WO2019123951A1 - Accumulateur au lithium-ion - Google Patents

Accumulateur au lithium-ion Download PDF

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Publication number
WO2019123951A1
WO2019123951A1 PCT/JP2018/042840 JP2018042840W WO2019123951A1 WO 2019123951 A1 WO2019123951 A1 WO 2019123951A1 JP 2018042840 W JP2018042840 W JP 2018042840W WO 2019123951 A1 WO2019123951 A1 WO 2019123951A1
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Prior art keywords
layer
ion secondary
lithium ion
secondary battery
positive electrode
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PCT/JP2018/042840
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English (en)
Japanese (ja)
Inventor
晴章 内田
坂脇　彰
安田　剛規
Original Assignee
昭和電工株式会社
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Priority claimed from JP2018192560A external-priority patent/JP2019114529A/ja
Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to US16/771,719 priority Critical patent/US20210175512A1/en
Priority to CN201880077375.4A priority patent/CN111418106A/zh
Publication of WO2019123951A1 publication Critical patent/WO2019123951A1/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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

Definitions

  • the present invention relates to a lithium ion secondary battery.
  • a lithium ion secondary battery is known as a secondary battery satisfying such a demand.
  • the lithium ion secondary battery has a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and an electrolyte that exhibits lithium ion conductivity and is disposed between the positive electrode and the negative electrode.
  • an organic electrolytic solution or the like has been used as an electrolyte.
  • a solid electrolyte inorganic solid electrolyte
  • the negative electrode current collector It has been proposed to provide a block region containing an active material (see Patent Document 1).
  • An object of the present invention is to suppress the leakage of lithium to the outside in an all solid lithium ion secondary battery.
  • the lithium ion secondary battery of the present invention is not composed of a metal or alloy having a solid structure containing an inorganic solid electrolyte exhibiting lithium ion conductivity, a holding layer capable of holding lithium, and an amorphous structure. And an amorphous metal layer in order.
  • the amorphous metal layer may be characterized by containing chromium (Cr).
  • the amorphous metal layer may be made of an alloy of chromium (Cr) and titanium (Ti).
  • the amorphous metal layer may be characterized by being made of a metal or an alloy which does not form an intermetallic compound with lithium.
  • the amorphous metal layer is characterized in that it is made of any of ZrCuAlNiPdP, CuZr, FeZr, TiZr, CoZrNb, NiNb, NiTiNb, NiP, CuP, NiPCu, NiTi, CrTi, AlTi, FeSiB, AuSi. can do.
  • the holding layer may be characterized by being made of a platinum group element (Ru, Rh, Pd, Os, Ir, Pt) having a porous structure, gold (Au), or an alloy thereof.
  • the holding layer can be characterized by being made of titanium having a plurality of columnar crystals each extending in the thickness direction.
  • the holding layer can be characterized by containing a negative electrode active material. Further, the holding layer can be characterized by containing a positive electrode active material. Further, a positive electrode layer containing a positive electrode active material is provided on the side opposite to the holding layer of the solid electrolyte layer, and the size of the plane of the holding layer is larger than the size of the plane of the positive electrode layer. can do. In addition, it is characterized by further comprising a noble metal layer composed of a platinum group element (Ru, Rh, Pd, Os, Ir, Pt) or gold (Au) or an alloy thereof, and laminated on the amorphous metal layer. can do.
  • Ru, Rh, Pd, Os, Ir, Pt platinum group element
  • Au gold
  • FIG. 1 is a view showing a cross-sectional configuration of a lithium ion secondary battery of Embodiment 1; 3 is a flowchart for illustrating a method of manufacturing the lithium ion secondary battery of Embodiment 1.
  • FIG. 2 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery after film formation and before initial charge according to Embodiment 1.
  • (A) to (c) are diagrams for explaining the procedure for making the holding layer porous.
  • A) is a cross section STEM photograph of the lithium ion secondary battery after film formation and before the first charge
  • (b) is a cross section STEM photograph of the lithium ion secondary battery after the first discharge.
  • FIG. 1 is a view showing a cross-sectional configuration of a lithium ion secondary battery of Embodiment 1
  • 3 is a flowchart for illustrating a method of manufacturing the lithium ion secondary battery of Embodiment 1.
  • FIG. 2 is a diagram showing a cross-sectional configuration
  • FIG. 5 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery of a first modified example of the first embodiment.
  • FIG. 7 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery of a second modified example of the first embodiment.
  • FIG. 16 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery of a third modified example of the first embodiment.
  • FIG. 18 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery of a fourth modified example of the first embodiment.
  • (A), (b) is a figure which shows the cross-sectional structure of the lithium ion secondary battery of Embodiment 2.
  • FIG. FIG. 10 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery of Embodiment 3.
  • 7 is a cross-sectional STEM photograph of a lithium ion secondary battery of another configuration example according to Embodiment 1.
  • FIG. 1 is a view showing a cross-sectional configuration of the lithium ion secondary battery 1 of the first embodiment.
  • the lithium ion secondary battery 1 of the present embodiment has a structure in which a plurality of layers (films) are stacked, as described later, and after forming a basic structure by a so-called film formation process, The structure is completed by the charge and discharge operation.
  • FIG. 1 shows the state after the first discharge, that is, the structure of the lithium ion secondary battery 1 is completed.
  • the lithium ion secondary battery 1 shown in FIG. 1 includes a substrate 10, a positive electrode current collector layer 20 stacked on the substrate 10, a positive electrode layer 30 stacked on the positive electrode current collector layer 20, and a positive electrode layer 30.
  • a solid electrolyte layer 40 laminated on the upper side, and a holding layer 50 laminated on the solid electrolyte layer 40 are provided.
  • the solid electrolyte layer 40 covers the peripheries of both the positive electrode current collector layer 20 and the positive electrode layer 30 and the end portions thereof are directly laminated on the substrate 10, whereby the positive electrode current collector layer 20 and the substrate 10 are obtained.
  • the positive electrode layer 30 is covered.
  • the lithium ion secondary battery 1 is stacked on the holding layer 50 and directly stacked on the solid electrolyte layer 40 at the periphery of the holding layer 50, thereby covering the solid electrolyte layer 40 with the holding layer 50.
  • a covering layer 60 Furthermore, the lithium ion secondary battery 1 is laminated on the covering layer 60 and directly laminated on the solid electrolyte layer 40 at the periphery of the covering layer 60, thereby covering the covering layer 60 with respect to the solid electrolyte layer 40.
  • a negative electrode current collector layer 70 is provided.
  • the substrate 10 is not particularly limited, and substrates made of various materials such as metal, glass, and ceramics can be used.
  • the substrate 10 is formed of a metal plate having electron conductivity. More specifically, in the present embodiment, a stainless steel foil (plate) having a mechanical strength higher than that of copper, aluminum or the like is used as the substrate 10. Further, as the substrate 10, a metal foil plated with a conductive metal such as tin, copper, chromium or the like may be used as the substrate 10.
  • the thickness of the substrate 10 can be, for example, 20 ⁇ m or more and 2000 ⁇ m or less. If the thickness of the substrate 10 is less than 20 ⁇ m, the strength of the lithium ion secondary battery 1 may be insufficient. On the other hand, when the thickness of the substrate 10 exceeds 2000 ⁇ m, the volume energy density and weight energy density decrease due to the increase in thickness and weight of the battery.
  • the positive electrode current collector layer 20 is not particularly limited as long as it is a solid thin film and has electron conductivity, and for example, a conductive material containing various metals or an alloy of various metals is used. Can.
  • the thickness of the positive electrode current collector layer 20 can be, for example, 5 nm or more and 50 ⁇ m or less. If the thickness of the positive electrode current collector layer 20 is less than 5 nm, the current collection function is lowered and it is not practical. On the other hand, when the thickness of the positive electrode current collector layer 20 exceeds 50 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge.
  • the positive electrode current collector layer 20 As a method of manufacturing the positive electrode current collector layer 20, known film forming methods such as various PVD (physical vapor deposition) and various CVD (chemical vapor deposition) may be used, but from the viewpoint of production efficiency It is desirable to use a method or a vacuum evaporation method.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the positive electrode current collector layer 20 may not be provided between the substrate 10 and the positive electrode layer 30.
  • the positive electrode current collector layer 20 may be provided between the substrate 10 and the positive electrode layer 30.
  • the positive electrode layer 30 is a solid thin film, and contains a positive electrode active material that desorbs lithium ions during charging and stores lithium ions during discharging.
  • a positive electrode active material constituting the positive electrode layer 30 for example, one type selected from manganese (Mn), cobalt (Co), nickel (Ni), iron (Fe), molybdenum (Mo), vanadium (V) It is possible to use one composed of various materials such as oxides, sulfides or phosphorus oxides containing the above metals.
  • the positive electrode layer 30 may be a composite positive electrode containing a solid electrolyte.
  • the thickness of the positive electrode layer 30 can be, for example, 10 nm or more and 40 ⁇ m or less. If the thickness of the positive electrode layer 30 is less than 10 nm, the capacity of the obtained lithium ion secondary battery 1 becomes too small to be practical. On the other hand, when the thickness of the positive electrode layer 30 exceeds 40 ⁇ m, it takes too long to form the layer, and the productivity is lowered. However, when the battery capacity required for the lithium ion secondary battery 1 is large, the thickness of the positive electrode layer 30 may be more than 40 ⁇ m.
  • the positive electrode layer 30 As a method of producing the positive electrode layer 30, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of production efficiency, it is desirable to use the sputtering method.
  • the solid electrolyte layer 40 is a solid thin film, and includes a solid electrolyte (inorganic solid electrolyte) made of an inorganic material.
  • the inorganic solid electrolyte constituting the solid electrolyte layer 40 is not particularly limited as long as it exhibits lithium ion conductivity, and is made of various materials such as oxides, nitrides, and sulfides. Can be used.
  • the thickness of the solid electrolyte layer 40 can be, for example, 10 nm or more and 10 ⁇ m or less.
  • the thickness of the solid electrolyte layer 40 is less than 10 nm, a short circuit (leakage) is likely to occur between the positive electrode layer 30 and the holding layer 50 in the obtained lithium ion secondary battery 1.
  • the thickness of the solid electrolyte layer 40 exceeds 10 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge.
  • the solid electrolyte layer 40 As a method of manufacturing the solid electrolyte layer 40, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of production efficiency, it is preferable to use the sputtering method.
  • the holding layer 50 is a solid thin film and has a function of holding lithium ions.
  • maintenance layer 50 shown in FIG. 1 is comprised by the porous part 51 in which the many void
  • the holding layer 50 can be made of a platinum group element (Ru, Rh, Pd, Os, Ir, Pt) or gold (Au) or an alloy of these. Among these, it is preferable that the holding layer 50 be made of platinum (Pt) or gold (Au) that is more resistant to oxidation.
  • the holding layer 50 (porous portion 51) of the present embodiment can be formed of the above-described noble metal or a polycrystal of an alloy of these.
  • the thickness of the holding layer 50 can be, for example, 10 nm or more and 40 ⁇ m or less. If the thickness of the retention layer 50 is less than 10 nm, the ability to retain lithium will be insufficient. On the other hand, when the thickness of the holding layer 50 exceeds 40 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge. However, when the battery capacity required for the lithium ion secondary battery 1 is large, the thickness of the holding layer 50 may be more than 40 ⁇ m.
  • the holding layer 50 As a method of manufacturing the holding layer 50, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of production efficiency, it is preferable to use the sputtering method. And as a manufacturing method of the holding layer 50 made porous, it is desirable to employ
  • the covering layer 60 as an example of the amorphous metal layer is made of a metal or an alloy which is a solid thin film and has an amorphous structure. And among these, from the viewpoint of corrosion resistance, it is preferable that it is chromium (Cr) alone or an alloy containing chromium, and it is more preferable that it is an alloy of chromium and titanium (Ti).
  • the covering layer 60 is preferably made of a metal or alloy which does not form an intermetallic compound with lithium (Li).
  • the covering layer 60 can also be configured by laminating a plurality of amorphous layers different in constituent material (for example, a laminated structure of an amorphous chromium layer and an amorphous chromium titanium alloy layer).
  • amorphous layers different in constituent material for example, a laminated structure of an amorphous chromium layer and an amorphous chromium titanium alloy layer.
  • the range of the composition ratio to become an amorphous structure depends on the conditions for forming the layer, and thus the range of the preferred composition ratio can not be defined. It may be selected in combination with
  • the “amorphous structure” in the present embodiment includes not only one having an amorphous structure as a whole but also one having microcrystals precipitated in the amorphous structure. .
  • the thickness of the covering layer 60 can be, for example, 10 nm or more and 40 ⁇ m or less. When the thickness of the covering layer 60 is less than 10 nm, it is difficult for the covering layer 60 to stop the lithium that has passed through the holding layer 50 from the solid electrolyte layer 40 side. On the other hand, when the thickness of the covering layer 60 exceeds 40 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge.
  • the covering layer 60 As a method of manufacturing the covering layer 60, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of production efficiency, it is desirable to use the sputtering method.
  • the covering layer 60 is made of the above-described chromium titanium alloy, the chromium titanium alloy is likely to be amorphous if the sputtering method is employed.
  • Examples of metals (alloys) that can be used for the covering layer 60 include ZrCuAlNiPdP, CuZr, FeZr, TiZr, CoZrNb, NiNb, NiNb, NiTiNb, NiP, CuP, NiPCu, NiTi, CrTi, AlTi, FeSiB, and AuSi. be able to.
  • the negative electrode current collector layer 70 as an example of the noble metal layer is not particularly limited as long as it is a solid thin film and has electron conductivity, and includes, for example, various metals and alloys of various metals.
  • a conductive material can be used.
  • a chemically stable material for example, platinum group elements (Ru, Rh, Pd, Os, Ir, Pt) or gold (Au) Or preferably composed of these alloys.
  • the thickness of the negative electrode current collector layer 70 can be, for example, 5 nm or more and 50 ⁇ m or less. If the thickness of the negative electrode current collector layer 70 is less than 5 nm, the corrosion resistance and the current collection function are reduced, which is not practical. On the other hand, when the thickness of the negative electrode current collector layer 70 exceeds 50 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge.
  • the negative electrode current collector layer 70 As a method of manufacturing the negative electrode current collector layer 70, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of production efficiency, it is desirable to use the sputtering method.
  • the positive electrode layer 30 and the holding layer 50 face each other with the solid electrolyte layer 40 interposed therebetween. That is, the positive electrode layer 30 containing the positive electrode active material is positioned on the opposite side of the solid electrolyte layer 40 to the holding layer 50.
  • the size of the plane of the holding layer 50 is larger than the size of the plane of the positive electrode layer 30.
  • the entire peripheral edge of the plane of the positive electrode layer 30 is located inside the entire peripheral edge of the plane of the holding layer 50.
  • the lower surface (planar surface) of the holding layer 50 is opposed to the upper surface (planar surface) of the positive electrode layer 30 shown in FIG. 1 with the solid electrolyte layer 40 interposed therebetween.
  • FIG. 2 is a flowchart for explaining the method of manufacturing the lithium ion secondary battery of the first embodiment.
  • the substrate 10 is mounted on a sputtering apparatus (not shown), and a positive electrode current collector layer forming step of forming the positive electrode current collector layer 20 on the substrate 10 is performed (step 20).
  • the positive electrode layer forming step of forming the positive electrode layer 30 on the positive electrode current collector layer 20 is performed by the sputtering apparatus (step 30).
  • a solid electrolyte layer forming step of forming the solid electrolyte layer 40 on the positive electrode layer 30 is executed by the sputtering apparatus (step 40).
  • a holding layer forming step of forming the holding layer 50 on the solid electrolyte layer 40 is performed by the sputtering apparatus (step 50).
  • a covering layer forming step of forming a covering layer 60 on the solid electrolyte layer 40 and the holding layer 50 is performed (step 60).
  • the negative electrode current collector layer forming step of forming the negative electrode current collector layer 70 on the solid electrolyte layer 40 and the covering layer 60 is executed by the sputtering apparatus (step 70).
  • an initial charge step of performing the first charge on the lithium ion secondary battery 1 removed from the sputtering apparatus is performed (step 80).
  • an initial discharge step of performing a first discharge on the charged lithium ion secondary battery 1 is performed (step 90).
  • the holding layer 50 is made porous, that is, the porous portion 51 and the plurality of pores 52 are formed, and the lithium ion secondary battery 1 shown in FIG. 1 is obtained. The details of making the holding layer 50 porous by the first charge and discharge operation will be described later.
  • FIG. 3 is a view showing a cross-sectional configuration of the lithium ion secondary battery 1 after film formation and before initial charge according to the first embodiment.
  • FIG. 3 shows a state in which steps up to step 70 shown in FIG. 2 are completed.
  • FIG. 1 shows a state in which step 90 (all steps) shown in FIG. 2 is completed.
  • the basic configuration of the lithium ion secondary battery 1 shown in FIG. 3 is the same as that shown in FIG. However, the lithium ion secondary battery 1 shown in FIG. 3 is different in that the holding layer 50 is not made porous and is more compact than that shown in FIG. 1. Further, the lithium ion secondary battery 1 shown in FIG. 3 is different in that the thickness of the holding layer 50 is thinner than that shown in FIG. 1.
  • FIG. 4 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 the periphery thereof.
  • FIG. 4 (a) shows the state after film formation and before the first charge (after step 70)
  • FIG. 4 (b) shows the state after the first charge and before the first discharge (between step 80 and step 90).
  • FIG. 4C shows the state after the first discharge (after step 90), respectively. Therefore, FIG. 4 (a) corresponds to FIG. 3, and FIG. 4 (c) corresponds to FIG.
  • the holding layer 50 is densified.
  • the thickness of the holding layer 50 is a holding layer thickness t50
  • the thickness of the covering layer 60 is a covering layer thickness t60
  • the thickness of the negative electrode current collector layer 70 is a negative electrode current collector layer thickness t70. It is.
  • the substrate 10 (see FIG. 1) has a positive electrode of a DC power supply, and the negative electrode collector layer 70 has a DC power supply. Negative electrodes are connected respectively.
  • the lithium ions (Li + ) constituting the positive electrode active material in the positive electrode layer 30 move to the holding layer 50 via the solid electrolyte layer 40. That is, in the charging operation, lithium ions move in the thickness direction of the lithium ion secondary battery 1 (upward in FIG. 4B).
  • lithium ions moved from the positive electrode layer 30 side to the holding layer 50 side are alloyed with the noble 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 covering 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 reduced as compared with the holding layer 50 having a polycrystalline structure. There is. For this reason, the lithium ions that have reached the boundary between the holding layer 50 and the covering layer 60 hardly enter the covering layer 60, and therefore, the state of being held in the holding layer 50 is maintained.
  • the lithium ions transferred from the positive electrode layer 30 to the holding layer 50 are held by the holding layer 50 in the state where the initial charging operation is finished. At this time, it is considered that lithium ions transferred to the holding layer 50 are held in the holding layer 50 by alloying with platinum, precipitation of metal lithium in platinum, or the like.
  • the holding layer thickness t50 is after the film formation shown in FIG. 4 (a) and before the first charge. Increase from the state of That is, the volume of the holding layer 50 is increased by the first charge. This is considered to be attributable to the alloying of lithium and platinum in the holding layer 50.
  • the coating layer thickness t60 is substantially unchanged before and after the first charge. That is, the volume of the covering layer 60 is not substantially changed by the first charge. This is considered to be due to the fact that lithium does not easily enter the covering layer 60.
  • the negative electrode current collector layer thickness t70 does not substantially change before and after the initial charge, that is, the volume of the negative electrode current collector layer 70 does not substantially change before and after the initial charge (negative electrode collection). It is considered that the platinum that constitutes the collector layer 70 is supported by the fact that it is not made porous like the platinum that constitutes the holding layer 50 and remains compact.
  • the substrate 10 (see FIG. 1) has a positive electrode of the load and the negative electrode collector layer 70 of the negative electrode. The electrodes are connected respectively. Then, as shown in FIG. 4C, lithium ions (Li + ) held in the holding layer 50 move to the positive electrode layer 30 through the solid electrolyte layer 40. That is, in the discharge operation, lithium ions move in the thickness direction of the lithium ion secondary battery 1 (downward in FIG. 4C) and are held in the positive electrode layer 30. Along with this, a direct current is supplied to the load.
  • the dealloying of the alloy of lithium and platinum (the dissolution of metal lithium when metal lithium is deposited) is performed as lithium is separated. And as a result of performing dealloying by the holding
  • the porous portion 51 obtained in this manner is substantially composed of a noble metal (for example, platinum).
  • a noble metal for example, platinum
  • the holding layer thickness t50 is greater than the state after the first charge and before the first discharge shown in FIG. 4B. Decrease. This is considered to be due to the fact that the alloy of lithium and platinum is dealloyed in the retaining layer 50. This is supported by the fact that the shape of the holes 52 formed in the holding layer 50 by the initial discharge is flattened so that the thickness direction becomes smaller than the surface direction. Further, as shown in FIG. 4C, in the lithium ion secondary battery 1 after the first discharge, the holding layer thickness t50 is larger than the state after the film formation shown in FIG. 4A and before the first charge. Do.
  • the holding layer 50 is made porous by the first charge and the first discharge, that is, a large number of pores 52 are formed in the holding layer 50.
  • the coating layer thickness t60 and the negative electrode current collector layer thickness t70 are substantially the same before and after the first discharge.
  • FIG. 5 is a cross-sectional STEM (Scanning Transmission Electron Microscope) photograph of the lithium ion secondary battery 1 of the present embodiment, where (a) shows the state after film formation and before the first charge, and (b) shows the state after the first discharge. The state of each is shown.
  • the STEM photograph was taken using a Hitachi High-Technologies Corporation HD-2300 ultrathin film evaluation apparatus.
  • FIG. 5 (a) corresponds to FIG. 4 (a) (and FIG. 3) described above
  • FIG. 5 (b) corresponds to FIG. 4 (c) (and FIG. 1) described above.
  • the specific structure and manufacturing method of the lithium ion secondary battery 1 shown to Fig.5 (a) are as showing below.
  • Stainless steel (SUS304) was used for the substrate 10 (not shown in FIG. 5).
  • the thickness of the substrate 10 was 30 ⁇ m.
  • the positive electrode current collector layer 20 (not shown in FIG. 5), aluminum formed by sputtering was used. The thickness of the positive electrode current collector layer 20 was 100 nm.
  • lithium manganate Li 1.5 Mn 2 O 4
  • the thickness of the positive electrode layer 30 was 1000 nm.
  • LiPON a lithium phosphate (Li 3 PO 4 ) part of which oxygen was replaced with nitrogen
  • the thickness of the solid electrolyte layer 40 was 1000 nm.
  • the thickness of the holding layer 50 was 410 nm (after film formation and before initial charge).
  • a chromium titanium alloy (more specifically, Cr 50 Ti 50 ) formed by a sputtering method was used.
  • the thickness of the covering layer 60 was 50 nm.
  • the negative electrode current collector layer 70 platinum (Pt) formed by a sputtering method was used.
  • the thickness of the negative electrode current collector layer 70 was 100 nm.
  • the crystal structure was analyzed by electron beam diffraction, and it was as follows.
  • the substrate 10 made of SUS304, the positive electrode current collector layer 20 made of aluminum, the holding layer 50 made of platinum, and the negative electrode current collector layer 70 were each crystallized.
  • the positive electrode layer 30 made of lithium manganate, the solid electrolyte layer 40 made of LiPON, and the coating layer 60 made of a chromium titanium alloy were respectively made amorphous.
  • the solid electrolyte layer 40, and the covering layer 60 a ring was slightly observed by electron beam diffraction, and it was found that microcrystals were present in the amorphous structure.
  • FIG. 5A shows that the holding layer 50 is almost uniformly white
  • FIG. 5B shows that a plurality of gray spots are present on the white background.
  • the holding layer 50 is flattened on the side of the boundary with the covering layer 60 so that the thickness direction becomes smaller than the surface direction, and compared to other gray spots. It also shows that relatively large gray areas exist.
  • FIG. 5 (b) it is considered that the white part corresponds to the porous part 51 and the gray part corresponds to the air holes 52.
  • FIG.5 (b) it turns out also compared with FIG.5 (a) that the holding
  • the thickness of the holding layer 50 shown in FIG. 5B was 610 nm (after the first discharge).
  • both FIG. 5A and FIG. 5B it can be seen that the covering layer 60 and the negative electrode current collector layer 70 hardly change with respect to their respective shades. Furthermore, in both FIG. 5A and FIG. 5B, it can also be seen that the coating layer 60 and the negative electrode current collector layer 70 hardly change with respect to their respective thicknesses.
  • FIG. 12 is a cross-sectional STEM photograph of a lithium ion secondary battery 1 of another configuration example according to the present embodiment.
  • FIG. 12 shows the state after the first discharge. Similar to FIG. 5 described above, this STEM photograph was taken using an HD-2300 ultrathin film evaluation apparatus manufactured by Hitachi High-Technologies Corporation.
  • FIG. 12 corresponds to FIG. 4 (c) (and FIG. 1) described above.
  • the specific configuration and manufacturing method of the lithium ion secondary battery 1 shown in FIG. 12 are as follows.
  • Stainless steel (SUS304) was used for the substrate 10 (not shown in FIG. 12).
  • the thickness of the substrate 10 was 30 ⁇ m.
  • the positive electrode current collector layer 20 (not shown in FIG. 12), aluminum formed by sputtering was used. The thickness of the positive electrode current collector layer 20 was 100 nm.
  • lithium manganate Li 1.5 Mn 2 O 4
  • the thickness of the positive electrode layer 30 was 1000 nm.
  • lithium phosphate (Li 3 PO 4 ) formed by sputtering was used for the solid electrolyte layer 40.
  • the thickness of the solid electrolyte layer 40 was 1000 nm.
  • the thickness of the holding layer 50 was 70 nm (after film formation and before initial charge).
  • the covering layer 60 a CoZrNb alloy (more specifically, Co 91 Zr 5 Nb 4 ) formed by a sputtering method was used.
  • the thickness of the covering layer 60 was 200 nm.
  • the negative electrode current collector layer 70 platinum (Pt) formed by a sputtering method was used.
  • the thickness of the negative electrode current collector layer 70 was 70 nm.
  • the crystal structure of the lithium ion secondary battery 1 obtained as described above after film formation and before the first charge was analyzed by electron beam diffraction, and found to be as follows.
  • the substrate 10 made of SUS304, the positive electrode current collector layer 20 made of aluminum, the holding layer 50 made of platinum, and the negative electrode current collector layer 70 were each crystallized.
  • the positive electrode layer 30 made of lithium manganate, the solid electrolyte layer 40 made of lithium phosphate (Li 3 PO 4 ), and the coating layer 60 made of a CoZrNb alloy were amorphized, respectively.
  • the solid electrolyte layer 40, and the covering layer 60 a ring was slightly observed by electron beam diffraction, and it was found that microcrystals were present in the amorphous structure.
  • the holding layer 50 is flattened on the side of the boundary with the covering layer 60 so that the thickness direction becomes smaller than the surface direction, and It can be seen that relatively large gray areas exist as compared to gray spots.
  • the white area corresponds to the porous portion 51
  • the gray area corresponds to the air holes 52.
  • the thickness of the holding layer 50 shown in FIG. 12 was 105 nm (after the first discharge).
  • the coating layer 60 and the negative electrode current collector layer 70 hardly changed with respect to their respective shades and thicknesses before and after the first charge and discharge.
  • the coating layer 60 was laminated. Thereby, as compared with, for example, the case where the covering layer 60 having a polycrystalline structure is laminated on the holding layer 50, the covering layer 60 of lithium transferred from the positive electrode layer 30 to the holding layer 50 along with the charging operation Leaks to the outside can be suppressed.
  • the holding layer 50 made of porous platinum is provided on the solid electrolyte layer 40.
  • the negative electrode layer made of, for example, silicon (Si) or the like is provided on solid electrolyte layer 40, peeling within lithium ion secondary battery 1 accompanying expansion due to charge and contraction due to discharge. Can be suppressed.
  • the negative electrode current collector layer 70 made of platinum is provided on the covering layer 60.
  • the corrosion (deterioration) due to oxidation or the like of the metal or alloy constituting the covering layer 60 is suppressed as compared to the case where the negative electrode current collector layer 70 made of other than noble metal is provided on the covering layer 60 be able to.
  • the size of the flat surface of the positive electrode layer 30 and the holding layer 50 disposed with the solid electrolyte layer 40 therebetween is positive electrode layer 30 ⁇ holding layer 50.
  • movement in the lateral direction (surface direction) when lithium ions move from the positive electrode layer 30 to the holding layer 50 side is suppressed.
  • leakage of lithium ions from the side of the lithium ion secondary battery 1 to the outside can be suppressed.
  • platinum is used when the holding layer 50 is formed of platinum group elements (Ru, Rh, Pd, Os, Ir, Pt) or gold (Au) or their alloys.
  • the holding layer 50 can be made porous by charging and discharging, as in the case where the holding layer 50 is constituted alone, and lithium can be held in the holding layer 50.
  • substrate 10 and solid electrolyte layer 40 are used to cover positive electrode current collector layer 20 and positive electrode layer 30, and solid electrolyte layer 40 and covering layer 60. And although the structure which covers the holding layer 50 using the negative electrode collector layer 70 was employ
  • FIG. 6 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery 1 of a first modified example of the first embodiment.
  • FIG. 6 shows a state after the first discharge, that is, a state in which the structure of the lithium ion secondary battery 1 is completed (corresponding to FIG. 1 of the first embodiment).
  • the planar size of the positive electrode current collector layer 20 and the positive electrode layer 30 when viewed from the upper side of FIG. 6 is substantially the same as the planar size of the solid electrolyte layer 40.
  • This is different from the first embodiment.
  • the first modification after manufacturing lithium ion secondary battery 1 including dense holding layer 50 in the same procedure as in Embodiment 1 (see FIG. 2), charging for the first time after film formation is performed. By performing the discharge operation, the lithium ion secondary battery 1 (see FIG. 6) in which the holding layer 50 is made porous can be obtained.
  • FIG. 7 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery 1 according to a second modification of the first embodiment.
  • FIG. 7 shows a state after the first discharge, that is, a state in which the structure of the lithium ion secondary battery 1 is completed (corresponding to FIG. 1 of the first embodiment).
  • the size of the plane of the covering layer 60 when viewed from above in FIG. 7 is the same as the size of the plane of the holding layer 50, and when viewed from above in FIG.
  • the second embodiment differs from the first embodiment in that the size of the negative electrode current collector layer 70 is the same as the size of the flat surface of the covering layer 60.
  • charging for the first time after film formation is performed. By performing the discharge operation, it is possible to obtain the lithium ion secondary battery 1 (see FIG. 7) in which the holding layer 50 is made porous.
  • FIG. 8 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery 1 of a third modification of the first embodiment.
  • FIG. 8 shows a state after the first discharge, that is, a state in which the structure of the lithium ion secondary battery 1 is completed (corresponding to FIG. 1 of the first embodiment).
  • the size of the plane of the covering layer 60 when viewed from above in FIG. 8 is the same as the size of the plane of the holding layer 50, and when viewed from above in FIG.
  • This embodiment differs from the first modification in that the size of the negative electrode current collector layer 70 is the same as the size of the flat surface of the covering layer 60.
  • charging for the first time after film formation is performed. By performing the discharge operation, the lithium ion secondary battery 1 (see FIG. 8) in which the holding layer 50 is made porous can be obtained.
  • FIG. 9 is a diagram showing a cross-sectional configuration of a lithium ion secondary battery 1 of a fourth modification of the first embodiment.
  • FIG. 9 shows a state (corresponding to FIG. 1 of the first embodiment) after the first discharge, that is, the structure of the lithium ion secondary battery 1 is completed.
  • the size of the plane of the holding layer 50 when viewed from above in FIG. 9 is the same as the size of the plane of the solid electrolyte layer 40, Is different.
  • the fourth modification after manufacturing lithium ion secondary battery 1 including dense holding layer 50 in the same procedure as in Embodiment 1 (see FIG. 2), charging for the first time after film formation is performed. By performing the discharge operation, it is possible to obtain a lithium ion secondary battery 1 (see FIG. 9) in which the holding layer 50 is made porous.
  • the holding layer 50 is made of a noble metal having a porous structure.
  • the holding layer 50 is made of titanium (Ti) having a plurality of columnar crystals each extending in the thickness direction.
  • Ti titanium
  • the same components as those in Embodiment 1 are assigned the same reference numerals and detailed explanations thereof will be omitted.
  • FIG. 10 is a diagram showing a cross-sectional configuration of lithium ion secondary battery 1 of the second embodiment.
  • the lithium ion secondary battery 1 of the present embodiment has a structure in which a plurality of layers (films) are stacked, and after a basic structure is formed by a so-called film formation process, The structure is completed by the first (first) charging operation.
  • FIG. 10A shows the state after film formation and before the first charge
  • FIG. 10B shows the state after the first charge.
  • the lithium ion secondary battery 1 after film formation and before the first charge is the substrate 10, the positive electrode current collector layer 20, and the positive electrode layer 30 as in the first embodiment.
  • the solid electrolyte layer 40, the holding layer 50, the covering layer 60, and the negative electrode current collector layer 70 are stacked in this order.
  • the basic configuration of the lithium ion secondary battery 1 after the initial charge is substantially the same as the lithium ion secondary battery 1 after the film formation shown in FIG. 10 (a) and before the initial charge. However, the difference is that the negative electrode 80 is formed inside the holding layer 50.
  • the holding layer 50 of the present embodiment is a solid thin film, and has a structure in which a plurality of columnar crystals each made of titanium metal (Ti) and extending in the thickness direction are arranged side by side.
  • the columnar crystals of titanium constituting the holding layer 50 are usually composed of hexagonal columnar crystals.
  • the thickness of the holding layer 50 can be, for example, 10 nm or more and 40 ⁇ m or less. If the thickness of the retention layer 50 is less than 10 nm, the ability to retain lithium will be insufficient. On the other hand, when the thickness of the holding layer 50 exceeds 40 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge.
  • the holding layer 50 As a method for manufacturing the holding layer 50, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of efficiently forming an aggregate of columnar crystals of titanium, the sputtering method is used. It is desirable to use
  • the negative electrode 80 contains a negative electrode active material that stores lithium ions at the time of charge and releases lithium ions at the time of discharge.
  • the negative electrode 80 of the present embodiment is formed inside the holding layer 50 by the charging operation. More specifically, in the holding layer 50, the lithium ion is held at the boundary between adjacent columnar crystals, that is, the so-called crystal grain boundary, whereby the negative electrode 80 is formed.
  • metal lithium itself functions as a negative electrode active material.
  • the negative electrode 80 it is desirable to adopt a method of forming (depositing) the negative electrode 80 by charging.
  • the substrate 10 is mounted on a sputtering apparatus (not shown), and the positive electrode current collector layer 20, the positive electrode layer 30, the solid electrolyte layer 40, the holding layer 50, the covering layer 60 and the negative electrode current collector layer 70 are formed on the substrate 10.
  • the layers are formed (stacked) in this order.
  • the lithium ion secondary battery 1 after film formation and before the first charge shown in FIG. 10A is obtained.
  • the lithium ion secondary battery 1 is removed from the sputtering apparatus.
  • the lithium ion secondary battery 1 after film formation and before the first charge shown in FIG. 10A is charged for the first time.
  • the lithium ion secondary battery 1 shown in FIG. 10A lithium is precipitated at the crystal grain boundaries present inside the holding layer 50. That is, the negative electrode 80 made of lithium is formed inside the holding layer 50, and the lithium ion secondary battery 1 after the initial charge shown in FIG. 10 (b) is obtained.
  • the details of the charge and discharge operation of the lithium ion secondary battery 1 will be described later.
  • the lithium ions moved from the positive electrode layer 30 side to the holding layer 50 side reach the boundary between the solid electrolyte layer 40 and the holding layer 50.
  • the holding layer 50 is made of metallic titanium and has a plurality of columnar crystals each extending in the thickness direction, and the plurality of columnar crystals are arranged side by side.
  • the lithium ions reaching the boundary between the solid electrolyte layer 40 and the retention layer 50 enter the grain boundaries of the adjacent columnar crystals and move further along the thickness direction, and are retained in the retention layer 50. .
  • the covering layer 60 is made of an amorphized metal or alloy in which the number of grain boundaries is smaller than that of titanium metal (aggregation of columnar crystals) constituting the holding layer 50. For this reason, the lithium ions that have reached the boundary between the holding layer 50 and the covering layer 60 hardly enter the covering layer 60, and therefore, the state of being held in the holding layer 50 is maintained.
  • the lithium ions moved from the positive electrode layer 30 to the holding layer 50 side are held at the grain boundaries existing between the columnar crystals in the holding layer 50 to constitute the negative electrode 80.
  • the substrate 10 When discharging (using) the lithium ion secondary battery 1 in a charged state, the substrate 10 is connected to the positive electrode of the load, and the negative electrode current collector layer 70 is connected to the negative electrode of the load. Then, lithium ions contained in the negative electrode 80 present inside the holding layer 50 move along the thickness direction (downward direction in FIG. 10) to the positive electrode layer 30 via the solid electrolyte layer 40, and the positive electrode layer 30 constitute a positive electrode active material. Along with this, a direct current is supplied to the load.
  • the negative electrode 80 does not necessarily disappear inside the holding layer 50, and remains by part of lithium which is not moved by the discharge operation.
  • the coating layer 60 was laminated. Thereby, as compared with, for example, the case where the covering layer 60 having a polycrystalline structure is laminated on the holding layer 50, the covering layer 60 of lithium transferred from the positive electrode layer 30 to the holding layer 50 along with the charging operation Leaks to the outside can be suppressed.
  • the holding layer 50 formed by arranging columnar crystals made of titanium is provided on the solid electrolyte layer 40.
  • the negative electrode layer made of, for example, silicon (Si) or the like is provided on solid electrolyte layer 40, peeling within lithium ion secondary battery 1 accompanying expansion due to charge and contraction due to discharge. Can be suppressed.
  • the negative electrode current collector layer 70 made of platinum is provided on the covering layer 60.
  • the corrosion (deterioration) due to oxidation or the like of the metal or alloy constituting the covering layer 60 is suppressed as compared to the case where the negative electrode current collector layer 70 made of other than noble metal is provided on the covering layer 60 be able to.
  • Embodiment 3 In the first and second embodiments, between the solid electrolyte layer 40 and the covering layer 60, the holding layer 50 having the function of holding metallic lithium functioning as the negative electrode and not functioning itself as the negative electrode is provided. On the other hand, in the present embodiment, a layer functioning as a negative electrode is provided between the solid electrolyte layer 40 and the covering layer 60.
  • the same components as those in Embodiments 1 and 2 are assigned the same reference numerals and detailed explanations thereof will be omitted.
  • FIG. 11 is a diagram showing a cross-sectional configuration of lithium ion secondary battery 1 of the third embodiment.
  • the lithium ion secondary battery 1 according to the present embodiment has a structure in which a plurality of layers (films) are stacked as in the first and second embodiments, but unlike the first and second embodiments, The structure is completed by the film forming process.
  • the lithium ion secondary battery 1 of the present embodiment includes the substrate 10, the positive electrode current collector layer 20, the positive electrode layer 30, the solid electrolyte layer 40, the negative electrode layer 90, the covering layer 60, and the negative electrode current collector.
  • the layers 70 and 70 are stacked in this order. That is, in the lithium ion secondary battery 1 of the present embodiment, the negative electrode layer 90 is provided at the position of the holding layer 50 of the other embodiments.
  • the negative electrode layer 90 (an example of a holding layer) is a solid thin film, and contains a negative electrode active material that occludes lithium ions during charge and releases lithium ions during discharge.
  • the negative electrode layer 90 of the present embodiment is made of amorphous silicon (Si) to which a dopant is added. Note that in this embodiment, silicon functions as a negative electrode active material which occludes and releases lithium ions.
  • the negative electrode layer 90 may be made of materials other than silicon, and the dopant is not essential.
  • the dopant to be added to the silicon forming the negative electrode layer 90 is not particularly limited as long as it enhances the conductivity of silicon, and one or two or more elements composed of various elements are used. be able to.
  • zinc (Zn), cadmium (Cd), boron (B), aluminum (Al), gallium (Ga), indium (In) which makes the anode layer 90 p-type by functioning as an acceptor.
  • the thickness of the negative electrode layer 90 can be, for example, 10 nm or more and 20 ⁇ m or less. If the thickness of the negative electrode layer 90 is less than 10 nm, the capacity of the obtained lithium ion secondary battery 1 becomes too small to be practical. On the other hand, when the thickness of the negative electrode layer 90 exceeds 20 ⁇ m, the internal resistance of the battery becomes high, which is disadvantageous for high-speed charge and discharge. However, when the battery capacity required for the lithium ion secondary battery 1 is large, the thickness of the negative electrode layer 90 may be more than 20 ⁇ m.
  • the negative electrode layer 90 As a method of manufacturing the negative electrode layer 90, known film forming methods such as various PVD and various CVD may be used, but from the viewpoint of production efficiency, it is desirable to use the sputtering method.
  • the substrate 10 is mounted on a sputtering apparatus (not shown), and the positive electrode current collector layer 20, the positive electrode layer 30, the solid electrolyte layer 40, the negative electrode layer 90, the covering layer 60 and the negative electrode current collector layer 70 are formed on the substrate 10.
  • the layers are formed (stacked) in this order.
  • the lithium ion secondary battery 1 shown in FIG. 11 is obtained.
  • the lithium ion secondary battery 1 is removed from the sputtering apparatus.
  • the lithium ions moved from the positive electrode layer 30 side to the negative electrode layer 90 side reach the boundary between the solid electrolyte layer 40 and the negative electrode layer 90.
  • the negative electrode layer 90 is made of silicon formed by adding boron as a dopant. As a result, lithium ions that have reached the boundary between the solid electrolyte layer 40 and the negative electrode layer 90 are held by the negative electrode layer 90.
  • the covering layer 60 is made of a metal or an alloy in which the number of grain boundaries is reduced by amorphizing. Therefore, the lithium ions that have reached the boundary between the negative electrode layer 90 and the covering layer 60 are unlikely to enter the covering layer 60, and therefore, the state held in the negative electrode layer 90 is maintained.
  • the substrate 10 When discharging (using) the lithium ion secondary battery 1 in a charged state, the substrate 10 is connected to the positive electrode of the load, and the negative electrode current collector layer 70 is connected to the negative electrode of the load. Then, lithium ions present inside the negative electrode layer 90 move along the thickness direction (downward direction in FIG. 11) to the positive electrode layer 30 through the solid electrolyte layer 40, and the positive electrode active material is Configure. Along with this, a direct current is supplied to the load.
  • the negative electrode layer 90 made of silicon containing boron is provided.
  • the capacity of the lithium ion secondary battery 1 at the same thickness (volume) is obtained. It can be enlarged.
  • the negative electrode current collector layer 70 made of platinum is provided on the covering layer 60.
  • the corrosion (deterioration) due to oxidation or the like of the metal or alloy constituting the covering layer 60 is suppressed as compared to the case where the negative electrode current collector layer 70 made of other than noble metal is provided on the covering layer 60 be able to.
  • the covering layer 60 is provided on the holding layer 50 (or the negative electrode layer 90), the present invention is not limited to this, and a layer equivalent to the covering layer 60 on the positive electrode layer 30 side.
  • a layer equivalent to the covering layer 60 on the positive electrode layer 30 side may be provided.
  • the positive electrode layer 30 is an example of the holding layer.
  • providing an amorphous metal layer (amorphous alloy layer) between the positive electrode collector layer 20 and the positive electrode layer 30 is mentioned as one method for realizing this.
  • the positive electrode current collector layer 20 itself may be formed of an amorphous metal layer (amorphous alloy layer).
  • a layer corresponding to the covering layer 60 may be provided on each of the positive electrode layer 30 side and the holding layer 50 (or negative electrode layer 90) side.

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Abstract

La présente invention concerne un accumulateur au lithium-ion (1) configuré par empilement, dans l'ordre indiqué : d'une couche d'électrode positive (30) contenant un matériau actif d'électrode positive ; d'une couche d'électrolyte solide (40) contenant un électrolyte solide inorganique ; d'une couche de maintien (50) configurée à partir de platine (Pt) qui a été rendue poreuse, la couche de maintien (50) contenant du lithium ; d'une couche de revêtement (60) configurée à partir d'un métal amorphe ou d'un alliage ; et d'une couche de collecteur d'électrode négative (70) configurée à partir de platine (Pt). Ainsi, une fuite de lithium dans un accumulateur au lithium-ion entièrement solide vers l'extérieur est inhibée.
PCT/JP2018/042840 2017-12-22 2018-11-20 Accumulateur au lithium-ion WO2019123951A1 (fr)

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US16/771,719 US20210175512A1 (en) 2017-12-22 2018-11-20 Lithium-ion rechargeable battery
CN201880077375.4A CN111418106A (zh) 2017-12-22 2018-11-20 锂离子二次电池

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07296812A (ja) * 1994-04-28 1995-11-10 Mitsubishi Cable Ind Ltd 負極及びＬｉ二次電池
JP2001250559A (ja) * 2000-03-08 2001-09-14 Sanyo Electric Co Ltd リチウム二次電池
WO2007135790A1 (fr) * 2006-05-23 2007-11-29 Incorporated National University Iwate University Batterie rechargeable totalement solide
JP2012146479A (ja) * 2011-01-12 2012-08-02 Idemitsu Kosan Co Ltd リチウムイオン電池
JP2017500710A (ja) * 2013-12-18 2017-01-05 エレクトリシテ・ドゥ・フランス 非晶質合金で作られるコレクターを有するアノードコンパートメント

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07296812A (ja) * 1994-04-28 1995-11-10 Mitsubishi Cable Ind Ltd 負極及びＬｉ二次電池
JP2001250559A (ja) * 2000-03-08 2001-09-14 Sanyo Electric Co Ltd リチウム二次電池
WO2007135790A1 (fr) * 2006-05-23 2007-11-29 Incorporated National University Iwate University Batterie rechargeable totalement solide
JP2012146479A (ja) * 2011-01-12 2012-08-02 Idemitsu Kosan Co Ltd リチウムイオン電池
JP2017500710A (ja) * 2013-12-18 2017-01-05 エレクトリシテ・ドゥ・フランス 非晶質合金で作られるコレクターを有するアノードコンパートメント

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