WO2020075352A1 - Accumulateur au lithium-ion et procédé de fabrication d'accumulateur au lithium-ion - Google Patents

Accumulateur au lithium-ion et procédé de fabrication d'accumulateur au lithium-ion Download PDF

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Publication number
WO2020075352A1
WO2020075352A1 PCT/JP2019/026271 JP2019026271W WO2020075352A1 WO 2020075352 A1 WO2020075352 A1 WO 2020075352A1 JP 2019026271 W JP2019026271 W JP 2019026271W WO 2020075352 A1 WO2020075352 A1 WO 2020075352A1
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Prior art keywords
layer
ion secondary
current collector
secondary battery
lithium ion
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PCT/JP2019/026271
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English (en)
Japanese (ja)
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安田　剛規
晴章 内田
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昭和電工株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery and a method for manufacturing a lithium ion secondary battery.
  • a lithium ion secondary battery has a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and an electrolyte having lithium ion conductivity and disposed between the positive electrode and the negative electrode.
  • an organic electrolyte or the like has been used as an electrolyte.
  • an all-solid-state and thin-film laminated lithium-ion secondary battery has been proposed in which a solid electrolyte (inorganic solid electrolyte) made of an inorganic material is used as the electrolyte, and the positive electrode, the solid electrolyte, and the negative electrode are all thin films.
  • Patent Document 1 a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated on a substrate made of an insulating resin, and the positive electrode layer, the solid electrolyte layer, and the negative electrode layer formed on the substrate are described. It is described that an overall protective film made of an ultraviolet curable resin is formed so as to cover the entire laminated body including the same.
  • An object of the present invention is to simplify the structure of a thin film type lithium ion secondary battery including a solid electrolyte.
  • the lithium-ion secondary battery of the present invention includes a first current collector layer that is conductive and that collects current, a first polar layer that occludes and releases lithium ions with a first polarity, and a lithium-ion conductive layer.
  • Solid electrolyte layer having an inorganic solid electrolyte exhibiting conductivity, a second polar layer that occludes and releases lithium ions with a second polarity opposite to the first polarity, and has conductivity and current collection.
  • the coating portion may be made of a synthetic resin material. Further, the coating portion may be made of a photoresist material. Further, the coating portion may be composed of a cyclized polymer of perfluorobutenyl vinyl ether.
  • the first current collector layer may be made of SUS316L.
  • the first current collector layer may be made of a metal material having a surface plated with Ni—P.
  • the method for manufacturing a lithium ion secondary battery according to the present invention includes a first current collector layer that has conductivity and that collects current.
  • the liquid organic material is a photoresist material, and the method further comprises an exposure step of exposing the heated liquid organic material over the entire area.
  • the liquid organic material may be a raw material of a cyclized polymer of perfluorobutenyl vinyl ether.
  • the structure of a thin film type lithium ion secondary battery including a solid electrolyte can be simplified.
  • FIG. 4 is a sectional view taken along line IV-IV of FIGS. (A), (b) is a figure showing an example of section composition of a substrate which constitutes a battery part. 4 is a flowchart for explaining a method of manufacturing a lithium ion secondary battery according to an embodiment.
  • (A), (b) is a figure for explaining the outline of a base layer formation process.
  • (A), (b) is a figure for demonstrating the outline of a positive electrode layer forming process.
  • (A), (b) is a figure for explaining the outline of a solid electrolyte layer formation process.
  • (A), (b) is a figure for demonstrating the outline of a holding layer formation process.
  • (A), (b) is a figure for explaining the outline of a diffusion prevention layer forming process.
  • (A), (b) is a figure for demonstrating the outline of a negative electrode electrical power collector layer forming process.
  • (A), (b) is a figure for explaining the outline of a division process.
  • (A), (b) is a figure which shows the structure of the battery part obtained through the division process.
  • (A), (b) is a figure for explaining the outline of a supply process.
  • (A), (b) is a figure for explaining the outline of a coating process.
  • (A), (b) is a figure for demonstrating the outline of a heating process.
  • (A), (b) is a figure for explaining the outline of an exposure process.
  • (A)-(c) is a figure for demonstrating the outline of a battery-ized process. It is a figure which shows the initial charging / discharging characteristic of the lithium ion secondary battery of embodiment. It is a figure which shows the cycle charge / discharge characteristic of the lithium ion secondary battery of embodiment. It is a figure which shows the discharge capacity maintenance factor of the lithium ion secondary battery of embodiment.
  • FIG. 1 is a perspective view showing the overall configuration of a lithium ion secondary battery 100 of this embodiment.
  • FIG. 2 is a perspective view of the battery unit 1 that constitutes the lithium-ion secondary battery 100.
  • FIG. 3A is a front view of the lithium ion secondary battery 100
  • FIG. 3B is a rear view thereof.
  • FIG. 4 is a IV-IV sectional view (longitudinal sectional view of the lithium-ion secondary battery 100) of FIGS. 3A and 3B.
  • the lithium-ion secondary battery 100 of the present embodiment includes a battery unit 1 that functions as a rechargeable battery that can be charged and discharged, that is, a secondary battery, and a coating unit 2 that has an insulating property and covers a main part of the battery unit 1. I have it.
  • the battery unit 1 includes a substrate 10, a base layer 20 laminated on the substrate 10, a positive electrode layer 30 laminated on the base layer 20, and a solid electrolyte layer laminated on the positive electrode layer 30. 40 and 40.
  • the solid electrolyte layer 40 covers the peripheral edges of both the base layer 20 and the positive electrode layer 30 and the end portions thereof are directly laminated on the substrate 10, thereby covering the base layer 20 and the positive electrode layer 30 together with the substrate 10.
  • the lithium ion secondary battery 100 includes a holding layer 50 laminated on the solid electrolyte layer 40, a diffusion preventing layer 60 laminated on the holding layer 50, and a negative electrode collector laminated on the diffusion preventing layer 60. And an electric body layer 70.
  • the substrate 10 as an example of the first current collector layer serves as a base for laminating the base layer 20 to the negative electrode current collector layer 70 by a film forming process.
  • the substrate 10 has a front surface 10a and a back surface 10b, and the base layer 20 to the negative electrode current collector layer 70 are stacked on the front surface 10a. The details of the substrate 10 will be described later.
  • the underlayer 20 is a solid thin film, which enhances the adhesion between the substrate 10 and the positive electrode layer 30, as well as a material (particularly a metal material) forming the substrate 10 and a Li 3 PO 4 (phosphorus) forming the positive electrode layer 30.
  • Li 3 PO 4 phosphorus
  • Li 3 PO 4 and Li + unlikely to occur corrosion by (Li-ion) or PO 4 3- (phosphate ions) constituting formed of a metal or metal compound such as Can be used.
  • the underlayer 20 is made of LiNiO 2 (nickel phosphate). LiNiO 2 is sometimes used as a positive electrode material of the lithium ion secondary battery 100.
  • the thickness of the underlayer 20 can be, for example, 5 nm or more and 50 ⁇ m or less. When the thickness of the underlayer 20 is less than 5 nm, the function as a barrier is lowered and it becomes impractical. On the other hand, if the thickness of the underlayer 20 exceeds 50 ⁇ m, the internal resistance of the battery increases, which is disadvantageous for high-speed charging and discharging.
  • a known film forming method such as various PVD (physical vapor deposition) and various CVD (chemical vapor deposition) may be used, but from the viewpoint of production efficiency, the sputtering method or the vacuum method. It is desirable to use the vapor deposition method.
  • the positive electrode layer 30 as an example of the first polar layer is a solid thin film and contains a positive electrode active material that releases lithium ions during charging and absorbs lithium ions during discharging.
  • the positive electrode active material constituting the positive electrode layer 30 is, for example, a kind selected from manganese (Mn), cobalt (Co), nickel (Ni), iron (Fe), molybdenum (Mo), and vanadium (V). Materials composed of various materials such as oxides, sulfides, and phosphorus oxides containing the above metals can be used.
  • the positive electrode layer 30 may be a composite positive electrode further containing a solid electrolyte.
  • the positive electrode layer 30 is composed of a composite positive electrode including a positive electrode active material and a solid electrolyte made of an inorganic material (inorganic solid electrolyte). More specifically, the positive electrode layer 30 of the present embodiment has a solid electrolyte region mainly containing an inorganic solid electrolyte and a positive electrode region mainly containing a positive electrode active material. Then, in the positive electrode layer 30, the inorganic solid electrolyte forming the solid electrolyte region and the positive electrode active material forming the positive electrode region are mixed in a state of maintaining each. As a result, in the positive electrode layer 30, one is a matrix (base material) and the other is a filler (particles). Here, in the positive electrode layer 30, it is desirable that the solid electrolyte region be a matrix and the positive electrode region be a filler.
  • the positive electrode active material forming the positive electrode layer 30 the same LiNiO 2 as the underlayer 20 is used.
  • Li 3 PO 4 lithium phosphate
  • the ratio between the positive electrode active material and the inorganic solid electrolyte in the positive electrode layer 30 may be appropriately selected.
  • the molar ratio of the positive electrode active material to the inorganic solid electrolyte is from 9: 1 (90%: 10%) to 3: 2 (60%: 40%).
  • the thickness of the positive electrode layer 30 can be, for example, not less than 10 nm and not more than 40 ⁇ m.
  • the thickness of the positive electrode layer 30 is less than 10 nm, the capacity of the obtained lithium ion secondary battery 100 becomes too small, which is not practical.
  • the thickness of the positive electrode layer 30 exceeds 40 ⁇ m, it takes too much time to form the layer, and the productivity is reduced.
  • the thickness of the positive electrode layer 30 may be greater than 40 ⁇ m.
  • a known film forming method such as various PVD or various CVD may be used, but it is preferable to use a sputtering method from the viewpoint of production efficiency.
  • the solid electrolyte layer 40 is a solid thin film made of an inorganic material, and includes an inorganic solid electrolyte capable of moving lithium ions by an externally applied electric field.
  • the solid electrolyte layer 40 of the present embodiment is made of the same Li 3 PO 4 as the inorganic solid electrolyte in the positive electrode layer 30. Further, the solid electrolyte layer 40 of the present embodiment contains Li 3 PO 4 , while LiPON (Li 3 PO 4-x N x (0 ⁇ x ⁇ ) in which part of oxygen in Li 3 PO 4 is replaced by nitrogen. 1)) is not included.
  • the thickness of the solid electrolyte layer 40 can be, for example, 400 nm or more and 800 nm or less.
  • the thickness of the solid electrolyte layer 40 is less than 400 nm, in the obtained lithium ion secondary battery 100, current leakage between the positive electrode layer 30 and the holding layer 50 is likely to occur.
  • the thickness of the solid electrolyte layer 40 exceeds 800 nm, the internal resistance of the battery increases, which is disadvantageous for high-speed charging and discharging.
  • the thickness of the solid electrolyte layer 40 is preferably, for example, not less than 600 nm and not more than 800 nm.
  • the thickness of the positive electrode layer 30 As for the relationship between the thickness of the positive electrode layer 30 and the thickness of the solid electrolyte layer 40, whichever may be thicker or the same. However, from the viewpoint of suppressing an increase in the internal resistance of the battery, it is preferable that the thickness of the solid electrolyte layer 40 be smaller than the thickness of the positive electrode layer 30.
  • a known film forming method such as various PVD or various CVD may be used, but from the viewpoint of production efficiency, it is preferable to use a sputtering method.
  • the holding layer 50 as an example of the second polar layer is a solid thin film, and has a function of holding lithium ions during charging and releasing lithium ions during discharging.
  • the point that the holding layer 50 of the present embodiment does not itself include a negative electrode active material and is configured to hold lithium functioning as a negative electrode active material therein is different from a general negative electrode layer. Is different.
  • the holding layer 50 of the present embodiment has a porous structure, and is constituted by a porous portion (not shown) in which a large number of holes are formed.
  • the porousization of the holding layer 50 that is, the formation of the porous portion, is performed in the first charge / discharge operation after the film formation, and the details will be described later.
  • a platinum group element Ru, Rh, Pd, Os, Ir, Pt
  • gold Au
  • aluminum Al
  • an alloy thereof it is desirable that the holding layer 50 be made of platinum or gold, which is less likely to be oxidized.
  • the holding layer 50 of the present embodiment can be made of the above-mentioned noble metal and metal or a polycrystal of an alloy thereof.
  • the holding layer 50 is made of platinum.
  • the thickness of the holding layer 50 can be, for example, not less than 10 nm and not more than 40 ⁇ m.
  • the thickness of the holding layer 50 is less than 10 nm, the ability to hold lithium becomes insufficient.
  • the thickness of the holding layer 50 exceeds 40 ⁇ m, the internal resistance of the battery increases, which is disadvantageous for high-speed charging and discharging.
  • the thickness of the retaining layer 50 may exceed 40 ⁇ m.
  • a known film forming method such as various PVD or various CVD may be used, but from the viewpoint of production efficiency, it is preferable to use a sputtering method.
  • a method for manufacturing the porous holding layer 50 it is desirable to employ a method of performing charging and discharging, as described later.
  • the diffusion prevention layer 60 is a solid thin film and is for suppressing the diffusion of lithium ions held by the holding layer 50 to the outside of the lithium ion secondary battery 100.
  • a layer made of metal or alloy having an amorphous structure can be used as the diffusion prevention layer 60.
  • the diffusion prevention layer 60 is preferably made of a metal or an alloy that does not form an intermetallic compound with lithium. Among these, from the viewpoint of corrosion resistance, chromium (Cr) alone or an alloy containing chromium is preferred. Is preferred.
  • the diffusion prevention layer 60 may be formed by laminating a plurality of amorphous layers having different constituent materials (for example, a laminated structure of an amorphous chromium layer and an amorphous chromium titanium alloy layer).
  • the “amorphous structure” in the present embodiment includes not only a structure having an amorphous structure as a whole but also a structure in which microcrystals are precipitated in the amorphous structure. .
  • the diffusion preventing layer 60 is made of an alloy of chromium and titanium (CrTi).
  • the metals (alloys) that can be used for the diffusion preventing layer 60 include, in addition to CrTi, ZrCuAlNiPdP, CuZr, FeZr, TiZr, CoZrNb, NiNb, NiTiNb, NiP, CuP, NiPCu, NiTi, AlTi, FeSiB, AuSi And the like.
  • the thickness of the diffusion preventing layer 60 can be, for example, not less than 10 nm and not more than 40 ⁇ m.
  • the thickness of the diffusion preventing layer 60 is less than 10 nm, it is difficult for the lithium that has passed through the holding layer 50 from the solid electrolyte layer 40 side to be blocked by the diffusion preventing layer 60.
  • the thickness of the diffusion prevention layer 60 exceeds 40 ⁇ m, the internal resistance of the battery increases, which is disadvantageous for high-speed charging and discharging.
  • the diffusion preventing layer 60 As a method for manufacturing the diffusion preventing layer 60, a known film forming method such as various PVD or various CVD may be used, but from the viewpoint of production efficiency, it is preferable to use a sputtering method.
  • a sputtering method when the diffusion preventing layer 60 is made of the above-described chromium titanium alloy, if the sputtering method is adopted, the chromium titanium alloy is likely to become amorphous.
  • the negative electrode current collector layer 70 as an example of the second polar layer is a solid thin film having electronic conductivity, and has a function of collecting current to the holding layer 50.
  • the material constituting the negative electrode current collector layer 70 is not particularly limited as long as it has electron conductivity, and various metals and conductive materials including alloys of various metals may be used. it can.
  • a chemically stable material for example, a platinum group element (Ru, Rh, Pd, Os, Ir, Pt) or gold ( Au) or an alloy thereof is preferable.
  • the negative electrode current collector layer 70 is made of the same platinum as the holding layer 50. However, unlike the holding layer 50, the negative electrode current collector layer 70 does not have a porous structure.
  • the thickness of the negative electrode current collector layer 70 can be, for example, not less than 5 nm and not more than 50 ⁇ m. If the thickness of the negative electrode current collector layer 70 is less than 5 nm, the corrosion resistance and the current collecting function will be reduced, and it will not be practical. On the other hand, if the thickness of the negative electrode current collector layer 70 exceeds 50 ⁇ m, the internal resistance of the battery increases, which is disadvantageous for high-speed charging and discharging.
  • the negative electrode current collector layer 70 As a method of manufacturing the negative electrode current collector layer 70, a known film forming method such as various PVD or various CVD may be used, but from the viewpoint of production efficiency, it is preferable to use a sputtering method.
  • the substrate 10 of the present embodiment has a rectangular shape (square shape in this example), one surface being a front surface 10a and the other surface being a back surface 10b.
  • the substrate 10 of this embodiment is made of a conductive material having electronic conductivity.
  • the substrate 10 of the present embodiment functions as a positive electrode current collector layer that collects current to the positive electrode layer 30 via the underlayer 20.
  • the thickness of the substrate 10 can be, for example, not less than 20 ⁇ m and not more than 2000 ⁇ m. When the thickness of the substrate 10 is less than 20 ⁇ m, the strength of the lithium ion secondary battery 100 may be insufficient. On the other hand, if the thickness of the substrate 10 exceeds 2000 ⁇ m, the volume energy density and the weight energy density decrease due to the increase in the thickness and weight of the battery.
  • FIG. 5 is a diagram showing a cross-sectional configuration example of the substrate 10 that constitutes the lithium-ion secondary battery 100 of the embodiment.
  • the substrate 10 shown in FIG. 5A will be referred to as a first configuration example
  • the substrate 10 shown in FIG. 5B will be referred to as a second configuration example.
  • the substrate 10 includes a base material 11 formed of a single-layer metal plate.
  • various metals, alloys thereof, or the like can be used as the metal material forming the base material 11.
  • stainless steel whose coefficient of thermal expansion is close to that of LiNiO 2 is used as the metal material forming the base material 11. Is preferred.
  • the substrate 10 is also used as the positive electrode current collector layer as in the present embodiment, as the metal material forming the base material 11, stainless steel that is resistant to corrosion even under a high voltage environment and is resistant to over-discharge. Is preferably used.
  • the base material 11 forming the substrate 10 is not limited to a single-layer metal plate, and may be formed of a laminate of a plurality of metal plates.
  • the substrate 10 includes a base material 11 formed of a single-layer metal plate and a coating layer 12 that covers the entire surface of the base material 11.
  • the metal material forming the base material various metals, their alloys, metal compounds, and the like can be used.
  • the base material 11 is not limited to a single-layer metal plate, and may be formed of a laminate of a plurality of metal plates.
  • the coating layer 12 As a material forming the coating layer 12, various metals, their alloys, metal compounds, or the like can be used.
  • the substrate 10 in which the coating layer 12 is formed on the base material 11 is adopted, from the viewpoint of suppressing corrosion caused by lithium, CrTi, ZrCuAlNiPdP, CuZr, FeZr, TiZr, CoZrNb, NiNb, It is preferable to use NiTiNb, NiP, CuP, NiPCu, NiTi, AlTi, FeSiB, AuSi, or the like.
  • NiP nickel-phosphorous
  • the method for forming the coating layer 12 is not limited to the plating method, and various film forming methods may be employed.
  • the substrate 10 is formed by covering the entire surface of the base material 11 with the coating layer 12, but the present invention is not limited to this.
  • the coating layer 12 is formed on at least the side of the substrate 11 that becomes the surface 10a. It should be provided.
  • the maximum and minimum height difference Rmm of the substrate 10 of the present embodiment is a measure for defining the smoothness of the laminated surface of the battery structure on the substrate 10 (the surface 10a of the substrate 10 in the present embodiment).
  • the maximum-to-minimum height difference Rmm in the present embodiment is the height between the maximum height and the minimum height obtained by measuring irregularities in a range of 20 ⁇ m ⁇ 20 ⁇ m (square region) with an AFM (Atomic Force Microscope). Defined by the difference. Therefore, the definition of the maximum and minimum height difference Rmm is different from the maximum height Rz defined in, for example, JIS B0601.
  • the maximum / minimum height difference Rmm in the present embodiment is obtained, for example, by using a Bruker D3100, which is an AFM device (atomic force microscope system), and after acquiring data in a region of 20 ⁇ m ⁇ 20 ⁇ m, a reference plane for each scan line.
  • a cubic expression as an approximation polynomial, prepare an image that has been converted (“smoothed”) into displacement from the reference plane (+ displacement and ⁇ displacement may exist), It can be obtained by the "maximum value-minimum value" of the direction (z displacement).
  • the maximum and minimum height difference Rmm of the surface 10a of the substrate 10 is set to 78 nm or less.
  • the maximum / minimum height difference Rmm of the base material 11 located on the front surface 10a side is set to 78 nm or less.
  • the maximum / minimum height difference Rmm of the coating layer 12 located on the front surface 10a side is set to 78 nm or less.
  • the arithmetic average roughness Ra is, for example, specified in JIS B 0601.
  • the arithmetic mean roughness Ra of the surface 10a of the substrate 10 is preferably 1.1 nm or less.
  • the covering portion 2 of the present embodiment is a solid thin film, which protects the battery portion 1 and performs internal insulation and external insulation of the battery portion 1.
  • the coating portion 2 includes an upper surface of the negative electrode current collector layer 70, a side surface of the negative electrode current collector layer 70, a side surface of the diffusion prevention layer 60, a side surface of the holding layer 50, an upper surface (end side) and side surfaces of the solid electrolyte layer 40, Also, the side surface of the substrate 10 is covered. However, an opening 2a where the coating 2 does not exist is formed in substantially the center of the upper surface of the negative electrode current collector layer 70, and an exposed portion 71 from which the negative electrode current collector layer 70 is exposed is formed at this portion. It is provided. Further, the covering portion 2 does not cover the lower surface of the substrate 10, and the back surface 10b (see FIG. 5) of the substrate 10 is exposed at this portion.
  • the exposed portion 71 of the negative electrode current collector layer 70 functions as a negative electrode used for electrical connection with the outside, and the back surface 10b of the substrate 10 is formed. , But functions as a positive electrode used for electrical connection to the outside.
  • the covering part 2 various materials such as an organic material and an inorganic material can be used as long as they have insulation properties.
  • the battery unit 1 of the present embodiment has a structure that expands and contracts in the thickness direction with charging and discharging, as will be described later, the covering unit 2 is more flexible and expandable than an inorganic material. It is desirable to use an organic material (particularly a synthetic resin material), which is also expensive.
  • the covering portion 2 has good adhesion to each layer exposed to the outside of the battery portion 1 (in this example, the substrate 10, the solid electrolyte layer 40, the holding layer 50, the diffusion preventing layer 60, and the negative electrode current collector layer 70). It is desirable to use high materials. Further, from the viewpoint of making it easier to observe the state of the battery unit 1 from the outside of the lithium-ion secondary battery 100, the covering unit 2 has a light-transmitting property with respect to light having a wavelength in the visible region. Is desirable.
  • the covering portion 2 for example, silicon oxide (SiO 2 ) can be cited.
  • a synthetic resin material can be cited, and it is particularly preferable to use various photoresist materials and various engineering plastic materials.
  • the photoresist material may be either a positive type or a negative type, but a positive type is preferable from the viewpoint of simplifying the manufacturing process of the covering portion 2.
  • the engineering plastic material may be either a thermoplastic resin or a thermosetting resin, but from the viewpoint of obtaining high toughness, the thermoplastic resin is desirable.
  • a fluororesin from the viewpoint of ensuring durability against chemicals and electrical insulation, it is preferable to use an amorphous fluororesin. More desirable.
  • the amorphous fluororesin are those obtained by copolymerizing a fluoropolymer of a crystalline polymer to make it amorphous as a polymer alloy, and a perfluorodioxole copolymer (Teflon AF manufactured by DuPont). (Registered trademark)) and a cyclized polymer of perfluorobutenyl vinyl ether (trade name Cytop (registered trademark) manufactured by AGC Co.).
  • the thickness of the covering portion 2 can be, for example, 100 nm or more and 2 mm or less. If the thickness of the covering portion 2 is less than 100 nm, there is a high possibility that pinholes and the like will be formed, and Li may be oxidized by exposure to the atmosphere, or insulation may not be ensured. On the other hand, when the thickness of the covering portion 2 exceeds 2 mm, it becomes difficult to reduce the thickness of the lithium-ion secondary battery 100 as a whole, and it takes too much time to form the layer, which lowers the productivity.
  • a method for producing the covering portion 2 for example, when an inorganic material is used, a known film forming method such as various PVD or various CVD, or a sol-gel method can be adopted.
  • an organic material for example, a film forming method in which a liquid raw material is applied by dip coating, spin coating, a brush, or the like and then cured by heating or exposure can be adopted.
  • a film forming method in which the raw material is subjected to perforation processing, etc., and then placed on an object and cured by heating is adopted.
  • the solid raw material include a thermosetting epoxy resin sheet (a product of Kyocera Co., Ltd., a melting sheet).
  • FIG. 6 is a flowchart for explaining the method of manufacturing lithium-ion secondary battery 100 of the present embodiment.
  • the lithium-ion secondary battery 100 according to the present embodiment includes a battery part forming step (step 1) of forming the battery part 1, a covering part forming step of forming the covering part 2 on the battery part 1 (step 2), and a battery. It is manufactured through a battery forming step (step 3) of converting the basic structure of the lithium-ion secondary battery 100 in which the cover 2 is formed on the part 1 into a battery.
  • a substrate preparing process is performed to prepare the substrate 10 that has been surface-treated so that the maximum and minimum height difference Rmm of the surface 10a is 78 nm or less (step 11). Note that, here, the case where four (2 ⁇ 2) battery units 1 are formed using one substrate 10 is taken as an example, and the square substrate 10 is prepared.
  • the substrate 10 according to the first configuration example shown in FIG. 5A is manufactured by the following procedure, for example.
  • a metal plate is manufactured by a rolling method or the like, and the surface 10a side of the base material 11 obtained by cutting the metal plate is subjected to a general mechanical polishing treatment, and then further subjected to CMP (Chemical Mechanical Polishing).
  • CMP Chemical Mechanical Polishing
  • the substrate 10 according to the second configuration example shown in FIG. 5B is manufactured by the following procedure, for example.
  • a metal plate is manufactured by a rolling method or the like, and a coating layer 12 made of Ni—P is formed on the entire surface of a base material 11 obtained by cutting the metal plate by an electroless nickel plating method or the like.
  • a laminate of the material 11 and the coating layer 12 is obtained.
  • a polishing process using a CMP method or the like is performed, so that the surface 10a
  • the substrate 10 having the maximum and minimum height difference Rmm set to 78 nm or less is obtained.
  • FIG. 7 is a diagram for explaining the outline of the step 12 of forming the underlayer.
  • FIG. 7A shows a front view
  • FIG. 7B shows a VIIB-VIIB sectional view of FIG. 7A.
  • each base layer 20 has a rectangular shape (square shape), and the area of each is set to a common size. Therefore, the area of each underlayer 20 is smaller than the area of the substrate 10 (less than 1/4 in this example).
  • the surface 10a of the substrate 10 is exposed between two adjacent underlayers 20 by providing a gap between the underlayers 20 so that the underlayers 20 do not contact each other.
  • substrate 10 is called a 1st laminated body.
  • FIG. 8 is a diagram for explaining the outline of the positive electrode layer forming step of step 13.
  • FIG. 8A is a front view
  • FIG. 8B is a sectional view taken along line VIIIB-VIIIB of FIG. 8A.
  • substrate 10 is called a 2nd laminated body.
  • FIG. 9 is a diagram for explaining the outline of the solid electrolyte layer forming step of step 14.
  • FIG. 9A shows a front view
  • FIG. 9B shows a sectional view taken along line IXB-IXB of FIG. 9A.
  • the solid electrolyte layer 40 is formed on the surface of the second laminated body on which the positive electrode layer 30 is formed.
  • the solid electrolyte layer 40 has a rectangular shape (square shape), and the area of the solid electrolyte layer 40 is the same as the area of the substrate 10.
  • the solid electrolyte layer 40 is formed so as to cover the surface and the side surface of the positive electrode layer 30, the side surface of the base layer 20, and the region of the surface 10 a of the substrate 10 that is not in contact with the base layer 20.
  • the solid electrolyte layer 40 is formed so as not to contact the side surface of the substrate 10 or the back surface 10b.
  • substrate 10 is called a 3rd laminated body.
  • FIG. 10 is a diagram for explaining the outline of the holding layer forming step of step 15.
  • FIG. 10A shows a front view
  • FIG. 10B shows a sectional view taken along the line XB-XB of FIG. 10A.
  • each holding layer 50 has a rectangular shape (square shape), and the area of each is set to a common size.
  • the area of each holding layer 50 is made larger than the area of each of the base layer 20 and each of the positive electrode layers 30 described above.
  • each holding layer 50 is arranged so as to overlap each positive electrode layer 30 when viewed from above, and the entire outer peripheral edge of each holding layer 50 is located outside the entire outer peripheral edge of each positive electrode layer 30. There is.
  • FIG. 11 is a diagram for explaining the outline of the diffusion prevention layer forming step of step 16.
  • FIG. 11A shows a front view
  • FIG. 11B shows a sectional view taken along the line XIB-XIB of FIG. 11A.
  • substrate 10 is called the 5th laminated body.
  • FIG. 12 is a diagram for explaining the outline of the negative electrode current collector layer forming step of step 17.
  • FIG. 12A shows a front view
  • FIG. 12B shows a sectional view taken along line XIIB-XIIB of FIG. 12A.
  • the sixth laminated body obtained in this way has a structure in which four battery parts 1 are integrated. Then, this sixth laminated body is removed from the sputtering apparatus.
  • FIG. 13 is a diagram for explaining the outline of the dividing process in step 18.
  • FIG. 13A shows a front view
  • FIG. 13B shows a sectional view taken along the line XIIIB-XIIIB of FIG. 13A.
  • FIG. 14 is a diagram showing a configuration of the battery unit 1 obtained through the division process of step 18.
  • FIG. 14A shows a front view
  • FIG. 14B shows a sectional view taken along the line XIVB-XIVB of FIG. 14A.
  • the battery unit 1 is formed by cutting the sixth laminated body along a plurality (vertical x 1, lateral x 1) of the dividing lines D into individual pieces. More specifically, the sixth laminated body is divided into a plurality of layers (4) by dividing the sixth laminated body so as to include the independent underlayer 20, the positive electrode layer 30, the holding layer 50, the diffusion prevention layer 60, and the negative electrode current collector layer 70. Individual battery parts 1 are obtained.
  • the method for cutting the sixth stacked body include a method using a dicing blade and a method using a laser.
  • step 2 (Coating part forming process) Subsequently, the covering portion forming step of step 2 will be described.
  • FIG. 15 is a diagram for explaining the outline of the supply process in step 21.
  • FIG. 15A shows a front view
  • FIG. 15B shows a sectional view taken along the line XVB-XVB of FIG. 15A.
  • the battery unit 1 is mounted on a stage (not shown) of a spin coater so that the negative electrode current collector layer 70 side faces upward. Then, a liquid photoresist 200 (an example of a liquid organic material) is annularly supplied onto the negative electrode current collector layer 70 in the battery unit 1. At this time, the photoresist 200 can be supplied to the battery unit 1 by, for example, dropping. By thus supplying the photoresist 200 in a ring shape, the opening 2a surrounded by the photoresist 200 is formed in the negative electrode current collector layer 70, and this portion is the negative electrode current collector. It becomes the exposed portion 71 in the layer 70.
  • a liquid photoresist 200 an example of a liquid organic material
  • FIG. 16 is a diagram for explaining the outline of the coating process in step 22.
  • FIG. 16A shows a front view
  • FIG. 16B shows a cross-sectional view taken along the line XVIB-XVIB of FIG. 16A.
  • the stage of the spin coater equipped with the battery unit 1 to which the photoresist 200 is supplied is rotated, and the photoresist 200 is radially extended by the centrifugal force.
  • the photoresist 200 reaches the upper surface of the solid electrolyte layer 40 from the upper surface of the negative electrode current collector layer 70 through each side surface of the negative electrode current collector layer 70, the diffusion prevention layer 60, and the holding layer 50, and , Reach each side surface of the solid electrolyte layer 40 and the substrate 10. That is, the photoresist 200 covers the upper surface and the side surface of the battery unit 1.
  • the opening 2a formed by the photoresist 200 on the upper surface of the battery portion 1, that is, the central portion of the upper surface of the negative electrode current collector layer 70 is maintained as it is, and the exposed portion 71 is covered with the negative electrode current collector. Part of the upper surface of the electric body layer 70 is exposed. Further, the lower surface of the battery unit 1, that is, the lower surface of the substrate 10 is not covered with the photoresist 200 and is kept exposed.
  • FIG. 17 is a diagram for explaining the outline of the heating process of step 23.
  • FIG. 17A shows a front view
  • FIG. 17B shows a sectional view taken along the line XVIIB-XVIIB of FIG. 17A.
  • the battery unit 1 coated with the photoresist 200 is removed from the spin coater stage and mounted on a hot plate (not shown) so that the negative electrode current collector layer 70 side faces upward. Then, the hot plate is operated to heat (bak) the battery unit 1 coated with the photoresist 200. Then, with heating, the organic solvent contained in the photoresist 200 is volatilized, and the photoresist 200 adheres to the battery unit 1.
  • the photoresist may be heated in an oven.
  • FIG. 18 is a diagram for explaining the outline of the exposure process in step 24.
  • FIG. 18A shows a front view
  • FIG. 18B shows a sectional view taken along the line XVIIIB-XVIIIB of FIG. 18A.
  • the photoresist 200 that is brought into close contact with the battery unit 1 is irradiated with light having a wavelength at which the photoresist 200 has sensitivity, over the entire area without particularly interposing a mask or the like.
  • the photoresist 200 that is brought into close contact with the battery unit 1 is cured by exposure and becomes the solid coating unit 2.
  • the basic structure of the lithium ion secondary battery 100 having the battery part 1 and the covering part 2 is obtained.
  • step 3 In the battery conversion process of step 3, first, the initial charging process is performed to charge the basic structure of the lithium-ion secondary battery 100 in which the battery part 1 is formed with the coating part 2 for the first time (step). 31).
  • the initial discharging process for discharging the basic structure of the charged lithium-ion secondary battery 100 for the first time is performed (step 32).
  • the holding layer 50 is made porous, that is, the porous portion and a large number of pores are formed, and the lithium ion secondary battery 100 shown in FIG. 1 is obtained.
  • FIG. 19 is a view for explaining the procedure for making the holding layer 50 porous, and is an enlarged view of the holding layer 50 and its periphery.
  • FIG. 19A shows a state before the first charge (before step 31)
  • FIG. 19B shows a state after the first charge and before the first discharge (between step 31 and step 32).
  • 19 (c) shows the state after the initial discharge (after step 32), respectively.
  • the holding layer 50 is densified.
  • the thickness of the holding layer 50 is the thickness of the holding layer t50
  • the thickness of the diffusion prevention layer 60 is the thickness of the diffusion prevention layer t60
  • the thickness of the negative electrode current collector layer 70 is the thickness of the negative electrode current collector layer. It is t70.
  • the lithium ions that have moved from the positive electrode layer 30 side to the holding layer 50 side are alloyed with the metal constituting the holding layer 50.
  • the holding layer 50 is made of platinum (Pt)
  • platinum and platinum are alloyed (solid solution, formation of an intermetallic compound, or eutectic).
  • the diffusion prevention layer 60 of the present embodiment is made of a metal or an alloy having an amorphous structure, and the number of grain boundaries is significantly smaller than that of the holding layer 50 having a polycrystalline structure. ing. For this reason, the lithium ions that have reached the boundary between the holding layer 50 and the diffusion prevention layer 60 are less likely to enter the diffusion prevention layer 60, and thus maintain the state held in the holding layer 50.
  • the lithium ions that have moved from the positive electrode layer 30 to the holding layer 50 are held by the holding layer 50.
  • the lithium ions that have moved to the holding layer 50 are held by the holding layer 50 by alloying with platinum or by precipitating metallic lithium in the platinum.
  • the holding layer thickness t50 is after the film formation and before the initial charge shown in FIG. 19A.
  • the volume of the holding layer 50 increases with the first charge. This is considered to be due to the fact that lithium and platinum are alloyed in the holding layer 50.
  • the thickness t60 of the diffusion prevention layer does not substantially change before and after the first charge. That is, the volume of the diffusion prevention layer 60 is not substantially changed by the first charge. This is considered to be due to the fact that lithium hardly enters the diffusion preventing layer 60.
  • the thickness t70 of the negative electrode current collector layer does not substantially change before and after the first charge, that is, the volume of the negative electrode current collector layer 70 does not substantially change before and after the first charge (negative electrode current collector). It is considered that the platinum constituting the electric conductor layer 70 is not made porous and remains dense like the platinum constituting the holding layer 50).
  • the alloy of lithium and platinum is dealloyed (dissolution of the metallic lithium when metallic lithium is precipitated) with the release of lithium. Then, as a result of dealloying in the holding layer 50, the holding layer 50 is made porous, and becomes a porous portion 51 in which a large number of holes 52 are formed.
  • the porous portion 51 obtained in this way is almost composed of metal (for example, platinum).
  • metal for example, platinum
  • the holding layer thickness t50 is larger than that after the initial charge and before the initial discharge shown in FIG. 19B. Decrease. This is considered to be due to the fact that the alloy of lithium and platinum is dealloyed in the holding layer 50. This is supported by the fact that the shape of the holes 52 formed in the holding layer 50 by the first discharge is flattened so that the thickness direction is smaller than the plane direction. Further, as shown in FIG. 19C, in the lithium-ion secondary battery 100 after the initial discharge, the holding layer thickness t50 is larger than that after the film formation shown in FIG. 19A and before the initial charge. To do.
  • the holding layer 50 is made porous by the first charging and the first discharging, that is, a large number of holes 52 are formed in the holding layer 50.
  • the thickness t60 of the diffusion prevention layer and the thickness t70 of the negative electrode current collector layer are not substantially changed before and after the first discharge.
  • An Al substrate plated with NiP was used as the substrate 10.
  • the size of the substrate 10 (when viewed from above: the same hereinafter) was 12 mm ⁇ 12 mm, and the thickness was 8 mm.
  • lithium nickel oxide (LiNiO 2 ) formed by a sputtering method was used.
  • the size of the underlayer 20 was 8 mm ⁇ 8 mm, and the thickness was 200 nm.
  • lithium nickel oxide (LiNiO 2 ) and lithium phosphate (Li 3 PO 4 ) formed by a sputtering method were used.
  • the size of the positive electrode layer 30 was 8 mm ⁇ 8 mm, and the thickness was 800 nm.
  • lithium phosphate (Li 3 PO 4 ) formed by a sputtering method was used for the solid electrolyte layer 40.
  • the size of the solid electrolyte layer 40 was 12 mm ⁇ 12 mm, and the thickness was 1000 nm.
  • platinum (Pt) formed by the sputtering method was used for the holding layer 50.
  • the holding layer 50 had a size of 10 mm ⁇ 10 mm and a thickness of 60 nm.
  • a CoZrNb alloy (more specifically, Co 91 Zr 5 Nb 4 ) formed by a sputtering method was used for the diffusion prevention layer 60.
  • the diffusion prevention layer 60 had a size of 10 mm ⁇ 10 mm and a thickness of 200 nm.
  • Platinum (Pt) formed by a sputtering method was used for the negative electrode current collector layer 70.
  • the negative electrode current collector layer 70 had a size of 10 mm ⁇ 10 mm and a thickness of 60 nm.
  • the lithium-ion secondary battery 100 was manufactured according to the manufacturing method shown in FIG. More specifically, each layer of the battery unit 1 was formed by using the sputtering method.
  • the coating portion 2 was obtained by applying the photoresist 200 made of S1813G described above to the battery portion 1 by spin coating, and then performing heating (baking) and exposure.
  • the initial charge / discharge characteristics are charge / discharge characteristics when the basic structure of the lithium ion secondary battery 100 is repeatedly charged and discharged including initial charging and initial discharging three times (3 cycles).
  • Table 1 shows the evaluation conditions of the initial charge and discharge.
  • the charging and discharging currents were set to 80 ( ⁇ A), 400 ( ⁇ A), 800 ( ⁇ A), 1300 ( ⁇ A) and 2700 ( ⁇ A), respectively.
  • FIG. 20 is a diagram showing the initial charge / discharge characteristics of the lithium-ion secondary battery 100 of the present embodiment. 20, the horizontal axis represents the battery capacity ( ⁇ Ah) and the vertical axis represents the battery voltage (V). Further, in FIG. 20, the charging characteristic is shown in the upper right of the figure, and the discharging characteristic is shown in the lower right of the figure.
  • the lithium-ion secondary battery 100 of the present embodiment can be charged / discharged within a charge / discharge current range of 80 ( ⁇ A) to 2700 ( ⁇ A).
  • the cycle charge / discharge characteristic is the charge / discharge characteristic when the basic structure of the lithium ion secondary battery 100 is repeatedly charged / discharged.
  • Table 2 shows the evaluation conditions of the cycle charge / discharge.
  • CC Constant current
  • the number of times of charging / discharging in cycle charging was set to 1 time (1 cycle), 500 times (500 cycles) and 1000 times (1000 cycles).
  • FIG. 21 is a diagram showing the cycle charge / discharge characteristics of the lithium ion secondary battery 100 of the present embodiment.
  • the horizontal axis represents the battery capacity ( ⁇ Ah), and the vertical axis represents the battery voltage (V).
  • the charging characteristic is shown in the upper right of the figure, and the discharging characteristic is shown in the lower right of the figure.
  • the lithium-ion secondary battery 100 of the present embodiment can maintain a substantially constant level in the range of 1 to 1000 times of charge / discharge cycles, in other words, the number of charge / discharge cycles. It can be seen that the deterioration of the charge / discharge performance due to the increase of is suppressed.
  • the discharge capacity retention ratio is the discharge capacity (n-th time) of the lithium-ion secondary battery 100 when the charge-discharge is performed n times with respect to the discharge capacity (first discharge capacity) when the first charge-discharge is executed.
  • the discharge capacity) of the above is expressed as a percentage. That is, "nth discharge capacity / first discharge capacity" is expressed in percentage. In this case, the higher the discharge capacity retention rate, the better, and the maximum value is 100%.
  • the discharge capacity retention rate was obtained based on the result of measuring the charge / discharge characteristics according to the evaluation conditions for the cycle charge / discharge characteristics (see Table 2) described above.
  • the number of charge / discharge cycles was 1300 (1300 cycles).
  • FIG. 22 is a diagram showing the capacity maintenance rate of the lithium-ion secondary battery 100 of the present embodiment.
  • the horizontal axis represents the number of times charging and discharging are repeated (the number of cycles), and the vertical axis represents the discharge capacity retention rate (%).
  • the lithium-ion secondary battery 100 of the present embodiment has a lower discharge capacity maintenance rate as the number of charge / discharge cycles increases.
  • the discharge capacity maintenance ratio of the lithium-ion secondary battery 100 of the present embodiment can be secured at about 86%, which means that the charge / discharge cycle increases and decreases. It can be seen that the deterioration of discharge performance can be suppressed.
  • the underlayer 20, the positive electrode layer 30, the solid electrolyte layer 40, the holding layer 50, the diffusion prevention layer 60, and the negative electrode current collector layer 70 are laminated in this order on the surface 10 a of the substrate 10.
  • the battery unit 1 was configured. That is, a configuration is adopted in which the positive electrode layer 30 is arranged on the side closer to the substrate 10 and the holding layer 50 is arranged on the side farther from the substrate 10.
  • the configuration is not limited to this, and a configuration in which the holding layer 50 is arranged on the side closer to the substrate 10 and the positive electrode layer 30 is arranged on the side farther from the substrate 10 may be adopted.
  • the stacking order of the layers on the substrate 10 is opposite to that described above, and the substrate 10 functions as the negative electrode current collector layer 70.
  • the battery unit 1 includes the substrate 10, the base layer 20, the positive electrode layer 30, the solid electrolyte layer 40, the holding layer 50, the diffusion prevention layer 60, and the negative electrode current collector layer 70.
  • the configuration of the battery unit 1 may be changed as appropriate.
  • the coating portion 2 is formed using the photoresist 200 as a raw material
  • the present invention is not limited to this.
  • the covering portion 2 is formed using the product name Cytop (registered trademark) manufactured by AGC Co. as a raw material
  • the exposure step of step 24 in the covering portion forming step of step 2 is unnecessary.
  • the covering portion 2 is formed by using a meltable sheet manufactured by Kyocera Co., Ltd. as a raw material, this sheet is subjected to perforation processing corresponding to the opening 2a, and then stacked on the battery portion 1, It suffices to perform heating. Therefore, in this case, the supply step of step 21, the coating step of step 22 and the exposure step of step 24 in the coating portion forming step of step 2 are unnecessary.
  • SYMBOLS 1 Battery part, 2 ... Covering part, 2a ... Opening part, 10 ... Substrate, 10a ... Front surface, 10b ... Back surface, 11 ... Base material, 12 ... Coating layer, 20 ... Underlayer, 30 ... Positive electrode layer, 40 ... Solid Electrolyte layer, 50 ... Retaining layer, 51 ... Porous part, 52 ... Hole, 60 ... Diffusion preventive layer, 70 ... Negative electrode current collector layer, 71 ... Exposed part, 100 ... Lithium ion secondary battery, 200 ... Photoresist

Abstract

L'invention concerne un accumulateur au lithium-ion 100 comprenant : une unité de batterie 1 obtenue par stratification, sur un substrat 10 qui a une électroconductivité et qui sert également de couche collectrice d'électrode positive, une couche de base 20, une couche d'électrode positive 30, une couche d'électrolyte solide 40, une couche de maintien 50, une couche de prévention de diffusion 60 et une couche collectrice d'électrode négative 70 ; et une partie de revêtement 2 qui a des propriétés isolantes et recouvre la partie latérale de l'unité de batterie 1. La partie de revêtement 2 est configurée de façon à ne pas recouvrir la partie centrale de la surface supérieure de la couche collectrice d'électrode négative 70 positionnée sur le côté supérieur de l'unité de batterie 1, ou la surface arrière du substrat 10 positionnée sur le côté inférieur de l'unité de batterie 1, et ces sections sont utilisées pour une connexion électrique avec l'extérieur.
PCT/JP2019/026271 2018-10-10 2019-07-02 Accumulateur au lithium-ion et procédé de fabrication d'accumulateur au lithium-ion WO2020075352A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002117851A (ja) * 2000-07-31 2002-04-19 Kawasaki Steel Corp 炭素材料、リチウムイオン二次電池用負極およびリチウムイオン二次電池
WO2007086218A1 (fr) * 2006-01-24 2007-08-02 Murata Manufacturing Co., Ltd. Pile à microcircuit
JP2011258477A (ja) * 2010-06-10 2011-12-22 Sumitomo Electric Ind Ltd 非水電解質電池
JP2014032966A (ja) * 2013-10-15 2014-02-20 Sony Corp 電池パック
JP2015072849A (ja) * 2013-10-04 2015-04-16 国立大学法人鳥取大学 二次電池用負極材、二次電池用負極材の製造方法および二次電池用負極
JP2019040674A (ja) * 2017-08-22 2019-03-14 昭和電工株式会社 リチウムイオン二次電池、リチウムイオン二次電池の正極

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002117851A (ja) * 2000-07-31 2002-04-19 Kawasaki Steel Corp 炭素材料、リチウムイオン二次電池用負極およびリチウムイオン二次電池
WO2007086218A1 (fr) * 2006-01-24 2007-08-02 Murata Manufacturing Co., Ltd. Pile à microcircuit
JP2011258477A (ja) * 2010-06-10 2011-12-22 Sumitomo Electric Ind Ltd 非水電解質電池
JP2015072849A (ja) * 2013-10-04 2015-04-16 国立大学法人鳥取大学 二次電池用負極材、二次電池用負極材の製造方法および二次電池用負極
JP2014032966A (ja) * 2013-10-15 2014-02-20 Sony Corp 電池パック
JP2019040674A (ja) * 2017-08-22 2019-03-14 昭和電工株式会社 リチウムイオン二次電池、リチウムイオン二次電池の正極

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