueous electrolyte storage element was produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0280] [Example 25] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the thickness of the inorganic particle layer on the negative electrode was 25 μm and the second mixed layer of inorganic particles and porous resin and the porous resin layer were not provided. A nonaqueous electrolyte storage element was then produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0281] [Example 26] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the thickness of the porous resin film on the negative electrode was set to 50 μm. A nonaqueous electrolyte storage element was then produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0282] Comparative Example 7 Only a negative electrode composite layer was provided on the negative electrode, and the first mixed layer of the negative electrode composite and inorganic particles, the inorganic particle layer, the second mixed layer of inorganic particles and a porous resin, and the porous resin layer were not provided. The negative electrode and positive electrode were fabricated under the same conditions as in Example 22, except that a polyolefin separator with a thickness of 20 μm was provided between the negative electrode and the positive electrode. Then, a nonaqueous electrolyte storage element was fabricated in the same manner as in Example 22, and Evaluations 3 to 5 were performed.

[0283] [Comparative Example 8] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the first mixed layer of the negative electrode mixture and inorganic particles was not formed on the negative electrode. Then, a nonaqueous electrolyte storage element was produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0284] Comparative Example 9 A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that no inorganic particle layer was provided on the negative electrode and the thickness of the resin porous layer was set to 15 μm. A nonaqueous electrolyte storage element was then produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0285] [Comparative Example 10] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the second mixed layer of inorganic particles and porous resin on the negative electrode was not provided and the thickness of the porous resin layer was set to 15 μm. A nonaqueous electrolyte storage element was then produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0286] [Comparative Example 11] A negative electrode and a positive electrode were fabricated under the same conditions as in Example 22, except that the first mixed layer of the negative electrode mixture and inorganic particles was not provided on the negative electrode, the inorganic particle layer was not provided, the second mixed layer of inorganic particles and a porous resin was not provided, and the film thickness of the porous resin layer was set to 0.5 μm. A nonaqueous electrolyte storage element was then fabricated in the same manner as in Example 22, and initial charging was performed, but a short circuit occurred and normal charging was not possible.

[0287] [Comparative Example 12] A negative electrode and a positive electrode were produced under the same conditions as in Example 22, except that the thickness of the porous resin film on the negative electrode was 150 μm. A nonaqueous electrolyte storage element was then produced in the same manner as in Example 22, and evaluations 3 to 5 were carried out.

[0288] The thickness of each layer in each example and comparative example is shown in Table 1. If a corresponding layer was not formed, it is marked as "none" in Table 1. The evaluation results for each example and comparative example are shown in Table 2.

[0289] [Table 1]

[0290] [Table 2] [Comparison between Example 22 and Comparative Example 7] Regarding the nonaqueous electrolyte storage element of Example 22 and the nonaqueous electrolyte storage element of Comparative Example 7, the results of Evaluation 3 showed that Example 22 had a power density of 3150 Wh / kg and Comparative Example 7 had a power density of 2700 Wh / kg. Furthermore, the results of Evaluation 4 showed that Example 22 was rated as good and Comparative Example 7 was rated as bad, and the results of Evaluation 5 showed that Example 22 was rated as good and Comparative Example 7 was rated as bad.

[0291] The difference between the nonaqueous electrolyte storage elements of Example 22 and Comparative Example 7 is the presence or absence of a first mixed layer of the negative electrode composite and inorganic particles on the negative electrode composite layer. It was confirmed that providing the first mixed layer of the negative electrode composite and inorganic particles on the negative electrode composite layer as in Example 22 suppresses lithium deposition near the surface of the negative electrode composite layer, thereby improving life characteristics.

[0292] Another difference between the nonaqueous electrolyte storage elements of Example 22 and Comparative Example 7 is the presence or absence of an inorganic particle layer. It was confirmed that the presence of the inorganic particle layer improved safety, as in Example 22.

[0293] Another difference between the nonaqueous electrolyte storage elements of Example 22 and Comparative Example 7 is the presence or absence of a second mixed layer of inorganic particles and porous resin. In the nonaqueous electrolyte storage elements of Example 22 and Comparative Example 7, the insulating layer between the negative electrode and positive electrode (in Example 22, it is the sum of the inorganic particle layer, the second mixed layer of inorganic particles and porous resin, and the porous resin layer, while in Comparative Example 7 it corresponds to the polyolefin separator) has the same thickness of 20 μm. However, it was confirmed that the presence of the second mixed layer of inorganic particles and porous resin in Example 22 improves the ionic conductivity of the porous resin, resulting in improved output performance.

[0294] [Results of Example 23] The evaluation results of the nonaqueous electrolyte storage element of Example 23 were as follows: Evaluation 3: output density 3, 300 Wh / kg; Evaluation 4: ○; and Evaluation 5: ○. The output density is further improved compared to Example 22. Compared to Example 22, the resin porous layer is not provided, but the film thickness of the second mixed layer of inorganic particles and porous resin is increased. In this case, the total film thickness of the inorganic particle layer, the second mixed layer of inorganic particles and porous resin, and the resin porous layer of Example 22 was set to be equal to the total film thickness of the inorganic particle layer and the second mixed layer of inorganic particles and porous resin of Example 23.

[0295] Comparing the results of Evaluation 3, Example 22 had a power density of 3150 Wh / kg, while Example 23 had a power density of 3300 Wh / kg. It was confirmed that by increasing the film thickness of the second mixed layer of inorganic particles and porous resin as in Example 23, the ion conductivity in the porous resin improved, resulting in improved output performance.

[0296] [Results of Example 24] In the nonaqueous electrolyte storage element of Example 24, the film thickness of the first mixed layer of the negative electrode composite and inorganic particles was set to 5 μm. In Example 24, the result of Evaluation 4 was ○, and an improvement in life characteristics was confirmed compared to Comparative Example 7, which did not have the first mixed layer of the negative electrode composite and inorganic particles.

[0297] [Results of Example 25] In Example 25, in order to prevent short circuits between the positive and negative electrodes, only an inorganic particle layer with a thickness of 25 μm was provided on the first mixed layer of the negative electrode. In this nonaqueous electrolyte storage element, short circuits between the positive and negative electrodes were prevented and the element functioned normally as a nonaqueous electrolyte storage element. In other words, it was confirmed that as long as the element had the first mixed layer and the inorganic particle layer, the element could function normally as a nonaqueous electrolyte storage element even if it did not have the second mixed layer and the resin porous layer.

[0298] [Results of Example 26] Although the nonaqueous electrolyte storage element of Example 26 had a thicker resin porous layer thickness of 50 μm compared to Example 22, the result of Evaluation 3 showed an output density of 2800 Wh / kg, confirming good output characteristics.

[0299] [Results of Comparative Example 8] The first mixed layer of the negative electrode mixture and inorganic particles was not provided in the nonaqueous electrolyte storage element of Comparative Example 8. The result of Evaluation 4 was ×, and the result was that the life was inferior to Examples 22 to 26 in which the negative electrode mixture and inorganic particle layer were provided.

[0300] [Results of Comparative Example 9] No inorganic particle layer was provided in the nonaqueous electrolyte storage element of Comparative Example 9. The result of evaluation 5 was x, which indicated that the element was inferior in safety compared to Examples 22 to 26 in which an inorganic particle layer was provided.

[0301] [Results of Comparative Example 10] The nonaqueous electrolyte of Comparative Example 10 did not have a second mixed layer of inorganic particles and porous resin. The results of Evaluation 3 showed that the power density was 2700 Wh / kg, which was inferior to Examples 22 to 24 in power density characteristics, in which a second mixed layer of inorganic particles and porous resin was provided.

[0302] [Results of Comparative Example 11] In the nonaqueous electrolyte storage element of Comparative Example 11, only a 0.5 μm-thick resin porous layer was provided on the negative electrode. When this nonaqueous electrolyte storage element was initially charged, a short circuit occurred and it was not charged normally. This was because the thickness of the resin porous layer was too small, which reduced the inter-electrode distance between the negative and positive electrodes and made it impossible to prevent a short circuit.

[0303] [Comparison with Comparative Example 12 / Example 22] The nonaqueous electrolyte storage element of Comparative Example 12 had a resin porous layer with a film thickness of 150 μm, which was thicker than that of Example 22. The results of Evaluation 3 showed that Comparative Example 12 had a power density of 2500 Wh / kg and Example 22 had a power density of 3150 Wh / kg, indicating that Comparative Example 12, which had a larger inter-electrode distance between the negative electrode and the positive electrode, had a power density characteristic inferior to that of Example 22.

[0304] Although the preferred embodiments have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications and substitutions can be made to the above-described embodiments without departing from the scope of the claims.

[0305] For example, in each of the above embodiments, an example was shown in which the negative electrode 17, etc. was used in a non-aqueous electrolyte storage element, but this is not limited thereto, and the negative electrode 17, etc. can also be used in a storage element that uses a gel electrolyte, and in that case, the same effects as when used in a non-aqueous electrolyte storage element are achieved. [Explanation of symbols]

[0306] 1, 1A, 1B, 1C, 1D Non-aqueous electrolyte storage element 10, 10A, 17, 17A, 17B, 17C negative electrode 11 Electrode base for negative electrode 12 Negative electrode composite layer 13 Inorganic particle layer 14, 15 mixed layer 16. Porous resin layer 20, 27 positive electrode 21 Electrode base for positive electrode 22 Positive electrode mixture layer 30 Separator 40, 40A, 40B, 40C, 40D electrode elements 41 Negative electrode lead wire 42 Positive electrode lead wire 51 Electrolyte layer 52 Exterior 60 Core-shell structure 61 Inorganic particles 62 Polymer [Prior art documents] [Patent documents]

[0307] [Patent Document 1] Special Publication No. 2015-518644

Claims

1. insulating inorganic particles having a surface potential; a polymer having an ionic functional group (A) and an ion-conductive functional group (B) that are charged oppositely to the surface potential of the inorganic particles; a binder; The binder is contained in an amount of 0.5% by mass or more and 5% by mass or less relative to the inorganic particles, The polymer is contained in an amount of 40% by mass or more and 100% by mass or less relative to the binder, the inorganic particles and the polymer are bonded to each other, The inorganic particles are alumina particles, and the ionic functional group (A) is an anionic functional group. A liquid composition for forming an inorganic particle layer of an electrode, for forming an inorganic particle layer having an area resistance of 0.01 Ω·cm 2 or more and 1.0 Ω·cm 2 or less.

2. An inorganic particle layer coating step of coating the liquid composition for forming an inorganic particle layer of an electrode according to claim 1 onto an electrode mixture layer. A method for manufacturing an electrode comprising:

3. A first mixed layer forming step of forming a first mixed layer on an electrode mixture layer; an inorganic particle layer coating step of coating the liquid composition for forming an inorganic particle layer of an electrode according to claim 1 onto the first mixed layer, The first mixed layer is an electrode mixture; Inorganic particles; The inorganic particle is characterized by comprising a polymer having an ionic functional group (A) and an ion-conductive functional group (B) that are charged oppositely to the surface potential of the inorganic particle. Electrode manufacturing method.

4. The film thickness of the first mixed layer is in the range of 1% to 20% of the film thickness of the electrode mixture layer. The method for manufacturing the electrode according to claim 3 .

5. On the inorganic particle layer formed by applying the composition for forming an inorganic particle layer of the electrode, A second mixed layer forming step of forming a second mixed layer containing inorganic particles and resin porous material. The method for manufacturing an electrode according to claim 3 or 4, comprising:

6. The thickness of the second mixed layer is 0.1 μm or more and 100 μm or less. The method for manufacturing the electrode according to claim 5 .

7. a resin porous layer forming step of forming a resin porous layer on the second mixed layer; The method for manufacturing an electrode according to claim 5 or 6, comprising:

8. The resin porous layer has a thickness of 0.1 μm or more and 100 μm or less. The method for manufacturing the electrode according to claim 7 .

9. the total thickness of the inorganic particle layer, the second mixed layer, and the resin porous layer is 0.1 μm or more and 100 μm or less; The method for producing the electrode according to claim 7 or 8.

10. insulating inorganic particles having a surface potential; a polymer having an ionic functional group (A) and an ion-conductive functional group (B) that are charged oppositely to the surface potential of the inorganic particles; a binder; The binder is contained in an amount of 0.5% by mass or more and 5% by mass or less relative to the inorganic particles, The polymer is contained in an amount of 40% by mass or more and 100% by mass or less relative to the binder, the inorganic particles and the polymer are bonded to each other, The inorganic particles are alumina particles, and the ionic functional group (A) is an anionic functional group. a coating step of coating, onto the electrode mixture layer, a liquid composition for forming an inorganic particle layer having an area resistance of 0.01 Ω·cm 2 or more and 1.0 Ω·cm 2 or less; The electrode mixture layer is characterized in that it contains an electrode active material. Electrode manufacturing method.

11. insulating inorganic particles having a surface potential; a polymer having an ionic functional group (A) and an ion-conductive functional group (B) that are charged oppositely to the surface potential of the inorganic particles; a binder; The binder is contained in an amount of 0.5% by mass or more and 5% by mass or less relative to the inorganic particles, The polymer is contained in an amount of 40% by mass or more and 100% by mass or less relative to the binder, the inorganic particles and the polymer are bonded to each other, The inorganic particles are alumina particles, and the ionic functional group (A) is an anionic functional group. a coating step of coating the first mixed layer with a liquid composition for forming an inorganic particle layer having an area resistance of 0.01 Ω·cm 2 or more and 1.0 Ω·cm 2 or less; The first mixed layer is characterized in that it contains an electrode mixture, inorganic particles, and a polymer having an ionic functional group (A) and an ion-conductive functional group (B) that are charged oppositely to the surface potential of the inorganic particles. Electrode manufacturing method.

12. On the inorganic particle layer formed by applying a liquid composition on the first mixed layer, A second mixed layer forming step of forming a second mixed layer containing inorganic particles and resin porous material. The method for manufacturing an electrode according to claim 11 , comprising:

13. a resin porous layer forming step of forming a resin porous layer on the second mixed layer; The method for manufacturing an electrode according to claim 12, comprising:

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