Method for manufacturing or recycling components for electrochemical devices, method for manufacturing electrochemical devices, components for electrochemical devices, and electrochemical devices

Abstract

A purpose of the present invention is to provide a method for manufacturing, etc., a member for an electrochemical device in which the problem of unavoidable change in the composition of the electrochemical device due to solvent depletion, moisture absorption, etc., during manufacturing of the electrochemical device is unlikely to occur. This method for manufacturing a member for an electrochemical device includes performing at least one molding operation disclosed in the present specification on a formation material composition that: includes at least one filling agent (F), a plasticizer (P-S) that is water, an ionic liquid, or a mixture of these, and a polymer (P1); does not substantially include an organic solvent; and has plasticity and is self-supporting.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing or recycling components for electrochemical devices, a method for manufacturing electrochemical devices, components for electrochemical devices, and electrochemical devices. [Background technology]

[0002] Conventionally, electrodes containing active materials have been used in primary batteries such as lithium primary batteries; non-aqueous secondary batteries such as lithium-ion secondary batteries, lithium metal secondary batteries, sodium-ion secondary batteries, potassium-ion secondary batteries, magnesium secondary batteries, and aluminum secondary batteries; air batteries; solar cells such as dye-sensitized solar cells; capacitors such as electric double-layer capacitors and lithium-ion capacitors; electrochromic display devices; electrochemical light-emitting devices; electric double-layer transistors; and electrochemical actuators.

[0003] For example, Patent Document 1 describes that the problem is to provide an electrode paste in which the contact surface area of ​​the active material particles with the solution is uniform, and that an electrode paste is manufactured by mixing a solid particle component of the active material with a liquid non-volatile plasticizer component and a volatile anhydrous grinding solvent using chemically dried material to form a slurry, grinding the slurry until the particle size and particle size distribution reach desired values, and removing the volatile anhydrous grinding solvent.

[0004] Furthermore, for example, Patent Document 2 describes a method for manufacturing a positive electrode plate for a non-water battery, which involves applying a paste mainly containing a solution of an active material powder such as manganese dioxide, a binder made of fluororesin that is fibrous in an unsintered state and forms a bonding network, and a viscous agent made of polyethylene oxide to an electrode core, and then heat-treating it at a temperature below the decomposition temperature of the polyethylene oxide to remove moisture.

[0005] Furthermore, for example, Patent Document 3 describes an electrolyte composition for an electrochemical device comprising an ionic substance and a plasticizer consisting of an organic compound including a high-boiling point organic compound, and an electrode for an electrochemical device comprising an electrode composite layer obtained by molding a mixture obtained by mixing the electrolyte composition for an electrochemical device with an electrode active material, as well as methods for manufacturing these. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-334886 [Patent Document 2] Japanese Patent Application Publication No. 61-91861 [Patent Document 3] Japanese Patent Publication No. 2019-114390 [Overview of the project] [Problems that the invention aims to solve]

[0007] The technologies described in Patent Documents 1 and 3 involve manufacturing electrodes by applying a molding material (paste, slurry, compound) obtained by kneading an active material with an electrolyte to a current collector or molding it on the current collector, while ensuring that the non-aqueous organic solvent in the electrolyte does not completely evaporate. However, with such a manufacturing method, if the non-aqueous organic solvent evaporates excessively when the molding process is in an open atmosphere, it becomes difficult to replenish the evaporated organic solvent. Furthermore, if moisture absorption occurs, it becomes difficult to remove the absorbed moisture, making it difficult to recover the quality once it has changed. Therefore, there is a problem in that the amount of evaporation must be controlled in order to obtain stable production and stable device performance. In addition, in electrode manufacturing, if proper control is not implemented, there is a risk that workers will be exposed to evaporating non-aqueous organic solvents, which is also a problem.

[0008] Furthermore, while the technology described in Patent Document 2 has been examined for its applicability to the manufacture of positive electrodes for lithium primary batteries, its applicability to the manufacture of components used in other batteries such as lithium-ion secondary batteries has not been examined. In addition, the technology described in Patent Document 2 has not examined the quality changes and recovery of the components due to fluctuations in the amount of solvent during the manufacturing process. In particular, the accuracy of electrode measurements (e.g., electrode thickness, accuracy of electrode surface roughness) is more important in secondary batteries than in primary batteries, but the technology described in Patent Document 2 has not examined the accuracy of electrode measurements. Furthermore, the formation of components by shaping operations has not been performed.

[0009] Therefore, the present invention aims to provide a method for manufacturing components for electrochemical devices that is less prone to problems such as irreversible changes in the composition of electrochemical devices due to solvent reduction, moisture absorption, etc., during the manufacturing of electrochemical devices. [Means for solving the problem]

[0010] As a result of diligent research to achieve the above objective, the inventors have discovered that by performing a predetermined shaping operation on a molding material composition comprising a filler, a plasticizer which is water, an ionic liquid, or a mixture thereof, and a polymer, substantially free of organic solvents, having plasticity and self-supporting properties, and in which the polymer is plasticized with the plasticizer, it is possible to manufacture an electrochemical device component in which irreversible quality changes during the manufacturing process are suppressed, thus completing the present invention.

[0011] In other words, the present invention aims to advantageously solve the above problems, and the method for manufacturing electrochemical device components of the present invention is At least one type of filler (F); Plasticizers (PS) which are water, ionic liquids, or mixtures thereof; and Polymer (P1) The present invention is characterized by performing at least one shaping operation selected from the following group A on a molding material composition that contains, substantially does not contain organic solvents, and is plastic and self-supporting. [Group A: Extrusion, injection into a mold, stretching, compression molding, reduction in thickness by pressure, thickness uniformity by pressure, cutting, hole drilling, cutting, bending into the final shape to be housed in an electrochemical device container, bonding of molding material compositions with different compositions]

[0012] If an electrochemical device (e.g., an electrode) is manufactured using the member for an electrochemical device thus produced, irreversible changes in the electrochemical device composition due to solvent reduction, moisture absorption, etc. during the manufacture of the electrochemical device can be suppressed.

[0013] Polymer (P1) may be a polymer that can also be plasticized with an electrolyte solvent (E-S). Further, polymer (P1) may be a deliquescent polymer. Polymer (P1) is preferably a polymer containing ethylene oxide (EO) as a monomer unit, a polyoxazoline-based polymer, a poly-N-vinylacetamide-based polymer, or an epichlorohydrin-organic amine condensate.

[0014] Filler (F) may contain active material (A). Further, filler (F) may contain an inorganic solid electrolyte. Further, filler (F) may contain a fibrous substance. Further, filler (F) may contain a solid lubricant.

[0015] The fibrous substance may have a fiber length of 10 μm or more. Further, the fibrous substance may have a fiber length equal to or greater than the thickness of the member for an electrochemical device. Further, the fibrous substance may have a fiber diameter of nanosize.

[0016] The solid lubricant may be selected from the following Group B. [Group B: graphite, graphene, boron nitride, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), molybdenum sulfide, tungsten disulfide, mica, talc, graphite fluoride, melamine cyanurate, metal soap]

[0017] The filler (F) may be nano-sized. The volume fraction of the molded material composition that is filled by the filler (F) may be 50% by volume or more.

[0018] The molding material composition may further contain a polymer (P2) that is plasticized by a plasticizer (PS) but does not dissolve in the electrolyte.

[0019] The method for manufacturing components for electrochemical devices of the present invention may include irreversibly crosslinking a polymer (P1). The crosslinking method may be thermal crosslinking. Alternatively, the crosslinking method may be UV crosslinking. Furthermore, the crosslinking agent may be added to the molding material composition. Alternatively, the crosslinking agent may be added to the electrolyte. Furthermore, the polymer (P1) may be a self-crosslinking polymer.

[0020] The present invention's method for manufacturing electrochemical device components may include controlling and providing feedback on the basis weight by measuring the thickness of the component. Furthermore, the present invention's method for manufacturing electrochemical device components may include forming a sheet by crushing multiple strands made of a molding material composition. Furthermore, the present invention's method for manufacturing electrochemical device components may include obtaining a component by scraping it from a block of molding material composition.

[0021] Furthermore, the method for manufacturing an electrochemical device component of the present invention may include attaching the molding material composition to a substrate. The method for manufacturing an electrochemical device component of the present invention may include attaching the molding material composition to a substrate after shaping it to a desired thickness. Furthermore, the method for manufacturing an electrochemical device component of the present invention may include attaching the molding material composition to both the front and back surfaces of the substrate substantially simultaneously. Furthermore, the method for manufacturing an electrochemical device component of the present invention may include attaching the molding material composition to the front surface of the substrate and then to the back surface. The substrate may have a conductive coating on the surface in contact with the molding material composition. Furthermore, the substrate may mainly contain polymers. In the method for manufacturing an electrochemical device component of the present invention, after attaching the molding material composition to the substrate, it is not necessary to cut or drill holes in the component together with the substrate.

[0022] The component may be an electrode or an insulating layer.

[0023] The shaping operation selected from group A may be performed at least once while the molding material composition is not in contact with the current collector foil. Furthermore, the shaping operation selected from group A may be performed at least once while the molding material composition is not in contact with the porous separator film.

[0024] When the plasticizer (PS) is water or a mixture of water and an ionic liquid, the method for manufacturing an electrochemical device component of the present invention may include shaping the molding material composition to the final shape when the component is placed in the device, and then removing the moisture by a drying operation to bring it to a non-plasticized state. The drying operation may be carried out by vacuum or heating. The drying operation may also be carried out when the molding material composition is not in contact with the current collector foil. The drying operation may also be carried out when the molding material composition is not in contact with the porous separator film.

[0025] The method for manufacturing an electrochemical device component of the present invention may include a step of peeling off a molding material composition that is already attached to a substrate from the substrate. The method for manufacturing an electrochemical device component of the present invention may also include restoring the plasticity state by adding water or humidifying the molding material composition or the molding material composition that has undergone a crosslinking operation after it has become non-plasticized. Furthermore, the method for manufacturing an electrochemical device component of the present invention may also include manufacturing the next component using scraps of the molding material composition generated in the process of shaping the molding material composition.

[0026] Furthermore, the method for recycling electrochemical device components of the present invention includes, in the above-described method for manufacturing electrochemical device components, a step of peeling off the molding material composition already attached to the substrate from the substrate. In another embodiment, in the above-described method for manufacturing electrochemical device components, the method includes restoring the plasticity state by adding water or humidifying the molding material composition again after it has become non-plasticized. In yet another embodiment, in the above-described method for manufacturing electrochemical device components, the method includes manufacturing the next component again using the scraps of the molding material composition generated in the process of shaping the molding material composition.

[0027] The molding material composition used in the present invention can suppress irreversible changes in the composition of electrochemical devices due to solvent reduction, moisture absorption, etc., during the manufacture of electrochemical devices, so that components for electrochemical devices can be recycled without changing their quality.

[0028] The present invention provides a method for manufacturing an electrochemical device, which includes obtaining components by the manufacturing method or recycling method described above.

[0029] In the method for manufacturing the electrochemical device of the present invention, the polymer (P1) may be a polymer that can be plasticized in the electrolyte solvent (ES). Furthermore, in the method for manufacturing the electrochemical device of the present invention, the molding material composition may further contain a polymer (P2) that can be plasticized with a plasticizer (PS) but does not dissolve in the electrolyte. Furthermore, in the method for manufacturing the electrochemical device of the present invention, the crosslinking agent may be added to the electrolyte.

[0030] The electrochemical device component of the present invention is obtained by the manufacturing or recycling method described above. The electrochemical device component may be an electrode or an insulating layer.

[0031] The electrochemical device of the present invention includes the electrochemical device components described above.

[0032] The electrochemical device of the present invention may include an electrode obtained by the manufacturing or recycling method described above, and a counter electrode for said electrode, the counter electrode may include at least one selected from alkali metals, alkaline earth metals, metallic aluminum, and silver.

[0033] The electrochemical device of the present invention may be a water-containing electrochemical device in which the carrier ions are at least one of alkali metal ions, alkaline earth metal ions, aluminum ions, silver ions, organic nitrogen cations, and halide anions, bis(fluoromethanesulfonyl)imidobis(trifluoromethanesulfonyl)imido anions, and trifluoromethanesulfonic acid anions. Examples of water-containing electrochemical devices include electrochemical devices in which water is contained in the electrolyte (e.g., water-containing lithium-ion secondary batteries, manganese-zinc primary batteries, and other water-containing batteries).

[0034] The electrochemical device of the present invention may be a non-aqueous electrochemical device. Furthermore, the electrochemical device of the present invention may be a non-aqueous electrochemical device in which the carrier ions are at least one of alkali metal ions, alkaline earth metal ions, aluminum ions, silver ions, organic nitrogen cations, and halide anions, bis(fluoromethanesulfonyl)imidobis(trifluoromethanesulfonyl)imido anions, and trifluoromethanesulfonic acid anions. Examples of non-aqueous electrochemical devices include electrochemical devices in which the electrolyte is dissolved in an organic solvent and does not contain water (e.g., non-aqueous lithium-ion secondary batteries, lithium primary batteries, manganese lithium primary batteries, and other non-aqueous batteries). [Effects of the Invention]

[0035] According to the present invention, it is possible to provide a method for manufacturing and recycling components for electrochemical devices that is less prone to problems such as irreversible changes in the composition of electrochemical devices due to solvent reduction, moisture absorption, etc., during the manufacturing of electrochemical devices. Furthermore, according to the present invention, it is possible to provide an electrochemical device component that is less susceptible to problems such as irreversible changes in the composition of an electrochemical device due to solvent reduction, moisture absorption, etc., during the manufacture of an electrochemical device, and an electrochemical device using said electrochemical device component. [Modes for carrying out the invention]

[0036] The method for manufacturing and recycling components for electrochemical devices of the present invention is not particularly limited and can be used, for example, when manufacturing or recycling components used in non-aqueous or aqueous primary batteries such as lithium primary batteries and manganese primary batteries (e.g., manganese-zinc primary batteries, manganese-lithium primary batteries); non-aqueous or aqueous secondary batteries such as lithium-ion secondary batteries (non-aqueous, aqueous), lithium metal secondary batteries, sodium-ion secondary batteries, potassium-ion secondary batteries, magnesium secondary batteries, and aluminum secondary batteries; air batteries; solar cells such as dye-sensitized solar cells; capacitors such as electric double-layer capacitors and lithium-ion capacitors; electrochromic display devices; electrochemical light-emitting elements; electric double-layer transistors; and electrochemical actuators. Furthermore, the electrochemical device component of the present invention may be manufactured or recycled by the method for manufacturing or recycling the electrochemical device component of the present invention. Furthermore, the electrochemical device of the present invention may also utilize the electrochemical device components of the present invention. Furthermore, the electrochemical device described above is preferably a non-aqueous secondary battery, and more preferably a lithium-ion secondary battery.

[0037] (Method for manufacturing components for electrochemical devices) The method for manufacturing a component for an electrochemical device of the present invention is as follows: At least one type of filler (F); Plasticizers (PS) which are water, ionic liquids, or mixtures thereof; and Polymer (P1) The process involves performing at least one shaping operation selected from group A below on a molding material composition that contains, is substantially free of organic solvents, and is plastic and self-supporting. Preferably, the polymer (P1) may be plasticized with a plasticizer (PS). [Group A: Extrusion, injection molding, stretching, compression molding, thickness reduction by pressurization, thickness uniformization by pressurization, cutting, drilling, machining, bending into the final shape for housing electrochemical device containers, bonding of molding material compositions with different compositions]

[0038] <Molding material composition> A "molding material composition" is a semi-solid material for forming components for electrochemical devices. A molding material composition can be obtained by mixing at least one filler (F), a plasticizer (PS), and a polymer (P1) as described above, along with optionally additional components, under conditions that are substantially free of organic solvents. These components may be mixed simultaneously or sequentially, and the order in which the components constituting the molding material composition are added does not matter. The mixing operation may be carried out using a batch mixer, a continuous kneader, or a combination of both. The polymer may be added as a powder or as a solution dissolved in a solvent. From the viewpoint of uniform dispersion, it is preferable to mix the powdered materials together beforehand. The mixing operation is not particularly limited and can be carried out using known mixing equipment such as a multi-screw extruder, a bead mill, a roll kneader, a closed-type kneader (e.g., a kneader, a Banbury mixer, a planetary agitator, etc.), a high-speed agitator mixer (e.g., a Henschel mixer, a coffee mill, etc.), a rolling granulator, or a fluidized bed granulator. The mixing temperature is preferably below the melting point of the polymer (P1), and usually below room temperature (35°C or below). The mixing temperature is preferably above the freezing point of the plasticizer (PS), and usually above 0°C. If the molding material composition is in powder form, there is a high risk that the fine powder will enter the inside of electrochemical devices (e.g., batteries) or manufacturing equipment. Therefore, the molding material composition of the present invention is handled in a clay-like (compound-like) form.

[0039] The molding material composition used in the present invention is plastic and self-supporting. In this specification, "plastic" means that, under conditions of 25°C, a single block of the molding material composition can be divided into two or more parts and then reassembled into a single block. In this specification, "self-supporting" means that it has resistance to deformation and collapse due to its own weight when stationary and when moved in space, and that its shape is maintained. That is, when the material is left stationary for a long time, it maintains its shape without being affected by its own weight, and can be moved in the air while maintaining its shape. Specifically, "self-supporting" means that, under conditions of 25°C, it can be molded into a sheet of at least 10 × 10 × 2 mm, the sheet does not flow when placed on a flat surface, its shape does not change for at least 1 hour or more, and this can be maintained from the edge of the sheet up to 1 / 10 cm. 2 This refers to the ability to grasp and lift an object with tweezers of the following area. The larger the area and the thinner the thickness, the higher the object's ability to stand on its own.

[0040] <Filler (F)> Filler (F) refers to a solid substance that forms a component for an electrochemical device. Filler (F) is usually in granular or powder form. Preferably, filler (F) may be a solid substance having a short diameter smaller than at least the thickness of the component. Examples of filler (F) include active material (A), inorganic solid electrolyte, fibrous material, solid lubricant, conductive material (e.g., conductive carbon), reinforcing material, power enhancer, flame retardant, gas generating agent, resistance-increasing plastic particles, and other simple fillers with no particular function. These classifications of filler (F) are based on function, application, physical properties, etc., and the same substance may belong to multiple classifications.

[0041] When the filler is in particulate form, reducing the particle size is preferable because it increases the specific surface area and strengthens the cohesive force. In particular, it is preferable to use a nano-sized filler (maximum diameter less than 1 μm) as the filler (F), and more preferably a filler with a volume-average particle diameter of 100 nm to 900 nm. By using a nano-sized filler, the contact area with the electrolyte is increased, making it possible to form a component (e.g., electrode) with excellent strength and a component (e.g., electrode) that can carry out electrochemical reactions smoothly. It is preferable that the diameter of the filler is smaller than the thickness of the component itself, but even if the major axis is larger than the thickness of the component itself, it can be used as long as the minor axis is smaller than the thickness of the component, as it will be oriented laterally. In this invention, the volume-average particle size of the particulate filler can be measured in accordance with JIS K8825.

[0042] Furthermore, the content of the filler (F) in the molding material composition is preferably 50% by volume or more, and more preferably 60% by volume or more. If the content of the active material (A) is above the lower limit mentioned above, it is possible to form a component (e.g., an electrode) capable of producing an electrochemical device with high functionality (e.g., high capacity).

[0043] When the molding material composition is not crosslinked, a higher solid content in the components (e.g., electrodes, separators) is preferable because it improves self-supporting properties. The solid content in the molding material composition is preferably 40 vol% or more, 50 vol% or more, 60 vol% or more, or 70 vol% or more. A solid content exceeding 80 vol% is preferable because plasticity deteriorates if it exceeds 80 vol%. If the device is an energy storage element, a higher active material density is preferable from the viewpoint of energy density.

[0044] <Active material (A)> The active material (A) is not particularly limited, and any active material can be used depending on the type of electrochemical device. The active material (A) contained in the molding material composition may consist of only one type of active material, or it may be a mixture of two or more types of active materials.

[0045] Examples of the active material (A) include an electrode active material (when the member for the electrochemical device is an electrode).

[0046] <Electrode active material> When the member for the electrochemical device is an electrode, the electrode contains an electrode active material as the active material (A). As the electrode active material, an electrode active material corresponding to the type of the electrochemical device in which the electrode to be manufactured is used can be used. As an example, when the electrochemical device is a battery (e.g., a non-aqueous or aqueous secondary battery such as a lithium ion secondary battery (non-aqueous, aqueous), a lithium primary battery, a non-aqueous or aqueous primary battery such as a manganese primary battery (manganese zinc primary battery, manganese lithium primary battery), etc.), as the electrode active material, the following electrode active materials can be used without particular limitation.

[0047] <Positive electrode active material> Examples of the positive electrode active material incorporated in the positive electrode mixture layer of the positive electrode of a battery (e.g., a non-aqueous or aqueous secondary battery such as a lithium ion secondary battery (non-aqueous, aqueous), a lithium primary battery, a non-aqueous or aqueous primary battery such as a manganese primary battery (manganese zinc primary battery, manganese lithium primary battery), etc.) include compounds containing a transition metal, such as transition metal oxides, transition metal sulfides, composite metal oxides of lithium and transition metals, elemental sulfur, and redox-active organic compounds. Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, etc. Specifically, the positive electrode active material can be, without particular limitation, lithium-containing cobalt oxide (LiCoO2), lithium manganate (LiMn2O4), lithium-containing nickel oxide (LiNiO2), lithium-containing composite oxide of Co-Ni-Mn, lithium-containing composite oxide of Ni-Mn-Al, lithium-containing composite oxide of Ni-Co-Al, olivine-type lithium iron phosphate (LiFePO4), olivine-type lithium manganese phosphate (LiMnPO4), lithium excess spinel compound represented by Li 1+x Mn 2-x O4 (0 < X < 2), Li[Ni0.17 Li 0.2 Co 0.07 Mn 0.56 O2, LiNi 0.5 Mn 1.5 O4, MOF (Metal-Organic-Framework), benzoquinone, manganese dioxide, etc. can be mentioned. In addition, the above-described positive electrode active material may be used alone or in combination of two or more kinds.

[0048] <Negative electrode active material> As the negative electrode active material blended in the negative electrode composite material layer of the negative electrode of a battery (for example, a non-aqueous or aqueous secondary battery such as a lithium ion secondary battery (non-aqueous, aqueous), a lithium primary battery, a manganese primary battery (manganese zinc primary battery, manganese lithium primary battery), etc.), for example, a carbon-based negative electrode active material, a metal-based negative electrode active material, and a negative electrode active material combining these can be mentioned. Here, the carbon-based negative electrode active material refers to an active material having carbon as a main skeleton into which lithium can be inserted (also referred to as "doped"). And as the carbon-based negative electrode active material, specifically, carbonaceous materials such as coke, mesocarbon microbeads (MCMB), mesophase pitch-based carbon fiber, pyrolytic vapor deposition carbon fiber, phenol resin fired body, polyacrylonitrile-based carbon fiber, quasi-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon, and graphite materials such as natural graphite and artificial graphite can be mentioned. In addition, the metal-based negative electrode active material is an active material containing a metal, and usually contains an element into which lithium can be inserted in the structure, and refers to an active material having a theoretical capacitance per unit mass of 500 mAh / g or more when lithium is inserted. And as the metal-based active material, for example, lithium metal, simple metals that can form a lithium alloy (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Mg, Ni, P, Pb, Sb, Si, Sn, Sr, Zn, Ti, etc.) and their oxides, sulfides, nitrides, silicides, carbides, phosphides, oxalates, formates, etc. can be mentioned. Furthermore, oxides such as lithium titanate can be mentioned. The negative electrode active material described above may be used individually or in combination of two or more types.

[0049] <Filler for insulating layer> When the component for an electrochemical device is an insulating component (e.g., a separator), the insulating component may include a filler for the insulating layer. The filler for the insulating layer can be selected according to the type of electrochemical device that will use the insulating layer being manufactured. The filler for the insulating layer can be arbitrarily selected from substances other than electrically conductive materials, and may be selected in combination of one or more from, for example, simple fillers, solid electrolytes, fibrous materials, solid lubricants, reinforcing materials, power enhancers, flame retardants, gas generating agents, resistance-increasing plastics, etc. It is preferable to include at least one substance with high heat resistance. Even if a conductive material is included, it is sufficient if it is in an amount that does not exhibit conductivity as an insulating layer. As an example, when the electrochemical device is a lithium-ion secondary battery, the filler for the insulating layer is not particularly limited as long as it is not a conductive material, and includes particles made of inorganic materials (i.e., non-conductive inorganic particles) and particles made of organic materials (i.e., non-conductive organic particles) that are stable in the operating environment of the electrochemical device and are electrochemically stable. Among these, non-conductive inorganic particles are preferred. Preferred examples of non-conductive inorganic particles include simple fillers other than electrically conductive materials.

[0050] <Solid electrolyte> From the viewpoint of expecting improved ionic conductivity, the molding material composition may include an inorganic solid electrolyte as a filler (F). The inorganic solid electrolyte may be, for example, an ionic conductive ceramic. Examples of inorganic solid electrolytes include Li-Ge-PS conductors (e.g., Li 10 GeP2S 12 ), Li-Si-PS-Cl system conductors (e.g., Li 9.54 Si 1.74 P 1.44 S 11.7 Cl l0.3 ), Li-La-Zr-O conductors (e.g., Li7La3Zr2O 12(The above are lithium-ion conductors), β-alumina (sodium-ion conductor), Rb-Cu-IC system conductors (e.g., RbCu4I 1.75 C l3.25 Examples include copper ion conductors such as ) and silver ion conductors such as Ag-IWO system conductors (e.g., Ag6I4WO4).

[0051] <Fibrous material> The addition of fibrous material can bridge the gaps between fillers such as inorganic particles, helping to cohesive the molding material composition and improving the strength of components for electrochemical devices (e.g., electrodes). From this viewpoint, the molding material composition may further contain fibrous material as a filler (F). Preferably, the fibrous material has a fiber diameter of at least less than or equal to the thickness of the component and an aspect ratio of 100 or more. Examples of fibrous material include fibers of carbon, metal, plastic, natural polymer, and ceramic. Of these, nanofibers with a fiber diameter of 1 μm or less are preferred, and nano-sized (maximum diameter less than 1 μm) is preferred. Examples of nanofibers with such fiber diameters include carbon nanotubes (CNTs), carbon nanofibers, cellulose nanofibers, polytetrafluoroethylene (PTFE), and ceramic nanofibers. The fiber length of the fibrous material is not particularly limited, but from the viewpoint of joining the fillers together, it may be, for example, 10 μm or more, preferably 20 μm or more, and more preferably 50 μm or more. From the viewpoint of handling the raw materials, it may be, for example, 5 cm or less, preferably 1 cm or less, and more preferably 1 mm or less. Furthermore, from the viewpoint of orienting the fibers in the planar direction to improve tensile strength, the fiber length of the fibrous material is preferably greater than or equal to the thickness of the component for the electrochemical device (e.g., an electrode).

[0052] If too much fibrous material is added, the electrode density will decrease. Therefore, the amount of fibrous material may preferably be 8 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less, relative to the total molding material composition. There are conventional techniques that use only PTFE as a binder to make electrodes, but these require a large amount of PTFE, 10 parts by weight or more, and the electrode density tends to be low. In the present invention, the force that binds together fillers such as active material and conductive particles is mainly due to the adhesiveness of the plasticized polymer, so the fibrous material plays an auxiliary role and does not need to be added in large quantities.

[0053] <Solid Lubricant> From the viewpoint of smoothing the molding process and processing the molding material composition with less force, the molding material composition may contain a solid lubricant as a filler (F). Examples of solid lubricants include those listed in group B below. [Group B: Graphite, graphene, boron nitride, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes (PFA), molybdenum sulfide, tungsten disulfide, mica, talc, graphite fluoride, melamine cyanurate, metallic soaps]

[0054] Examples of metallic soaps include magnesium stearate, magnesium lauryl latate, magnesium palmitate, calcium stearate, calcium oleate, calcium lauryl latate, calcium 12-hydroxystearate, calcium montanate, barium stearate, barium oleate, barium lauryl latate, barium arachidinate, barium behenate, zinc stearate, zinc oleate, zinc lauryl latate, and lithium stearate.

[0055] The concentration of the solid lubricant in the molding material composition is not particularly limited, but from the viewpoint of exhibiting lubricity, it may be, for example, 0.5% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more. From the viewpoint of increasing the ratio of active material and insulating layer filler, it may be, for example, 5% by weight or less, preferably 8% by weight or less, and more preferably 10% by weight or less.

[0056] <Conductive material> From the viewpoint of improving the conductivity of the electrodes, the molding material composition may contain a conductive material as a filler (F). Examples of conductive materials include conductive carbon (e.g., graphite, expanded graphite, graphene, acetylene black, Ketjenblack®, carbon nanohorns, fullerene, CNT) and metal powder (e.g., aluminum, zinc, iron, copper, silver, gold, nickel, titanium). The concentration of the conductive material in the molding material composition is not particularly limited, but from the viewpoint of exhibiting conductivity, it may be, for example, 1% by weight or more, preferably 3% by weight or more, and more preferably 5% by weight or more. From the viewpoint of increasing the ratio of active material, it may be, for example, 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less.

[0057] <Reinforcement material> From the viewpoint of providing reinforcement to electrochemical devices, the molding material composition may include a reinforcing material as a filler (F). Examples of reinforcing materials include whiskers with a large aspect ratio.

[0058] <Power booster> From the viewpoint of improving the output of electrochemical devices, the molding material composition may include an output enhancer as a filler (F). Examples of output enhancers include fillers that provide ion dissociation assistance and fillers that provide output to electrochemical devices. Examples of fillers that provide ion dissociation assistance include nanofillers (e.g., silica, alumina, zirconia, titania). Examples of fillers that provide output to electrochemical devices include ferroelectric materials such as barium titanate.

[0059] <Flame retardant> From the viewpoint of enhancing the safety of electrochemical devices, the molding material composition may contain a flame retardant as a filler (F). Examples of flame retardants include red phosphorus, aluminum hydroxide, magnesium hydroxide, antimony-based (e.g., antimony trioxide), phosphinate metal salts, cyclophosphazene oligomers, polyphosphazenes, aliphatic phosphate amides (e.g., DAIGUARD-850: Daihachi Chemical Industry), chlorinated paraffins (e.g., Enpara 70: Ajinomoto Fine Techno), and melamine cyanurate. The concentration of the flame retardant in the molding material composition is not particularly limited, but from the viewpoint of exhibiting flame retardancy, it may be, for example, 5% by weight or more, preferably 8% by weight or more, and more preferably 10% by weight or more. From the viewpoint of not interfering with the operation of the electrochemical device, it may be, for example, 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less.

[0060] <Gas Generating Agent> From the viewpoint of enhancing safety by providing an effect that increases electrode resistance by generating gas when an electrochemical device overheats abnormally, the molding material composition may include a gas generating agent (which has the effect of generating gas and increasing electrode resistance when an abnormal heat is generated) as a filler (F). Examples of gas generating agents include melamine, melamine cyanurate, ammonium carbonate, ammonium chloride, sodium bicarbonate, and OBSH.

[0061] <Resistance-increasing plastic particles> From the viewpoint of enhancing safety by providing an effect that increases electrode resistance by melting during abnormal heat generation in electrochemical devices, the molding material composition may include resistance-increasing plastic particles as a filler (F). Examples of resistance-increasing plastic particles include polyethylene and polypropylene.

[0062] <Simple filler> The molding material composition may also contain simple fillers with no particular function as a filler (F). Among the simple fillers, fillers composed of substances that do not have electrical conductivity can also be used as fillers for insulating layers. Examples of fillers that can be used as both simple fillers and fillers for insulating layers include inorganic oxide particles such as aluminum oxide (alumina, Al2O3), aluminum oxide hydrate (boehmite, AlOOH), gibbsite (Al(OH)3), silicon oxide, magnesium oxide (magnesia), magnesium hydroxide, calcium oxide, titanium oxide (titania), barium titanate (BaTiO3), ZrO, silica, and alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalent crystalline particles such as silicon and diamond; sparingly soluble ionic crystalline particles such as barium sulfate, calcium fluoride, and barium fluoride; and clay fine particles such as talc and montmorillonite. Among these, from the viewpoint of improving heat resistance, non-conductive particles are preferably particles made of alumina (alumina particles), particles made of boehmite (boehmite particles), particles made of titania (titania particles), and particles made of barium sulfate (barium sulfate particles), more preferably alumina particles, boehmite particles, and barium sulfate particles, and even more preferably alumina particles and barium sulfate particles. These particles may be subjected to elemental substitution, surface treatment, solid solution treatment, etc., as needed. Furthermore, these particles may be used individually or in combination of two or more types.

[0063] <Selection of filler (F)> The selection of the filler (F) may be based on the expectation of contributing to improved production efficiency or safety in the manufacturing of components for electrochemical devices, or to improved performance or safety of the components for electrochemical devices, or to standardization of quality. As a filler expected to improve ionic conductivity, for example, the inorganic solid electrolyte described above may be selected. As a filler that provides reinforcement to the electrochemical device, for example, the reinforcing material described above may be selected. As a filler that provides flame retardancy to the electrochemical device, for example, the flame retardant described above may be selected. As a filler that improves the output of the electrochemical device, for example, the output booster described above (e.g., a filler that provides ion dissociation assistance, a filler that provides output to the electrochemical device) may be selected. As a filler that provides the effect of increasing electrode resistance by generating gas when the electrochemical device overheats abnormally, for example, the gas generating agent described above may be selected. As a filler that melts when the electrochemical device overheats abnormally and has the effect of increasing electrode resistance, for example, the plastic particles described above may be selected. As a filler that improves the conductivity of the electrodes, for example, the conductive material described above may be selected. Furthermore, as a filler that has the effect of smoothing the molding process and enabling the processing of the molding material composition with less force, for example, the solid lubricant described above may be selected.

[0064] <Additional ingredients> The molding material composition used in the present invention may further contain a second polymer (P2) that is plasticized by a plasticizer (PS) but does not dissolve in the electrolyte. Furthermore, the molding material composition used in the present invention may further contain other additional components. Examples of additional components include crosslinking agents.

[0065] <polymer> The "polymers" (polymer(P1), polymer(P2)) contained in the molding material composition refer to molecules with a weight-average molecular weight of 10,000 or more. Examples of polymer main chains used in the present invention include aromatic rings, sugar chains, peptide chains, carbonate ester chains, methylene chains, polyether chains, chains containing nitrogen in the main chain, or composites thereof. In order to manufacture flexible electrochemical device components, from the viewpoint of imparting flexibility to the molding material composition, non-cellulose sugar chains, peptide chains, methylene chains, polyether chains, and polyethyleneimine chains are preferred as the main chains of the polymers used in the present invention, with methylene chains, polyether chains, and chains containing nitrogen in the main chain being the most preferred. Examples of substituents or side chains bonded to the main chain of the polymers used in the present invention include cyano groups, hydroxyl groups, carboxylic acids, carboxylates, linear esters, cyclic esters, linear amides, cyclic amides, pyridyl groups, oxazoline groups, polyether chains, amines, ammonium, and organic ammonium, and a single polymer may have multiple types of substituents or side chains. The substituents or side chains of the polymer used in the present invention may be appropriately selected from the viewpoint of adjusting solubility in plasticizers or electrolytes. For example, increasing the number of polar groups will result in water solubility, while decreasing them will result in water insolubility. Alternatively, the design may be based on the SP value. From the viewpoint of imparting viscosity to the polymer solution, a higher weight-average molecular weight is preferable, preferably 50,000 or more, and more preferably 100,000 or more. On the other hand, if there are too many components with excessively high molecular weights, the surface of the molded product may become rough or the molding speed may decrease. Therefore, it is preferable that components with molecular weights exceeding 10 million constitute 5% by weight or less of the total polymer solution, and it is even more preferable that components with molecular weights exceeding 5 million constitute 5% by weight or less of the total polymer solution.

[0066] Specific examples of polymers (polymer(P1), polymer(P2)) include polyethylene oxide, sodium polyacrylate, lithium polyacrylate, polyacrylic acid esters, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyvinyl acetate, polyoxazoline, polyacrylamide, poly-N-vinylacetamide, and copolymers containing their monomer units, as well as synthetic polymers such as hygroscopic polymers like epichlorohydrin-organic amine condensates (e.g., dimethylamine-epichlorohydrin-ethylenediamine copolymer, polyamidoamine epichlorohydrin), dextrin, cyclodextrins (α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin, etc.), tamarind gum, gum arabic, guar gum, carrageenan, quince seed, and pregelatinized dextrin. Examples of natural polymers include, but are not limited to, ammonium compounds, tragacanth gum, carob gum, pectin, galactan, karaya gum, agar, algae colloid, xanthan gum, dextran, succinoglucan, pullulan, collagen, gelatin, casein, albumin, alginic acid, glucomannan, mucin, fucoidan, sulfated fucose, polyglutamic acid (γ-polyglutamic acid), mannan, and mannose, as well as semi-synthetic polymers such as carboxymethyl starch, methylhydroxypropyl starch, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, sodium cellulose sulfate, sodium carboxymethylcellulose (CMC-Na), sodium alginate, and propylene glycol alginate.From the viewpoint of maintaining a plasticized state under a wide range of conditions, the polymers used in the present invention are preferably polymers containing ethylene oxide (EO) as a monomer unit (e.g., polyethylene oxide, high-ethylene oxide content ethylene oxide copolymer, low-ethylene oxide content ethylene oxide copolymer), polyoxazoline polymers (e.g., polyoxazoline, oxazoline copolymer), poly-N-vinylacetamide polymers (e.g., poly-N-vinylacetamide, N-vinylacetamide copolymer), poly-N-vinylpyrrolidone, polyvinyl acetate, and epichlorohydrin-organic amine condensates (e.g., dimethylamine-epichlorohydrin-ethylenediamine copolymer, polyamidoamine epichlorohydrin). In this specification, "high content" means that the ratio of monomer units to the total monomer units in the copolymer is, for example, 50 mol% or more, preferably 60 mol% or more, 70 mol% or more, 80 mol% or more, or 90 mol% or more. In this specification, "low content" means that the ratio of monomer units to the total monomer units in the copolymer is, for example, less than 50 mol%, preferably 40 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. When the molding material is alkaline, the polymer used in the present invention is preferably poly-N-vinylacetamide, poly-N-vinylpyrrolidone, polyacrylic acid-based, or alginic acid-based polymer. From the viewpoint of preventing moisture from escaping easily during molding, the polymer used in the present invention is preferably a hygroscopic polymer such as epichlorohydrin-dimethylamine condensate (e.g., dimethylamine-epichlorohydrin-ethylenediamine copolymer). From the viewpoint of good retention of the filler in the member, it is preferable that the viscosity of the polymer used in the present invention be high, and the viscosity of the polymer solution is preferably, for example, 100 cP or more, preferably 500 cP or more, more preferably 1000 cP or more, or 5000 cP or more. It is preferable that the polymer used in the present invention is not gelled. The viscosity of a polymer solution can be measured by the following method.

[0067] In this invention, "viscosity" refers to the viscosity measured at a temperature of 25°C using an EMS viscometer (Kyoto Electronics Manufacturing Co., Ltd., EMS-1000S) under sealed conditions, ensuring that the composition of the polymer solution does not change and that moisture from the air is not mixed in, at a rotation speed of 1000 rpm. The viscosity measured by this method is basically the same as the value measured in accordance with JIS Z8803.

[0068] The amount of polymer in the polymer solution is preferably 90 wt% or less from the viewpoint of the flexibility of components for electrochemical devices (e.g., electrodes), and at least 1 wt%, preferably 3 wt% or more, is necessary for moldability. To satisfy the requirement of "polymer" in the molding material composition, it must be a "polymer" at the time of molding, and it must not include materials that polymerize into polymers within the electrochemical device (e.g., battery). If the polymer is not plasticized in the electrolyte solvent, the flexibility of the electrode will be low, and there is a risk of damage due to deformation caused by external forces or deformation due to chemical reactions accompanying the operation of the device. If the component contains a polymer soluble in the electrolyte solvent, the flexibility of the electrode is maintained, and there is less risk of damage even if the device deforms.

[0069] <First polymer (P1)> In the method for manufacturing components for electrochemical devices of the present invention, the first polymer (P1) is plasticized with a plasticizer (PS), so the polymer (P1) used is a polymer that has the property of being plasticized with the plasticizer (PS) used in the present invention. Furthermore, from the viewpoint of maintaining flexibility even after becoming an electrochemical device, the polymer (P1) is preferably a polymer that has the property of being plasticized with an electrolyte solvent (ES). Furthermore, if the method for manufacturing components for electrochemical devices of the present invention includes crosslinking the polymer (P1), the polymer (P1) may be a crosslinkable polymer. Examples of crosslinkable polymers include irreversible crosslinkable polymers and reversible crosslinkable polymers, with irreversible crosslinkable polymers being preferred. Examples of crosslinkable polymers include thermally crosslinkable polymers and UV crosslinkable polymers. Examples of crosslinkable polymers include polymers that are crosslinked with a crosslinking agent and self-crosslinkable polymers. Examples of polymers that are crosslinked with a crosslinking agent include those that have crosslinkable groups such as unsaturated bonds, epoxy groups, and oxetane groups in their molecules. The polymer (P1) can be appropriately selected from the polymers described above, depending on the type of plasticizer (PS) and electrolyte solvent (ES). Examples of combinations of polymer (P1), plasticizer (PS), and electrolyte solvent (ES) are shown below.

[0070] <Second polymer (P2)> The molding material composition may further contain a second polymer (P2) that is plasticized by a plasticizer (PS) but does not dissolve in the electrolyte. In this case, in the method for manufacturing electrochemical device components of the present invention, the first polymer (P1) and the second polymer (P2) are plasticized by the plasticizer (PS). Including polymer (P2) in the molding material composition is advantageous in that it limits contact between the filler and the electrolyte. Limiting contact between the filler and the electrolyte suppresses unnecessary reactions and extends the lifespan of the electrochemical device. Polymer (P1) can be appropriately selected from the polymers described above, depending on the type of plasticizer (PS) and electrolyte. Examples of combinations of polymer (P1), plasticizer (PS), and electrolyte are, for example, those described later.

[0071] <Plasticizer (PS)> The plasticizer (PS) is water, an ionic liquid, or a mixture thereof. Examples of ionic liquids include, but are not limited to, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEME-TFSI, a water-insoluble ionic liquid), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI, a water-insoluble ionic liquid), and N,N-diethyl-N-methyl-N-(2-methoxyethyl)-tetrafluoroborate (DEME-BF4, a water-soluble ionic liquid). A wide range of plasticizers that can plasticize polymers (P1) at 25°C can be selected. Furthermore, if the electrochemical device has non-sealed parts, such as actuators or air batteries, moisture in the air is also included in the electrolyte solvent (ES). When processing using both water and an ionic liquid, even if all the water evaporates, the ionic liquid remains, so a certain degree of flexibility in the battery material is maintained. When processing with only an ionic liquid, the battery material is always flexible. There are no specific regulations regarding the amount of plasticizer (PS) needed to plasticize a polymer, but it is often 5% by weight or more relative to the polymer weight, and plasticization is possible in most cases if it is 10% by weight or more. Furthermore, the plasticizer (PS) content in the molding material composition may be, for example, 3% by weight or more, preferably 5% by weight or more. In any case, it is best to check the actual properties rather than the quantity.

[0072] <Electrolyte solvent (ES) and electrolyte> The electrolyte solvent (ES) and electrolyte are not particularly limited, and any electrolyte used in electrochemical devices can be used. Examples of electrolyte solvents (ES) include substances used as plasticizers (PS) (water, ionic liquids, or mixtures thereof), propylene carbonate (PC), ethylene carbonate, linear carbonate esters, lactones, linear carboxylic acid esters, acetonitrile, sulfolanes, glimes, linear sulfones, dinitrile compounds, cyclic ethers, fluorinated ethers, and other organic solvents. Examples of electrolytes include solutions obtained by dissolving electrolytes (e.g., sodium chloride, potassium chloride, ammonium chloride, zinc chloride, lithium sulfate, magnesium sulfate, sulfuric acid, sodium hydroxide, lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium tetrafluoroborate (LiBF4), magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI)) in an electrolyte solvent (ES), and electrolyte solvents (ES) that are also electrolytes (e.g., ionic liquids, mixtures of water and ionic liquids). Examples of ionic liquids include those mentioned above. For devices with electrodes thicker than 100 μm, it is preferable to select solvents and salts with high ionic conductivity. Specifically, the solvent is preferably one of the following: water, acetonitrile, ethylene glycol dimethyl ether, methyl acetate, bis(2,2,2-trifluoroethyl) ether, or 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether. The electrolyte salt is preferably a salt of an FSI anion.

[0073] <Examples of polymers (P1) and (P2)> When the plasticizer (PS) is water and the electrolyte solvent (ES) is propylene carbonate (PC), examples of polymers that can be selected as polymer (P1) include polyethylene oxide (PEO), ethylene oxide (EO) high-content EO copolymer, polyoxazoline, poly-N-vinylacetamide, carboxymethylcellulose (CMC), sodium polyacrylate, sodium alginate, and polyvinyl alcohol (PVOH). In this case, examples of polymers that can be selected as polymer (P1) that are also plasticized by the electrolyte solvent (ES) include PEO, EO high-content EO copolymer, polyoxazoline, and poly-N-vinylacetamide. In this case, examples of polymers that can be selected as polymer (P2) include CMC, sodium polyacrylate, sodium alginate, and PVOH.

[0074] When the plasticizer (PS) is water and the electrolyte solvent (ES) is water, examples of polymers that can be selected as polymer (P1) include PEO, EO-high content EO copolymer, CMC, sodium polyacrylate, sodium alginate, PVOH, polyethyleneimine, polyoxazoline, and poly-N-vinylacetamide. In this case, the polymer (P1) that is also plasticized by the electrolyte solvent (ES) may also be selected from these polymers.

[0075] When the plasticizer (PS) is an ionic liquid and the electrolyte solvent (ES) is an ionic liquid, examples of polymers (P1) include PEO, high-EO content EO copolymers, low-EO content EO copolymers, styrene-acrylic copolymers, cellulose, polyoxazoline, and poly-N-vinylacetamide. In this case, the polymer (P1) that is also plasticized by the electrolyte solvent (ES) may be selected from these polymers.

[0076] When the plasticizer (PS) is an ionic liquid and the electrolyte solvent (ES) is a mixed liquid of an ionic liquid and water, examples of polymers (P1) include PEO, high-EO content EO copolymers, polyoxazoline, poly-N-vinylacetamide, low-EO content EO copolymers, styrene-acrylic copolymers, and cellulose. In this case, examples of polymers that can be selected as polymers (P1) that are also plasticized by the electrolyte solvent (ES) include PEO, high-EO content EO copolymers, polyoxazoline, and poly-N-vinylacetamide. In this case, examples of polymers that can be selected as polymers (P2) include low-EO content EO copolymers, styrene-acrylic copolymers, and cellulose.

[0077] <Plasticized polymers> A polymer is said to be "plasticized" when mixed with a solvent (e.g., plasticizer (PS), electrolyte solvent (ES), electrolyte), resulting in a loss of its shape (liquid or rubbery), and when a mass of plasticized polymer is divided into two or more parts, it can be reunited to form a single mass. However, since this cannot be determined after a crosslinking operation, the properties of the uncrosslinked state are applied to the crosslinked product as well. If the plasticizer (PS) is an ionic liquid with a repeating structure, the ionic liquid itself is considered a "polymer (P1) plasticized with the plasticizer (PS)."

[0078] The amount of plasticizer (PS) used to plasticize the polymer (P1) is not particularly limited, but any amount that plasticizes the polymer (P1) is sufficient. The amount of plasticizer (PS) is usually 5% by weight or more relative to the polymer (P1), and in most cases, 10% by weight or more is sufficient for plasticization.

[0079] <organic solvents> The molding material composition used in this invention is substantially free of organic solvents. "Organic solvent" refers to a nonionic organic compound with a molecular weight of 1000 or less, which is neither a polymer nor an ionic liquid. Although the presence of organic solvents is undesirable from the standpoint of fire and worker health, the addition of small amounts does not hinder the implementation of this invention, so it can be added up to 10% by weight or less relative to the total amount of polymer and plasticizer (PS) in the molding material composition.

[0080] <Pseudo-crosslinking agent> The molding material composition used in the present invention may further contain the following components and components (formation of pseudo-crosslinking). When the molding material composition contains the following components and components, pseudo-crosslinking can be formed, thereby increasing the strength of the member without losing plasticity. Polyvalent ions (especially polyethers and polyvalent cations, carboxylic acids and polyvalent cations, polyvinyl alcohols and polyvalent cations, polymers with cationic groups and polyvalent anions, polyethyleneimines and polyvalent ions); Polyethyleneimines and polycarboxylic acid compounds; Polyvinyl alcohol and borates / borax (sodium tetraborate, lithium tetraborate); or A triblock polymer with hydrophobic ends.

[0081] <Components of other molding material compositions> The molding material composition used in the present invention may further contain an acid, a base, and an electrolyte salt for operating the device.

[0082] <Composition ratio of components in the molding material composition> To enhance the self-supporting properties of the molding material composition used in this invention, these properties can be improved by adding fiber components, increasing the amount of filler, reducing the particle size of the filler, or increasing the amount of polymer.

[0083] <Formation operation> The electrochemical device component of the present invention is manufactured by performing at least one shaping operation selected from the following group A on the above-described molding material composition. [Group A: Extrusion, injection molding, stretching, compression molding, thickness reduction by pressurization, thickness uniformization by pressurization, cutting, drilling, machining, bending into the final shape for housing electrochemical device containers, bonding of molding material compositions with different compositions] The molding material composition used in the present invention is plastic and self-supporting, so it can be given the desired shape for an electrochemical device component by shaping operations, and the given shape can be maintained throughout the manufacturing process. Furthermore, since the desired shape can be given without operations such as drying, it is possible to suppress changes in the quality of the component due to fluctuations in the amount of solvent such as water during the manufacturing process, compared to cases where a slurry is applied and dried to form a device component, and the quality can be restored by absorbing solvent such as water after formation.

[0084] The shaping operations selected from group A may be of different types, or the same operation may be repeated multiple times. The shaping operations may be performed at least once while the molding material composition is not in contact with the current collector foil. Furthermore, the shaping operations selected from group A may be performed at least once while the molding material composition is not in contact with the porous separator film.

[0085] The shaping operation can be carried out using known processing equipment such as rollers, presses, cutters, milling machines, and drills. The surface of rollers and the like is preferably made of metal, ceramic, glass, fluoropolymer, or silicone polymer. The surface is preferably non-stick. The stickiness can also be controlled by adding fine irregularities to the roller. When temporarily placing a workpiece during the shaping operation, it may be placed on a mesh, perforated plate, or a pull-up jig processed to have a textured or matte finish. In the shaping operation, a tape of constant thickness may be attached to the roller or the like to control the thickness. If a pattern is applied to the roller, the workpiece can be shaped by transferring that shape. When shaping a workpiece with a roller, a smaller diameter is preferable because less material adheres to it and cleaning is easier.

[0086] In the shaping operation, the molding material composition may be molded into a sheet shape. When molded into a sheet shape, the thickness accuracy is preferably within ±10%, and more preferably within ±5%. This improves adhesion to current collector foil and other components. When forming a sheet, it is preferable to make the sheet surface wavy so that it does not stick to shaping equipment such as rollers, and it is also easier to control the thickness because it becomes easier to crush. The operation to make the sheet surface wavy may be done by making the die exit shape to impart a wavy shape, or by extruding it in a flat shape and then shaping it with a roller that has cut grooves or an embossing roller, or by cutting notches with a blade. The height difference between the highest and lowest points of the unevenness is preferably 10% or more of the average thickness. Thicker components are easier to manufacture because they stick less to the equipment. The thickness of the component is preferably 100 μm or more. More preferably 200 μm or more. When the component is an insulating layer, it is preferable for the insulating layer to be thin from the viewpoint of adhesion to other components and conformability. If the insulating layer is too thick, it is prone to peeling at the interface. The thickness of the insulating layer may preferably be 100 μm or less, more preferably 50 μm or less, and even more preferably 20 μm or less.

[0087] When not in use, molding material compositions should be stored in airtight containers whenever possible. Additionally, a protective film may be applied to the molding material composition during processing or storage to prevent moisture absorption or drying.

[0088] <Additional steps> The method for manufacturing components for electrochemical devices of the present invention may further include, for example, the following additional steps.

[0089] <Crosslinking of polymer (P1)> The method for manufacturing components for electrochemical devices of the present invention may further include crosslinking a polymer (P1). Examples of crosslinking include irreversible crosslinking and reversible crosslinking, but irreversible crosslinking is preferred. Known crosslinking methods such as thermal crosslinking, UV crosslinking, electron beam crosslinking, and radiation crosslinking can be used. Thermal crosslinking and electron beam crosslinking are preferred for crosslinking electrodes and conductive layers. UV crosslinking is preferred for crosslinking insulating layers because the material is transparent. Examples of crosslinking include crosslinking with a crosslinking agent (e.g., UV initiator) and self-crosslinking. In the case of crosslinking with a crosslinking agent, the crosslinking agent is preferably added to the electrochemical device, for example, it may be added to the molding material composition, or it may be added to a part other than the molding material composition (e.g., electrolyte). In addition, low molecular weight co-crosslinking agents having multiple crosslinkable groups, such as TAIC (triallyl isocyanurate), may be used in combination. The polymer (P1) and the crosslinking agent can be appropriately selected according to the mode of crosslinking. For example, if the crosslinking is self-crosslinking, a self-crosslinkable polymer can be selected as the polymer (P1). To make a polymer self-crosslinkable, for example, a polymer containing acetoacetyl groups, epoxy groups, oxetane groups, azetidinium groups, pyrrolidonyl groups, etc., can be used. Such self-crosslinkable polymers can be self-crosslinked by heating. Crosslinking of polymer (P1) may be performed either during or after plasticization of polymer (P1) with plasticizer (PS), or before, during, or after the shaping operation. The crosslinking operation is preferably performed in the plasticized state of polymer (P1), and may be performed before device assembly or by heating the device itself after device assembly. Furthermore, in the manufacture of electrochemical devices, each component may be crosslinked before assembly, but it is preferable to crosslink after the structure of the electrochemical device is completed, as this allows for integration of the whole and increases durability.

[0090] <Feedback Management> The method for manufacturing components for electrochemical devices of the present invention may further include a feedback control step. The feedback control step may include, for example, managing and providing feedback on the basis weight by measuring the characteristics of the component (e.g., thickness). (This has been removed as it is not impossible to do this with other compositions.) As a feedback control step, for example, the basis weight can be measured by measuring the characteristics of the component (e.g., thickness). A manufacturing method can be implemented in which the basis weight is managed and feedback is provided by measuring the thickness. Such a feedback control step does not necessarily require the basis weight of the component using X-rays or gamma rays; measurement using a contact-type film thickness gauge or a laser-type film thickness gauge may also be used.

[0091] <Molding-related processes> The method for manufacturing an electrochemical device component of the present invention may include crushing a plurality of strands made of a molding material composition to form a sheet. Alternatively, the method for manufacturing an electrochemical device component of the present invention may include obtaining a component by scraping it from a block of molding material composition. Furthermore, the method for manufacturing an electrochemical device component of the present invention may include attaching the molding material composition to a substrate (e.g., a current collector, a porous separator film). Attachment to the substrate may be performed, for example, after shaping the molding material composition to a desired thickness. Attachment to the substrate may be performed, for example, by attaching the molding material composition to both sides of the substrate substantially simultaneously, or by attaching the molding material composition to the front side of the substrate and then to the back side. If the substrate is a conductive substrate (e.g., a current collector such as a current collector foil), the substrate may have a conductive coating on the surface in contact with the molding material composition. Examples of conductive coatings include carbon paint, ITO, and metal plating. The conductive coating may be applied to the current collector foil side, or applied or sprayed to the component side. If the conductive coating has sufficient strength and conductivity, it can itself be used as a conductive substrate (e.g., a current collector). The current collector may be made of metal or mainly composed of non-metals. For non-metallic current collectors, for example, conductive carbon or metal materials can be mixed with polymers such as polyethylene, polypropylene, cellulose, or rubber to make them conductive. If the substrate is an insulating substrate (e.g., a separator substrate such as a porous separator film), the substrate may mainly contain polymers. Examples of substrates mainly containing polymers include polyethylene, polypropylene, cellulose, and rubber. Furthermore, after the molding material composition is attached to the substrate, it is not necessary to cut or drill holes in the member together with the substrate. In addition, the method for manufacturing the electrochemical device member of the present invention may include a step of peeling off the molding material composition that is already attached to the substrate from the substrate.

[0092] <Deplasticization by drying process> The method for manufacturing a component for an electrochemical device of the present invention may include removing moisture by a drying operation to render it non-plastic. The drying operation may be performed before or after the molding material composition is incorporated into the final shape (e.g., shaped) when the component is placed in the device. The drying operation may be performed, for example, by vacuum, in a low-humidity atmosphere, or by heating. Vacuum means reducing the pressure to a degree sufficient to remove moisture contained in the component, for example, to 100 Pa, preferably 10 Pa, and more preferably 1 Pa. A low-humidity atmosphere means a humidity level sufficient to remove moisture contained in the component, for example, an atmosphere with a relative humidity of 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less at room temperature. Heating means placing the material at a temperature that removes moisture from the material and prevents deformation. The temperature may be, for example, 50°C or higher, preferably 80°C or higher, more preferably 100°C or higher, or for example, 300°C or lower, preferably 200°C or lower, more preferably 150°C or lower. The drying operation may also be performed when the molded material composition is not in contact with the current collector foil. The drying operation may also be performed when the molded material composition is not in contact with the porous separator film. When drying electrochemical device components (e.g., electrodes) in a plasticized state after they have been shaped into their final form, the preceding drying operation using a drying oven, which is usually present, can be omitted. In this case, since the material is shaped in a plasticized state, excessive force is not applied to form the final shape, preventing damage to the component.

[0093] <Restoration of plasticity after deplasticization> The method for manufacturing an electrochemical device component of the present invention may include restoring the plasticity of the molding material composition after it has become non-plasticized by adding water or humidifying it again. Water addition may be performed, for example, by dropping or spraying water for 1 second at 25°C. Humidification may be performed, for example, under conditions of 25°C and 99% RH. The molding material composition may be incorporated (e.g., shaped) into the final shape when the component is placed in the device after the plasticity has been restored.

[0094] <Storage of components for electrochemical devices> When storing components for electrochemical devices (e.g., electrodes) of the present invention, it is preferable to reduce the amount of plasticizer (PS) to prevent them from sticking together. The plasticizer (PS) reduction operation for storage does not need to be carried out until the polymer is no longer liquid or rubbery. The plasticizer (PS) reduction operation is preferably reduced to 90% or less of the total amount of added plasticizer (PS), and more preferably to 80% or less. However, if only ionic liquid is used as the plasticizer (PS), such a plasticizer (PS) reduction operation cannot be performed. If the components for electrochemical devices stick together strongly, it is preferable to sandwich them with a plastic film during storage. The material is not particularly limited, but PE, PP, PET, PTFE, etc. are preferred, and the film may be mold release treated or have a textured surface.

[0095] <Manufacturing method including recycling of scrap materials> The method for manufacturing electrochemical device components of the present invention may include manufacturing the next component using scraps of the molding material composition generated in the process of shaping the molding material composition. Since the molding material composition used in the present invention has plasticity and self-supporting properties, irreversible quality changes are suppressed during the manufacturing process, so scraps of the molding material composition can be used to manufacture the next component. When reusing scraps of the molding material composition, it is preferable from the viewpoint of quantitative accuracy to dry them to the equilibrium moisture content of the environment before rehydrating them. When rehydrating the component, operations such as increasing the ambient humidity, spraying, dropping, electrostatic spraying, and immersion can be suitably used. When adding ionic liquids, organic solvents, etc. to the component, operations such as spraying, dropping, electrostatic spraying, and immersion can be suitably used.

[0096] <Conditions for the manufacturing method> The method for manufacturing components for electrochemical devices of the present invention (e.g., manufacturing battery components) may be carried out in a normal humidity environment or in a dry environment (dry room, glove box). When carried out in a dry environment of 50% RH or less, it is preferable to add an ionic liquid. From the viewpoint of suppressing water dissipation, it is preferable to carry out the process in a low temperature and high humidity environment.

[0097] (Recycling methods for components used in electrochemical devices) The molding material composition used in the present invention has plasticity and self-supporting properties, which suppresses irreversible quality changes during the manufacturing process. For example, the molding material composition in the intermediate stages of manufacturing (e.g., the molding material composition already attached to the substrate, the molding material composition in a non-plasticized state, and scraps of the molding material composition) can be used to recycle components for electrochemical devices. The recycling method for electrochemical device components may include, for example, a step of peeling off the molding material composition that is already attached to the substrate from the substrate. The recycling method for electrochemical device components may also include, for example, restoring the plasticized state of the molding material composition after it has become non-plasticized by adding water or humidifying it again. The recycling method for electrochemical device components may also include, for example, manufacturing the next component using scraps of the molding material composition generated in the process of shaping the molding material composition.

[0098] (Method of manufacturing electrochemical devices) The present invention's method for manufacturing an electrochemical device includes obtaining a component using the method for manufacturing electrochemical device components or the recycling method described above.

[0099] (Components for electrochemical devices) The electrochemical device component of the present invention can be obtained by the manufacturing method or recycling method of the electrochemical device component described above. Examples of the electrochemical device component of the present invention include electrodes (e.g., positive electrode, negative electrode), insulating layers (e.g., insulating film), and adhesive layers. Electrodes or insulating layers are preferred for the electrochemical device component. Electrodes include the air electrode of an air battery. The insulating layer may be used as an insulating layer in energy storage devices such as lithium-ion batteries, or it can be attached to glass with a conductive ITO (indium tin oxide) layer and used in dye-sensitized solar cells or electrochromic devices. The insulating layer may be used in device assembly in a plasticized state, or it may be dried and used in an unplasticized state. It is also a preferred embodiment to assemble the device without crosslinking and then crosslink it at the end using ultraviolet light, heat, etc.

[0100] (Electrochemical devices) The electrochemical device of the present invention includes the electrochemical device components described above. Examples of the electrochemical device of the present invention include non-aqueous or aqueous primary batteries such as lithium primary batteries and manganese primary batteries (e.g., manganese-zinc primary batteries, manganese-lithium primary batteries); non-aqueous or aqueous secondary batteries such as lithium-ion secondary batteries (non-aqueous, aqueous), lithium metal secondary batteries, sodium-ion secondary batteries, potassium-ion secondary batteries, magnesium secondary batteries, and aluminum secondary batteries; air batteries; solar cells such as dye-sensitized solar cells; capacitors such as electric double-layer capacitors and lithium-ion capacitors; electrochromic display devices; electrochemical light-emitting elements; electric double-layer transistors; and electrochemical actuators. The electrochemical device is preferably a non-aqueous secondary battery, and more preferably a lithium-ion secondary battery.

[0101] The electrochemical device of the present invention may include, for example, electrodes as components for the electrochemical device. The electrochemical device of the present invention may include electrodes obtained by the manufacturing or recycling method described later, and one electrode (counter electrode). The counter electrode may include, for example, at least one selected from alkali metals (e.g., lithium, sodium, potassium, rubidium, cesium), alkaline earth metals (e.g., beryllium, magnesium, calcium, strontium, barium), metallic aluminum, and silver.

[0102] When the electrochemical device of the present invention is a lithium-ion battery, and a perforated current collector foil is used in the manufacturing of the lithium-ion battery, vertical pre-doping can be performed by placing a lithium metal electrode inside the cell in addition to the positive and negative electrodes. This is an effective method when using an active material with an initial irreversible capacity.

[0103] The electrochemical device of the present invention may be either a water-containing electrochemical device or a non-water-containing electrochemical device. Examples of water-containing electrochemical devices include electrochemical devices in which the electrolyte contains water (e.g., water-containing lithium-ion secondary batteries, manganese-zinc primary batteries, and other water-containing batteries). Examples of non-water-containing electrochemical devices include electrochemical devices in which the electrolyte is dissolved in an organic solvent and does not contain water (e.g., non-water-containing lithium-ion secondary batteries, lithium primary batteries, manganese-lithium primary batteries, and other non-water-containing batteries). Water-containing and non-water-containing electrochemical devices may also be non-water-containing electrochemical devices in which the carrier ions are at least one of alkali metal ions (e.g., lithium ions, sodium ions, potassium ions), alkaline earth metal ions (e.g., beryllium ions, magnesium ions, calcium ions), aluminum ions, silver ions, organic nitrogen cations (e.g., triethylmethylammonium 1-ethyl-3-methylimidazolium), and halide anions (e.g., bromide ions, iodide ions). [Examples]

[0104] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0105] In the following explanation, "able to bend" means that no damage was observed when the member was wrapped around a cylinder of a constant diameter and bent. "Self-supporting" and "plasticity" are as described above.

[0106] The following are experimental examples using lithium-ion batteries and manganese batteries, but the effects are similar for other devices.

[0107] (Example 1: Manufacturing and evaluation of electrode sheets using polyethylene oxide (PEO)) In a laboratory at 25°C and 90% RH humidity, 100g of lithium cobalt oxide (Cellseed C, manufactured by Nippon Chemical Industries, average particle size 20μm) as the active material, 3g of acetylene black as a conductive additive, 8g of deionized water as a processing solvent, 1g of polyethylene oxide (PEO) (Sigma-Aldrich) with a weight-average molecular weight of 1,000,000 as polymer P1, and 1g of polytetrafluoroethylene (PTFE) (Sigma-Aldrich) as a fibrous material were weighed into a mortar and mixed to form a homogeneous electrode composition. 1g of this electrode composition was taken and molded into a 200μm thick sheet on a release-type polyethylene terephthalate (PET) film using a 3cm diameter stainless steel hand roller (electrode sheet 1-1). Immediate evaluation revealed that the sheet possessed self-supporting and plastic properties and could be bent to a diameter of 2mm. At this time, the polyethylene oxide was in aqueous solution, which is thought to have contributed to the flexibility of the electrode. The thickness at the edges of the sheet tended to be slightly thinner than in the center, with an average thickness of 197 μm at 5 mm from the edge. The edges may be cut off if necessary. The cut pieces can be reused in electrode manufacturing.

[0108] (Example 2: Manufacturing, evaluation, and regeneration of electrode sheets using PEO-based polymers) In a laboratory at 25°C and 90% RH humidity, 100g of lithium cobalt oxide, 3g of acetylene black, 8g of deionized water, 1g of a random copolymer of ethylene oxide-propylene oxide with a weight-average molecular weight of 1,000,000 (molar ratio 9:1) as polymer P1, and 1g of PTFE were weighed into a mortar and mixed to form a homogeneous electrode composition. 1g of this electrode composition was taken and sandwiched between release-type PET films, and a sheet with an average thickness of 2mm was obtained using a 3cm diameter stainless steel hand roller (electrode sheet 2-1). Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a sheet with an average thickness of 200μm (195-205μm) (electrode sheet 2-2), which could be bent to a diameter of 2mm. At this time, the copolymer was in aqueous solution, which is thought to have contributed to the flexibility of the electrode.

[0109] When electrode sheet 2-2 was left in a laboratory at 25°C and 55% humidity, the surface felt dry and its tackiness decreased in about one minute. When it was left like that for a day, the thickness did not change, but the weight decreased by 7% from the initial weight. It is thought that 99% of the added water had evaporated from the sheet (comparative electrode sheet 2-2), and it was determined that the polyethylene oxide was not plasticized. When we tried to bend it, it broke at an internal angle of about 120° before it could be wrapped around a cylinder. The density of the electrode sheet before breaking in the dry state was 3 g / cm³ 3 The volume fraction of the filler in this electrode sheet was 61% by volume, with lithium cobalt oxide and acetylene black added together. The density can be further improved by pressing it with a high-pressure roll press.

[0110] Electrode sheet 2-2 is further pressed with a roller with a linear pressure of 200 N / cm to thin it to an average thickness of 50 μm (49-51 μm) (electrode sheet 2-3), and a 50 μm thick conductive polyethylene film containing conductive carbon, prepared separately, is used as a current collector (surface resistance 10 4 The lithium-ion battery positive electrode (positive electrode 2-4) was manufactured by bonding it to a material with a resistance of Ω / sq. or less.

[0111] When electrode sheets 2-1, 2-2, 2-3, and positive electrode 2-4 were cut with scissors in a laboratory at 25°C and 55% humidity, they could be cut in two straight lines. No fine powder or other small fragments were generated, and no molding material adhered to the scissors. When these were stacked again and rolled out with a hand roller, they merged to form a sheet similar to the original.

[0112] (Comparative Example 1: Evaluation of a sheet after moisture has evaporated) When the reference electrode sheet 2-2 was cut with scissors in the same manner as in Example 2, cracks occurred in areas other than the cut surface, a straight cut surface could not be obtained, and fine powder was generated. Fine powder also adhered to the scissors. The divided sheets were gathered together and rolled out with a hand roller, but they did not fuse together and instead became fragmented.

[0113] (Comparative Example 2: Manufacturing and Evaluation of Slurry-Coated Electrodes) Electrodes were fabricated using a slurry coating method, which is common in the manufacture of lithium-ion batteries and electric double-layer capacitor electrodes. While electrode slurries using lithium cobalt oxide, graphite, and activated carbon all showed plasticity, they did not exhibit self-supporting properties. When a graphite-based electrode slurry was coated onto 25 μm thick aluminum foil and cut with scissors while still wet, a large amount of slurry adhered to the blades. Furthermore, slurry leaked out of the current collector foil from the cut surface.

[0114] (Comparative Example 3: Manufacturing and Evaluation of Slurry-Coated Drying Electrodes) The coated electrode of Comparative Example 2 was dried in a 60°C oven, and an attempt was made to peel off the electrode composite material from 5 mm from the end of the electrode while it was dry. The interface between the aluminum and the composite material was peeled off with a plastic spatula, but fine powder was generated during the peeling process and adhered to the surrounding area.

[0115] (Example 3: Evaluation of adhesion of electrode sheets using PEO-based polymers) Electrode sheet 2-3 from Example 2 was cut to a size of 5 cm square and placed on 25 μm thick aluminum foil in a laboratory at 25°C and 55% humidity. When the entire surface of electrode sheet 2-3 was lightly pressed from above with a hand roller, electrode sheet 2-2 and the aluminum foil adhered tightly. Since the edges of the sheet were slightly thinner, a cut was made around the circumference, 5 mm from the outer edge, without reaching the current collector foil. The edges were then peeled off using tweezers, and the outer molding material was removed in the shape of a square frame without producing any small fragments or fine powder (positive electrode 3). The electrode sheet, now 4 cm square, was then left in a laboratory at 25°C and 55% humidity for 24 hours. Similar to Example 1, a weight loss due to moisture evaporation was observed, but the adhesion between electrode sheet 2-3 and the aluminum foil remained.

[0116] (Example 4: Manufacturing and evaluation of electrode sheets using polymers other than PEO-based polymers) A sheet was prepared in the same manner as in Example 1, except that polymer P1 was replaced with poly-2-ethyl oxazoline (Sigma-Aldrich) with a weight-average molecular weight of 500,000. Upon immediate evaluation, the sheet was found to be self-supporting and could be bent to a diameter of 2 mm.

[0117] (Example 5: Manufacturing and evaluation of an electrode sheet containing a second polymer (P2)) A lithium-ion battery cathode with a thickness of 50 μm was prepared in the same manner as in Example 2, except that 1 g of carboxymethylcellulose (CMC) was added as a second polymer (polymer P2) (Positive electrode 5). Positive electrodes 2-4 and 5 from Example 2 were vacuum-dried at 40°C for 48 hours. A lithium-ion battery was fabricated with a Li metal counter electrode and an electrolyte of LiFSI / EC = 1 / 4, and when charged and discharged at a 1C rate, the positive electrode capacity retention rate after 200 cycles relative to the initial capacity was 91% for positive electrode 2-4 and 95% for positive electrode 5, with the one containing polymer P2 being superior. This is thought to be because the component (polymer P2) that does not dissolve or swell after immersion in the electrolyte functioned as a protective film on the surface of the positive electrode active material.

[0118] (Example 6: Manufacturing and evaluation of electrode sheets using hygroscopic polymer) As polymer P1, a dimethylamine-epichlorohydrin-ethylenediamine copolymer (Sigma-Aldrich) with a weight-average molecular weight of 75,000 was used. This polymer exhibited deliquescent properties, absorbing moisture equivalent to 15% of its own weight in a laboratory setting at 25°C and 55% humidity, spontaneously plasticizing into an aqueous solution. 9 g of this spontaneously plasticized polymer solution, 100 g of lithium cobaltate, 3 g of acetylene black, and 1 g of PTFE were weighed into a mortar and mixed to obtain a homogeneous electrode composition. 1 g of this electrode composition was taken and sandwiched between release-type PET films, and a sheet with an average thickness of 2 mm was obtained using a 3 cm diameter SUS hand roller (electrode sheet 6). Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a sheet with an average thickness of 200 μm (195-205 μm) (electrode sheet 6-2), which could be bent to a diameter of 2 mm. The copolymer was in an aqueous solution, which is thought to have contributed to the flexibility of the electrode. When left for 24 hours, there was no change in weight, and the flexibility of the sheet was maintained.

[0119] (Example 7: Manufacturing and evaluation of electrode sheets using ionic liquids) The experiment was conducted in a dry room controlled to a dew point temperature of -40°C or lower, humidity of 25°C, and ambient temperature. The raw materials used were thoroughly dried beforehand. 100g of lithium cobalt oxide, 3g of acetylene black, 11g of DEME-TFSI (N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide) as a water-insoluble ionic liquid, 1g of a random copolymer of ethylene oxide and propylene oxide with a weight-average molecular weight of 1,000,000 (molar ratio 9:1), and 1g of PTFE were weighed into a mortar and mixed to form a homogeneous electrode composition. This electrode composition was divided and molded into a sheet with an average thickness of 60μm on a flat stainless steel platform using a stainless steel roller with a diameter of 3cm (electrode sheet 7). This sheet was self-supporting and plastic, and could be bent to a diameter of 1mm. The moisture content of this sheet was measured using a Karl Fischer moisture meter and found to be 46ppm.

[0120] To further remove moisture, electrode sheet 7 was vacuum-dried at 100°C for 24 hours. The moisture content of this sheet was measured using a Karl Fischer moisture meter and found to be 4 ppm.

[0121] (Example 8: Combined use of water and ionic liquid, and crosslinking of electrodes) In a closed-type stirrer, 100 g of lithium cobalt oxide, 3 g of acetylene black, 6 g of (N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide) as a water-insoluble ionic liquid, 4 g of deionized water, 1 g of a random copolymer of ethylene oxide-allyl glycidyl ether with a weight-average molecular weight of 1,000,000 (molar ratio 9:1), 1 g of PTFE, and 50 mg of perkmil D as a thermal polymerization initiator were mixed at room temperature to obtain a homogeneous electrode composition. This electrode composition was divided and sandwiched between release-type PET films, then formed into a 200 μm thick sheet using a 3 cm diameter SUS hand roller (sheet 8-1). This sheet was slightly adhesive, self-supporting, and plastic, and could be bent to a diameter of 2 mm.

[0122] When sheet 8-1 was left in a laboratory at 25°C and 55% humidity, the surface felt dry in about 1 minute and its tackiness decreased. Furthermore, to promote dehydration and crosslinking by heating, the sheet was vacuum-dried in a vacuum dryer at 150°C for 30 minutes. The weight decreased by 3.5%, suggesting that almost 100% of the added water had evaporated, resulting in a sheet (comparison sheet 8-2) that was plasticized by the polymer ionic liquid. Comparison sheet 8-2 retained its flexibility and could be bent to a diameter of 5 mm. When cut with scissors, it could be cut in two straight lines without generating any fine powder, but when these were stacked again and stretched with a hand roller, they did not coalesce. This confirmed that while electrode strength improved due to crosslinking, coalescence was lost due to the loss of fluidity.

[0123] The crosslinking operation is preferably performed in the plasticized state of the polymer (P1), and may be performed before device assembly as in this embodiment, or by heating the device itself after device assembly.

[0124] (Example 9: Manufacturing and evaluation of electrode sheets using cellulose nanofibers) In a laboratory with a temperature of 25 degrees Celsius and a humidity of 90% RH, 100 g of lithium cobalt oxide, 3 g of acetylene black, 8 g of deionized water, 1 g of a random copolymer of ethylene oxide-propylene oxide with a weight-average molecular weight of 1,000,000 (molar ratio 90:5:5), and 2 g of cellulose nanofiber (nanoforest-S, Chuetsu Pulp & Paper Co., Ltd.) were weighed into a mortar and mixed to obtain a homogeneous electrode composition. 1 g of this electrode composition was taken and sandwiched between release-type PET films, and a 2 mm thick sheet was obtained using a 3 cm diameter stainless steel hand roller (electrode sheet 9-1). Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a 200 μm thick sheet (sheet 9-2), which could be bent to a diameter of 2 mm. The polyethylene oxide was in aqueous solution, which is thought to have contributed to the flexibility of the electrode.

[0125] (Example 10: Spraying onto the electrode) When a small amount of water was sprayed onto the comparative sheet 2-2 obtained in Example 1, the electrodes absorbed the sprayed water, and its flexibility was restored. This sheet could be bent to a diameter of 2 mm. When the weight of the electrodes was measured, a weight recovery equivalent to 80% of the initial moisture content was observed.

[0126] (Example 11: Rehydration of the electrode) When the non-cohesive electrode fragments obtained in Comparative Example 1 were collected, an amount of deionized water equivalent to the lost water was added dropwise, and the mixture was mixed again, an electrode mixture similar to the initial one was obtained, and a sheet similar to Sheet 1 could be manufactured.

[0127] (Example 12: Impregnation of the electrode with electrolyte) A small amount of 1M LiTFSI / propylene carbonate solution, prepared separately, was dropped onto the comparative sheet 2-2 obtained in Example 1, ensuring that the electrolyte did not overflow from the electrode. The electrolyte was observed to permeate the electrode, and the electrode's flexibility was restored, allowing it to be bent to 2 mm. Since the random copolymer of ethylene oxide and propylene oxide (molar ratio 9:1) is soluble in propylene carbonate, it was confirmed that it can be plasticized with the electrolyte and maintain its flexibility even within the device.

[0128] (Example 13: Graphite electrode) In a laboratory with a temperature of 25 degrees Celsius and a humidity of 90% RH, 40 g of graphite (604A, manufactured by Nippon Carbon Co., Ltd.), 7 g of deionized water, 1 g of a random copolymer of ethylene oxide-propylene oxide with a weight-average molecular weight of 1,000,000 (molar ratio 9:1), and 0.2 g of PTFE were weighed into a mortar and mixed to obtain a homogeneous electrode composition. 1 g of this electrode composition was taken and sandwiched between release-type PET films, and a sheet with an average thickness of 2 mm was obtained using a 3 cm diameter stainless steel hand roller (electrode sheet 13-1). Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a sheet with an average thickness of 200 μm (195-205 μm) (electrode sheet 13-2), which could be bent to a diameter of 2 mm. This was further compressed with a hand roller to a thinned average thickness of 50 μm (49-51 μm) (electrode sheet 13-3), and then attached to a 25 μm thick electrolytic copper foil to manufacture the lithium-ion battery negative electrode (negative electrode 13-3).

[0129] The density of the electrode in a dry state is 1.74 g / cm³. 3 The volume fraction of the filler in this electrode is 70 vol% for graphite alone. The density can be further increased by pressing it with a high-pressure roll press.

[0130] (Example 14: Addition of solid lubricant) A molding material was prepared in the same manner as in Example 1, except that 5 g of graphite powder (KS4, manufactured by TIMCAL) was added as a solid lubricant. When this molding material was pressed with a roll bearing the same linear pressure of 200 N / cm as in Example 1, a sheet with an average thickness of 45 μm (44-46 μm) was obtained. By adding a solid lubricant, a thin sheet can be manufactured with the same processing force.

[0131] (Example 15: Electrode using nano-sized Si) 10 g of silicon powder (average particle size 100 nm) used as the negative electrode active material for lithium-ion batteries, 8 g of deionized water, and 1 g of a random copolymer of ethylene oxide-propylene oxide with a weight-average molecular weight of 1 million (molar ratio 9:1) were weighed into a mortar and mixed to obtain a uniform electrode composition. 1 g of this electrode composition was taken and sandwiched between release-type PET films, and a sheet with an average thickness of 2 mm was obtained using a 3 cm diameter stainless steel hand roller (electrode sheet 15-1). Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a sheet with an average thickness of 200 μm (195-205 μm) (electrode sheet 15-2), which could be bent to a diameter of 2 mm.

[0132] (Example 16: Activated carbon and carbon nanotubes (CNTs)) 10 g of activated carbon MSP-20 (Kansai Thermal Chemical), 0.1 g of carbon nanotubes (CNT) (Zeon Nanotechnology, ZEONANO SG101, average diameter: 4 nm, average length: 400 μm, BET specific surface area: 1150 m2 / g) as a component that serves as both a conductive material and a fibrous material, 11 g of DEME-BF4 (N,N-diethyl-N-methyl-N-(2-methoxyethyl)-tetrafluoroborate) as a water-soluble ionic liquid, and 1 g of a random copolymer of ethylene oxide-propylene oxide with a weight-average molecular weight of 1 million (molar ratio 9:1) were weighed into a mortar and mixed to obtain a homogeneous electrode composition. 1 g of this electrode composition was taken and sandwiched between release-type PET films, and a sheet with an average thickness of 2 mm was obtained using a 3 cm diameter SUS hand roller (electrode sheet 16-1). Upon immediate evaluation, this sheet was found to be slightly adhesive, self-supporting, and plastic. Furthermore, a sheet (electrode sheet 16-2) with an average thickness of 200 μm (195-205 μm) obtained by pressing with a hand roller could be bent to a diameter of 2 mm. Such sheets can be used as capacitor electrodes, fuel cell electrodes, air battery electrodes, electrochemical actuators, etc.

[0133] Furthermore, despite having fibers longer than the sheet thickness, no evidence of fibers protruding from the electrodes was observed.

[0134] (Example 17: Fabrication of an insulating layer) 40 g of Aerosil 380 (registered trademark) (manufactured by EVONIK) as a nano-sized filler, 10 g of ethylene oxide-propylene oxide random copolymer with a molecular weight of 1,000,000 (molar ratio of 90:10), and 70 g of 1-butyl-3-methylimidazolium tetrafluoroborate as a solvent were weighed into a mortar and mixed to obtain a homogeneous insulating layer composition. A 50 μm sheet (insulating layer 17) was obtained in the same manner as in Example 1. This sheet was self-supporting and plastic, and could be bent to a diameter of 1 mm.

[0135] Such insulating layers can be used as insulating layers in energy storage devices such as lithium-ion batteries, or they can be attached to glass with a conductive ITO (indium tin oxide) layer and used in dye-sensitized solar cells and electrochromic devices.

[0136] (Example 18: Crosslinking of the insulating layer) 40 g of Aerosil R711 (registered trademark) (manufactured by EVONIK, treated with methacryloxysilane) as a nano-sized filler, 20 g of alumina, 10 g of a random copolymer of ethylene oxide-propylene oxide-allyl glycidyl ether with a molecular weight of 1,000,000 (molar ratio of 90:5:5), 70 g of water as a solvent, and 500 mg of Irg651 as an ultraviolet crosslinking agent were weighed out, and a 50 μm sheet (insulating layer 18) was obtained in the same manner as in Example 1. This sheet was self-supporting and could be bent to a diameter of 1 mm. Without drying this insulating layer 1 while it was sandwiched between release PET films, ultraviolet light was irradiated to crosslink it while maintaining its plasticity, thereby obtaining a crosslinked insulating layer 18.

[0137] When the insulating layer 18 was cut into strips 1 cm wide and stretched while maintaining its plasticity without drying, it broke after stretching by 5%. When the cross-linked insulating layer 18 was stretched in the same way, it did not break even after stretching by 10%. The cross-linked insulating layer is less prone to breaking under mechanical stress and is expected to be more effective in preventing internal short circuits in the device.

[0138] The insulating layer may be used in device assembly while still in a plasticized state, or it may be dried and used in a non-plasticized state. It is also preferable to assemble the device without crosslinking and then crosslink it at the end using ultraviolet light, heat, etc.

[0139] (Example 19: Fabrication of a solid electrolyte-containing insulating layer) LAGP (Li) as a filler with lithium ion conductivity 1.5 Al 0.5 Ge 1.5 P3O 12 ) powder (average particle size 1μm, density 3.0g / cm 3 120 g of ) and 4.5 g of ethylene oxide-propylene oxide random copolymer with a molecular weight of 1,000,000 (molar ratio of 90:10), 42 g of 1-methyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide (Sigma-Aldrich) as a solvent, and 3 g of PTFE were weighed into a mortar and mixed to obtain a uniform insulating layer composition. A 50 μm sheet (insulating layer 19) was obtained in the same manner as in Example 17. This sheet was self-supporting and plastic, and could be bent to a diameter of 1 mm. The volume fraction of the filler in this sheet was 53 vol% for LAGP alone. The ionic conductivity of this sheet was measured by AC impedance method and was 1.0 × 10⁻⁶. -3 It has an ionic conductivity of S / cm and is suitable as an insulating layer for lithium-ion batteries.

[0140] (Example 20: Alkaline production example) 70g of lithium nickelate (Sigma-Aldrich), a strongly alkaline positive electrode active material for lithium-ion batteries, 3g of acetylene black, 8g of deionized water, 1g of carboxymethylcellulose (BSH-12, Daiichi Kogyo Seiyaku Co., Ltd.), and 1g of PTFE were weighed into a mortar and mixed to obtain a uniform electrode composition. 1g of this electrode composition was taken and sandwiched between release-type PET films, and a sheet with an average thickness of 2mm was obtained using a 3cm diameter SUS hand roller (electrode sheet 20-1). Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a sheet with an average thickness of 200μm (195~205μm) (electrode sheet 20-2), which could be bent to a diameter of 2mm. The CMC was in aqueous solution and is thought to have contributed to the flexibility of the electrode.

[0141] When this sheet was attached to 25μm thick aluminum foil and left for about 10 minutes before being peeled off, the surface of the aluminum foil was corroded and whitened by the alkali. This would lead to an increase in resistance when used as an electrode in a lithium-ion battery.

[0142] When the same procedure was performed after the sheet had dried, no whitening of the aluminum foil occurred.

[0143] When the same procedure was performed using an ionic liquid (DEME-TFSI(N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide)) as the processing solvent, no whitening of the aluminum foil occurred.

[0144] (Example 21: Bonding of electrodes and insulating layer) When the electrode sheet 7 prepared in Example 7 and the insulating layer 19 prepared in Example 19 were both plasticized and then bonded together in close contact, ensuring no air bubbles were trapped, a well-adhered, integrated sheet was obtained.

[0145] (Example 22: Fabrication and composite of low-density electrodes) A first electrode sheet (electrode sheet 22-1) was prepared in the same manner as in Example 1, except that the thickness was set to 100 μm. A second electrode sheet (electrode sheet 22-2) was then prepared using 50 g of lithium cobalt oxide, half the amount used in Example 1. The first electrode sheet was attached to a 25 μm thick aluminum foil, and the second electrode sheet was placed on top of it, pressing them together tightly to prevent air bubbles from forming. In this way, a composite electrode sheet with different densities in the upper and lower layers was manufactured. In this case, the bonding may be performed after the first electrode sheet has dried. The density of the second electrode sheet, after drying, was measured to be 2.64 g / cm³. 3 Therefore, the volume fraction of the filler in this electrode, when lithium cobalt oxide and acetylene black are added together, is 61 Vol% in the lower layer and 47 Vol% in the upper layer. Such electrodes, whose density decreases with distance from the current collector, have low ion conduction resistance relative to the electrode thickness, which is advantageous for increasing the power output and operating speed of the device.

[0146] (Example 23: Manufacturing method involving extruding into block form and slicing) Using the composition of Example 2, a molding material composition was manufactured by continuously extruding it in a cylindrical shape with a diameter of 15 mm from a twin-screw extruder (L / D=30) with a 15 mm diameter die. A steel cutter moving laterally to the cylinder was then installed to continuously slice the cylinder into discs with a thickness of 200 μm and a diameter of 15 μm, creating electrode sheets. By changing the die, it is also possible to manufacture hollow cylinders such as macaroni. If it is undesirable to produce metal powder due to metal friction, the die and cutter can be made of ceramic or plastic.

[0147] (Example 24: Manufacturing method involving extrusion into a tube and then cutting) Using the same extruder as in Example 23, the outlet was changed to a ring-shaped die with an outer diameter of 50 mm and an inner diameter of 49 mm, and the material was extruded into a tube with a film thickness of 500 μm. A steel cutter was placed about 100 mm from the die, and a continuous cut was made in one place in the cross-section of the tube. By continuously opening this cut tube, a sheet with a uniform thickness (494-506 μm) was obtained with the same thickness variation in the center and at the ends. If it is undesirable to produce metal powder due to metal friction, the die and cutter can be made of ceramic or plastic.

[0148] (Example 25: Manufactured with multiple strands) Using the same extruder as in Example 23, the die outlet was modified to consist of 20 cylindrical sections with a diameter of 300 μm, spaced 4 mm apart. This was then shaped by sandwiching it between two metal rollers (roll diameter 30 mm, linear pressure 200 N), resulting in the production of a sheet with an average thickness of 32 μm. If metal powder is to be avoided due to metal friction, the roller surface can be made of ceramic or plastic.

[0149] (Example 26: Device Manufacturing Example) A 10mm diameter coil was obtained by winding a 2mm diameter metal rod with a 25μm thick aluminum foil, electrode sheets 2-3 from Example 2, insulating layer 18 from Example 18 and electrode sheets 13-3 from Example 13, and 25μm thick rolled copper foil in that order. All sheets were flexible because they were in a plasticized state, and no damage occurred during winding. This coil was placed in an aluminum laminate package and flattened by lightly pressing from the outside. This was then transferred to a 100°C vacuum dryer and dried for 6 hours. 1MLiPF6 EC / DMC(30 / 70) was injected as the electrolyte, and the lithium-ion battery was created by sealing it under vacuum. When this was charged and discharged at 4.2V~3.0V and a 0.1C rate, a reversible capacity of 145mAh / g per positive electrode active material was obtained, indicating that it functioned as a battery.

[0150] (Example 27: Manganese battery manufacturing example) An aqueous solution containing 20% ​​by weight of zinc chloride and 5% by weight of ammonium chloride was prepared as the electrolyte. 100 parts of manganese dioxide (MnO2, 99.5%, Fujifilm Wako Pure Chemical Industries, 133-09681), 6 parts of acetylene black (Denka Black granular, manufactured by Denki Kagaku Kogyo Co., Ltd.), 2 parts of a random copolymer of ethylene oxide-propylene oxide with a weight-average molecular weight of 1,000,000 as polymer P1 (molar ratio 9:1), and 2 parts of PTFE were weighed into a mortar and pestle. These were thoroughly mixed to obtain a homogeneous electrode composition. 1 g of this electrode composition was taken and sandwiched between release-type PET films. A self-supporting sheet with an average thickness of 2 mm was obtained using a 3 cm diameter SUS hand roller. Immediate evaluation revealed that this sheet was slightly adhesive, self-supporting, and plastic. Further pressing with the hand roller resulted in a sheet with an average thickness of 500 μm (497-503 μm), which could be bent to a diameter of 2 mm. This sheet was cut into a 14mm diameter circle and attached to a graphite sheet (15mm diameter circle) to serve as the positive electrode. Furthermore, a 16mm diameter circle of paper (manufactured by Nippon Kodo Paper Industry, product name "TF4535", 35μm thickness) was prepared as a separator and immersed in the electrolyte solution. Next, zinc foil (manufactured by Niraco, 99.99% purity, 15mm diameter circle, 50μm thickness) was prepared as the negative electrode. These were then stacked in the order of positive electrode, separator, and negative electrode to form a manganese battery, which was assembled into a 2032 type coin cell. The voltage of this battery before discharge was measured at 1.55V, and when discharged with a 20Ω load connected, the discharge rate was 40mA / cm². 2 It was possible to discharge it, and the voltage drop at this time was 0.1V. [Industrial applicability]

[0151] According to the present invention, it is possible to provide a method for manufacturing and recycling components for electrochemical devices that is less prone to problems such as irreversible changes in the composition of electrochemical devices due to solvent reduction, moisture absorption, etc., during the manufacturing of electrochemical devices. Furthermore, according to the present invention, it is possible to provide an electrochemical device component that is less susceptible to problems such as irreversible changes in the composition of an electrochemical device due to solvent reduction, moisture absorption, etc., during the manufacture of an electrochemical device, and an electrochemical device using said electrochemical device component.

Claims

1. At least one type of filler (F); Plasticizers (P-S) which are water, ionic liquids, or mixtures thereof; and Polymer (P1) A molding material composition containing, substantially free of organic solvents, and possessing plasticity and self-supporting properties, is subjected to at least one shaping operation selected from the following group A; and The polymer (P1) is irreversibly crosslinked. A method for manufacturing an electrochemical device component which is an electrode or insulating layer, including The filler (F) contains the active material (A), Manufacturing method. [Group A: Extrusion, injection molding, stretching, compression molding, thickness reduction by pressurization, thickness uniformization by pressurization, cutting, drilling, machining, bending into the final shape for housing electrochemical device containers, bonding of molding material compositions with different compositions]

2. The manufacturing method according to claim 1, wherein the filler (F) includes a fibrous material.

3. At least one type of filler (F); Plasticizers (P-S) which are water, ionic liquids, or mixtures thereof; and Polymer (P1) A molding material composition containing, substantially free of organic solvents, and possessing plasticity and self-supporting properties, is subjected to at least one shaping operation selected from the following group A; and The polymer (P1) is irreversibly crosslinked. A method for manufacturing an electrochemical device component which is an electrode or insulating layer, including The filler (F) includes a fibrous material, Manufacturing method. [Group A: Extrusion, injection molding, stretching, compression molding, thickness reduction by pressurization, thickness uniformization by pressurization, cutting, drilling, machining, bending into the final shape for housing electrochemical device containers, bonding of molding material compositions with different compositions]

4. The manufacturing method according to claim 2 or 3, wherein the fibrous material has a fiber length of 10 μm or more.

5. The manufacturing method according to any one of claims 2 to 4, wherein the fibrous material has a fiber length equal to or greater than the thickness of the component for the electrochemical device.

6. The manufacturing method according to any one of claims 2 to 5, wherein the fibrous material has a nano-sized fiber diameter.

7. The manufacturing method according to any one of claims 1 to 6, wherein the polymer (P1) is a polymer that can be plasticized in an electrolyte solvent (E-S).

8. The manufacturing method according to any one of claims 1 to 7, wherein the polymer (P1) is a deliquescent polymer.

9. The method for producing polymer (P1) according to any one of claims 1 to 7, wherein the polymer (P1) is a polymer containing ethylene oxide (EO) as a monomer unit, a polyoxazoline polymer, a poly-N-vinylacetamide polymer, or an epichlorohydrin-organic amine condensate.

10. The manufacturing method according to any one of claims 1 to 9, wherein the filler (F) comprises an inorganic solid electrolyte.

11. The manufacturing method according to any one of claims 1 to 10, wherein the filler (F) includes a solid lubricant selected from group B below. [Group B: Graphite, graphene, boron nitride, polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes (PFA), molybdenum sulfide, tungsten disulfide, mica, talc, graphite fluoride, melamine cyanurate, metallic soaps]

12. The manufacturing method according to any one of claims 1 to 11, wherein the filler (F) is nano-sized.

13. The manufacturing method according to any one of claims 1 to 12, wherein the volume fraction of the molding material composition is 50% by volume or more, and the filler (F) accounts for 50% by volume or more.

14. The manufacturing method according to any one of claims 1 to 13, wherein the molding material composition further comprises a polymer (P2) that is plasticized by the plasticizer (P-S) but does not dissolve in the electrolyte.

15. The manufacturing method according to any one of claims 1 to 14, wherein the crosslinking method is thermal crosslinking.

16. The manufacturing method according to any one of claims 1 to 14, wherein the crosslinking method is UV crosslinking.

17. The manufacturing method according to any one of claims 1 to 16, wherein the crosslinking agent is added to the molding material composition.

18. The manufacturing method according to any one of claims 1 to 16, wherein the crosslinking agent is added to the electrolyte.

19. The manufacturing method according to any one of claims 1 to 16, wherein the polymer (P1) is a self-crosslinking polymer.

20. A manufacturing method according to any one of claims 1 to 19, comprising managing and providing feedback on the basis weight by measuring the thickness of the component.

21. A manufacturing method according to any one of claims 1 to 20, comprising crushing a plurality of strands made of a molding material composition to form a sheet.

22. A manufacturing method according to any one of claims 1 to 21, comprising obtaining a member by scraping it off from a block-like molding material composition.

23. A manufacturing method according to any one of claims 1 to 22, comprising attaching the molding material composition to a substrate.

24. The manufacturing method according to claim 23, comprising shaping the molding material composition to a desired thickness and then attaching it to the substrate.

25. The manufacturing method according to claim 23 or 24, comprising attaching the molding material composition to the front and back surfaces of the substrate substantially simultaneously.

26. The manufacturing method according to claim 23 or 24, further comprising attaching the molding material composition to the front side of the substrate and then attaching it to the back side.

27. The manufacturing method according to any one of claims 23 to 26, wherein the substrate has a conductive coating on the surface that is in contact with the molding material composition.

28. The manufacturing method according to any one of claims 23 to 27, wherein the substrate mainly contains a polymer.

29. The manufacturing method according to any one of claims 23 to 28, wherein after the molding material composition is attached to the substrate, the member is not cut or perforated together with the substrate.

30. The manufacturing method according to any one of claims 1 to 29, wherein the shaping operation selected from group A is performed at least once while the molding material composition is not in contact with the current collector foil.

31. The manufacturing method according to any one of claims 1 to 29, wherein the shaping operation selected from group A is performed at least once while the molding material composition is not in contact with the porous separator membrane.

32. A manufacturing method according to any one of claims 1 to 31, wherein the plasticizer (P-S) is water or a mixture of water and an ionic liquid, and the method comprises shaping the molding material composition to the final shape when the member is placed in the device, and then removing the moisture by a drying operation to bring it to a non-plasticized state.

33. The manufacturing method according to claim 32, wherein the drying operation is performed by vacuum or heating.

34. The manufacturing method according to claim 32 or 33, wherein the drying operation is performed while the molding material composition is not in contact with the current collector foil.

35. The manufacturing method according to claim 32 or 33, wherein the drying operation is performed while the molding material composition is not in contact with the porous separator membrane.

36. A manufacturing method according to any one of claims 21 to 27, comprising the step of peeling off the molding material composition that is already adhered to the substrate from the substrate.

37. A manufacturing method according to any one of claims 1 to 34, comprising restoring the plasticized state by adding water or humidifying the molding material composition or the molding material composition that has undergone a crosslinking operation after it has become non-plasticized.

38. The manufacturing method according to any one of claims 1 to 35, further comprising using scraps of the molding material composition generated in the process of shaping the molding material composition to manufacture the next member.

39. A method for recycling components for electrochemical devices, comprising the step of peeling off a molding material composition already attached to a substrate from a substrate, in a manufacturing method according to any one of claims 23 to 29.

40. A method for recycling components for electrochemical devices, comprising a manufacturing method according to any one of claims 1 to 36, wherein the molding material composition has become non-plasticized, and the plasticized state is restored by adding water or humidifying it again.

41. A method for recycling components for electrochemical devices, comprising manufacturing a component according to any one of claims 1 to 36, using scraps of the molding material composition generated in the process of shaping the molding material composition to manufacture the next component.

42. A method for manufacturing an electrochemical device, comprising obtaining a component by the method described in any one of claims 1 to 41.

43. The manufacturing method according to claim 42, wherein the polymer (P1) is a polymer that can be plasticized even in an electrolyte solvent (E-S).

44. The manufacturing method according to claim 42 or 43, wherein the molding material composition further comprises a polymer (P2) that is plasticized by the plasticizer (P-S) but does not dissolve in the electrolyte.

45. The manufacturing method according to any one of claims 42 to 44, wherein the crosslinking agent is added to the electrolyte.

46. A method for manufacturing an electrochemical device using an electrochemical device component obtained by the method described in any one of claims 1 to 45.

47. The method for manufacturing an electrochemical device according to claim 46, wherein the electrochemical device component is an electrode, and the electrochemical device further includes a counter electrode to the electrode, the counter electrode comprising at least one selected from alkali metals, alkaline earth metals, metallic aluminum, and silver.

48. The method for manufacturing an electrochemical device according to claim 46 or 47, wherein the electrochemical device is a water-containing electrochemical device whose carrier ions are at least one of alkali metal ions, alkaline earth metal ions, aluminum ions, silver ions, organic nitrogen cations, and halide anions.

49. The method for manufacturing an electrochemical device according to claim 46 or 47, wherein the electrochemical device is a non-aqueous electrochemical device.

50. The method for manufacturing an electrochemical device according to claim 49, wherein the electrochemical device is a non-aqueous electrochemical device whose carrier ions are at least one of alkali metal ions, alkaline earth metal ions, aluminum ions, silver ions, organic nitrogen cations, and halide anions.