WO2006043470A1 - 電池用負極とこれを用いた電池 - Google Patents
電池用負極とこれを用いた電池 Download PDFInfo
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- WO2006043470A1 WO2006043470A1 PCT/JP2005/018917 JP2005018917W WO2006043470A1 WO 2006043470 A1 WO2006043470 A1 WO 2006043470A1 JP 2005018917 W JP2005018917 W JP 2005018917W WO 2006043470 A1 WO2006043470 A1 WO 2006043470A1
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- current collector
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- H—ELECTRICITY
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- 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
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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
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M10/058—Construction or manufacture
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
- H01M4/0495—Chemical alloying
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- H—ELECTRICITY
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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
- H01M4/381—Alkaline or alkaline earth metals elements
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- H—ELECTRICITY
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- 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
- H01M4/40—Alloys based on alkali metals
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 negative electrode having a negative electrode active material layer and an inorganic compound layer, and a battery using the same.
- an organic electrolyte, or a gel polymer electrolyte that has been made non-fluidized using a polymer or a gelling agent, and various nonaqueous electrolytes such as a solid electrolyte are used as the electrolyte.
- Non-aqueous electrolyte lithium batteries using lithium ions as a charge transfer medium have been developed.
- LiMn O lithium manganate
- Lithium batteries have a much larger voltage and energy density than aqueous batteries, and currently occupy the mainstream of small batteries.
- batteries using carbon-based materials for the negative electrode have been recognized for manufacturing safety and reliability in terms of practical use.
- the current increase in capacity of carbon-based materials has reached its maximum theoretical capacity and is at its limit. Since the energy density of the battery is largely governed by the capacity density of the negative electrode material, a new lithium ion storage / release material is being sought to further improve the energy density.
- a simple substance of either silicon (Si) or tin (Sn), or an alloy material containing one or more of these elements is promising as a material excellent in reversible capacity that can replace carbon-based materials.
- lithium ion conductive inorganic compounds for example, Japanese Patent Application Laid-Open No. 2004-171875 discloses lithium halides such as lithium fluoride and lithium iodide, lithium phosphate (Li PO
- lithium phosphate nitride (LIPON) is disclosed as a material.
- the inorganic compound layer formed on the surface of the conductive metal material becomes a resistance, the impedance of the whole negative electrode increases, and the battery characteristics deteriorate.
- the negative electrode for a battery of the present invention includes an active material layer and a lithium ion conductive inorganic compound layer (hereinafter sometimes referred to as an inorganic compound layer) provided on the active material layer.
- the active material layer includes at least one of a simple substance of Sn or Si, an alloy containing at least one of these elements, or a group of compound forces.
- the inorganic compound layer is composed of a compound having a chemical composition represented by any of the following general formula 1 or general formula 2.
- At least one element selected from the prime group force which is powerful 2. 0 ⁇ x ⁇ 7.0, 0.01 ⁇ y ⁇ l.0, 3.5 ⁇ z ⁇ 8.0, preferably 2 0 ⁇ x ⁇ 3.0, 0.01 ⁇ y ⁇ 0.50, 3.5 ⁇ z ⁇ 4.0.
- General formula 2 Li MO N, where M is the element symbol Si, B, Ge, Al, C, Ga and S
- At least one element selected from the element group force with the strength 0. 6 ⁇ x ⁇ l. 0, 1. 05 ⁇ y ⁇ 1.99, 0. 01 ⁇ z ⁇ 0. 5, or 1. 6 ⁇ x ⁇ 2. 0, 2. 05 ⁇ y ⁇ 2. 99, 0. 01 ⁇ z ⁇ 0.5, or ⁇ 1. 6 ⁇ 2.0, 3. 05 ⁇ y ⁇ 3. 99 0. 01 ⁇ ⁇ ⁇ 0.5, and ⁇ 4. 4.6 ⁇ ⁇ ⁇ 5.0, 3. 05 ⁇ y ⁇ 3.99, 0. 01 ⁇ ⁇ ⁇ 0.5.
- the compounds constituting these inorganic compound layers have high lithium ion conductivity and excellent moisture resistance, a decrease in lithium ion conductivity is suppressed even in contact with an electrolyte in which moisture remains. As a result, excellent battery characteristics are maintained over a long charge / discharge cycle. That is, the stability of the negative electrode itself having an active material layer that occludes and releases lithium ions to water and the cycle characteristics of a battery using such a negative electrode are greatly improved.
- FIG. 1 is a schematic cross-sectional view showing the basic structure of the battery and the negative electrode used therefor in Embodiments 1 and 2 of the present invention.
- FIG. 2 is a cycle characteristic diagram according to the first embodiment of the present invention.
- FIG. 3 is a diagram showing the relationship between WZP and capacity retention rate in the composition of the inorganic compound layer in Embodiment 1 of the present invention.
- FIG. 4 is a diagram showing the relationship between WZP and capacity retention rate in the composition of the inorganic compound layer in Embodiment 1 of the present invention.
- FIG. 5 is a diagram showing the relationship between NZSi and the capacity retention rate in the composition of the inorganic compound layer in the second embodiment of the present invention.
- FIG. 1 is a cross-sectional view of a battery using a negative electrode according to Embodiment 1 of the present invention.
- the battery includes a negative electrode 1, a positive electrode 2 that faces the negative electrode 1 and reduces lithium ions during discharge, and an electrolyte 3 that is interposed between the negative electrode 1 and the positive electrode 2 and conducts lithium ions.
- the negative electrode 1 and the positive electrode 2 are accommodated in the case 6 using the gasket 4 and the lid 5 together with the electrolyte 3.
- the positive electrode 2 includes a positive electrode current collector 7 and a positive electrode active material layer (hereinafter referred to as an active material layer) 8 containing a positive electrode active material.
- the negative electrode 1 includes a current collector 9, a negative electrode active material layer (hereinafter referred to as an active material layer) 10 provided on the surface thereof, and a lithium ion conductive inorganic compound layer 11 formed on the surface of the active material layer 10.
- the active material layer 10 in addition to tin (Sn) and silicon (Si) as active material materials that occlude and release lithium ions, Ni Sn, Mg Sn ⁇ SnO (0 ⁇ x ⁇ 2), SnO, SiB, SiB, Mg Si ⁇ Ni
- an alloy, a compound, or a solid solution can be applied. These may constitute the active material layer 10 alone, or a plurality of them may constitute the active material layer 10 at the same time.
- Examples in which a plurality of types simultaneously constitute the active material layer 10 include a compound containing Si, oxygen, and nitrogen, and a composite of a plurality of compounds containing Si and oxygen and having different ratios of Si and oxygen.
- the active material layer 10 is composed of a simple substance of Sn, a simple substance of Si, an alloy containing at least one of Sn and Si, It includes at least one of the group consisting of compound powers including at least one of Sn and Si.
- the current collector 9 is made of a metal or alloy that is less reactive than lithium, and a conductor plate or sintered body having an arbitrary shape is formed and used.
- a conductor plate or sintered body having an arbitrary shape is formed and used.
- a conductor plate or sintered body having an arbitrary shape is formed and used.
- Cu copper
- Ni nickel
- one or more simple substances selected from titanium (Ti), molybdenum (Mo), tantalum (Ta), iron (Fe) and carbon (C) force or these It is possible to use alloys, steel, stainless steel, etc. containing at least one kind.
- the active material layer 10 contains a metal
- the metal of the active material layer 10 is alloyed with the current collector 9 at a part of the interface with the current collector 9.
- the active material layer 10 and the current collector 9 are more firmly bonded, so that excellent battery characteristics are maintained over a long charge / discharge cycle.
- Such an alloy is preferably formed when the active material layer 10 is formed on the current collector 9 using an active material.
- a method for forming such an alloy a method in which a molded active material layer is bonded to a current collector surface, a method in which an active material component powder is applied, a method in which a plating layer is formed, vapor deposition, sputtering, or the like is used.
- a layer forming method is applicable.
- the form of the alloy may be either an intermetallic compound or a solid solution.
- a thin film of the above current collector material may be formed by using a self-shape-holding support such as an oxide such as silica or carbon, and using sputtering or the like thereon.
- heat treatment for promoting alloying such as sintering, be provided after the formation of the active material layer 10.
- the active material layer 10 and the current collector 9 are more firmly bonded, and thus excellent battery characteristics are maintained over a long charge / discharge cycle.
- the inorganic compound layer 11 is made of a compound having a chemical composition represented by Li PTO.
- Component T is an element symbol Titanium (Ti), Copper (Cu), Zirconium (Zr), Molybdenum (Mo), Tantalum (Ta), Tungsten (W) Force Group force 2. 0 ⁇ x ⁇ 7.0, 0.01 ⁇ y ⁇ l.0, 3.5 ⁇ z ⁇ 8.0. Desirably 2. 0 ⁇ x ⁇ 3.0, 0.01 ⁇ y ⁇ 0.50, 3.5 ⁇ z ⁇ 4.0, or 2. 0 ⁇ x ⁇ 3.0, 0.01 ⁇ y ⁇ l 0, 3.5 ⁇ z ⁇ 7.0.
- the above Li PTO is a material with excellent lithium ion conductivity and moisture resistance discovered by the present inventors, and is disclosed in JP-A-2004-335455.
- Element group force may be at least one selected element. These elements are similar in nature to Ti, Cu, Zr, Mo, Ta, and W, and it can be reasonably inferred that the same effect can be obtained even when any of these powers is added.
- Li PTO is composed of a constituent element component of lithium phosphate and a transition metal group T.
- the transition metal component ⁇ When this compound is in contact with water molecules, the transition metal component ⁇ is considered to be reduced in preference to the phosphorus atom. Therefore, decomposition of the lithium phosphate component is suppressed, and a decrease in ion conductivity of the inorganic compound layer 11 itself is suppressed. As described above, in Li PTO, the presence of the transition metal component ⁇ may suppress the reduction of phosphorus. Therefore, the transition metal component ⁇ may be incorporated into the lithium phosphate at the atomic level or may be mixed with the lithium phosphate at the particle level.
- the metal component T when the metal component T is an oxide, the metal component T may be partially incorporated into lithium lithium phosphate at an atomic level, or may be mixed with lithium phosphate at the particle level. What! /
- the metal component T is a lithium oxide
- the lithium phosphate and the lithium oxide of the metal component T form a solid solution or are mixed at the particle level. It can be mixed at the particle level with the product and lithium oxide.
- Li PTO has excellent ionic conductivity and suppresses the decomposition of ionic conductive solids in a humid environment. 2. 0 ⁇ 7.0, 0.01 ⁇ It is desirable that y ⁇ l. 0, 3.5 ⁇ z ⁇ 8.0.
- This composition uses a transition metal as a target for the transition metal component T when forming Li PTO, in the case of 2.o ⁇ x ⁇ 3.0, 0.01 ⁇ y ⁇ 0.50, 3. It is desirable that 5 ⁇ z ⁇ 4.0.
- lithium transition metal oxide is used as the target, it is desirable that 2.0 ⁇ x ⁇ 7.0, 0. 01 ⁇ y ⁇ l. 0, 3.5 ⁇ z ⁇ 8.0 .
- each layer forming the negative electrode 1 will be described.
- the current collector 9, the active material layer 10, and the inorganic compound layer 11 are preferably laminated in order.
- the formation area and shape of each layer are arbitrary, but the active material layer 10 is completely covered with the inorganic compound layer 11. I like it.
- a configuration in which the active material layer 10 and the inorganic compound layer 11 are provided on both sides of the positive electrode 2 is preferable.
- the thickness of the inorganic compound layer 11 is arbitrary, but it is preferably a thin film having a thickness of 0.05 to LO m in consideration of the ability to protect against a moist environment, impedance, physical strength, and the like.
- lithium phosphate and component T such as transition metals such as W, Mo, and Ta, or their metal oxides are used as a target or vapor deposition source and formed by a dry thin film process.
- various deposition methods such as vapor deposition method, resistance heating vapor deposition method, high frequency heating vapor deposition method, laser ablation vapor deposition method, ion beam vapor deposition method, sputtering method, rf magnetron sputtering method, etc. in argon or vacuum environment It is preferable to form on the active material layer 10 by applying a thin film forming method.
- a mixture of Li 2 O and PO 2 may be applied as a target or a deposition source.
- the valences of the lithium atom, the phosphorus atom, and the oxygen atom are +1 valence, +5 valence, and 2 valence, respectively.
- the transition metal element component T has the same valence in the state of the compound when the compound is used as the target. On the other hand, when a transition metal unit is used as a target, component T is considered to be incorporated in the lithium phosphate in a metallic state.
- the ratio of phosphorus atoms is first set to 1.
- y is calculated by calculating the ratio between component T and phosphorus atom, including the force of inductively coupled plasma spectroscopy (ICP spectroscopy).
- z is calculated by calculating the ratio of oxygen to phosphorus atoms or transition metal atoms by techniques such as nitrogen oxygen analysis.
- nitrogen-oxygen analysis for example, oxygen and nitrogen contained in the material are extracted by an inert gas inson heating / melting method, which is thermal decomposition at a high temperature. Then, oxygen is detected as CO gas by a highly sensitive non-dispersive infrared detector, and nitrogen is detected as N gas and highly sensitive heat transfer.
- X is calculated using the above valence, assuming that the overall valence is zero.
- Electrolyte 3, case 6 and other components generally include lithium compounds and lithium All materials and shapes used in batteries constructed by applying an alloy to the negative electrode are applicable.
- the material of the active material layer 8 includes LiCoO, LiNiO, LiMn O, or a mixture thereof.
- a material that reversibly stores and releases lithium ions electrochemically such as a composite compound, is used.
- Electrolyte 3 an electrolyte solution in which a solute is dissolved in an organic solvent, or a so-called polymer electrolyte layer containing these and made non-fluidized with a polymer can be applied. At least when an electrolyte solution is used, it is preferable to use a separator such as polyethylene between the positive electrode 2 and the negative electrode 1 and impregnate the solution. Electrolyte 3 may be solid.
- the material of the electrolyte 3 is selected based on the oxidation-reduction potential of the active material contained in the positive electrode 2.
- preferred solutes to be used are lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitride, lithium phosphate, lithium silicate, lithium sulfide, phosphide Salts generally used in lithium batteries, such as lithium, can be applied.
- organic solvents for dissolving such supporting salts include propylene carbonate, ethylene carbonate, gethinole carbonate, methinoreethino carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, and ⁇ -butyl.
- a solvent used in a lithium battery such as a mixture of more than that can be applied.
- the electrolyte 3 is a solid, the electrolyte 3 is preferably composed of Li PTO constituting the inorganic compound layer 11. In this case, moisture enters the inorganic compound layer 11 directly from the battery external force.
- the inorganic compound layer 11 protects the active material layer 10 and a battery having good characteristics can be obtained. That is, by preparing the negative electrode 1 as described above, the moisture resistance of the negative electrode 1 is increased, and deterioration of charge / discharge cycle characteristics of a battery using the negative electrode 1 is suppressed.
- Such a negative electrode 1 can be applied to all lithium batteries that use a negative electrode active material that can store and release lithium, or S or Sn as a simple substance, a compound, or an alloy. Improved characteristics.
- lithium ions are directly applied to the electrolyte 3 through the inorganic compound layer 11. It is occluded by the active material layer 10 that is not in contact with it and functions as a negative electrode for the first time. That is, the inorganic compound layer 11 faces the electrolyte 3 and serves as a migration path of lithium ions to the active material layer 10 isolated from the electrolyte 3. In this configuration, even if the electrolyte 3 contains moisture, the inorganic compound layer 11 can continue the role of the ion transfer path without being affected by the moisture of the electrolyte 3.
- Embodiment 1 The features and effects of Embodiment 1 according to the present invention will be described below with specific examples.
- an active material layer 10 was formed on a current collector 9 made of Cu as described below, and an inorganic compound layer 11 made of a compound having a chemical composition represented by Li PTO was formed thereon.
- Si was used as a negative electrode active material material by using an electron beam vacuum deposition method on a current collector 9 having a thickness of 35 ⁇ m and a surface roughness of 2 ⁇ m and having an electrolytic copper foil force.
- An active material layer 10 having a thickness of 3 m was formed.
- Si with a purity of 99.9999% was used as the target.
- the acceleration voltage was set to -8 kV
- the emission was set to 500 mA
- the target was irradiated with an electron beam.
- the Si vapor was deposited on the current collector 9 installed on the fixed base, and an active material layer 10 such as S was formed. The deposition time was 20 minutes.
- the obtained negative electrode 1 was cut, and the vicinity of the interface between the current collector 9 and the active material layer 10 was subjected to XPS (X-ray Photoele ctron Spectrscopy) and AES (Auger Electron Spectr scopy). When analyzed by spectroscopy, at least a part of the interface was alloyed.
- an active material layer 10 having a thickness of 3 m using Sn as a negative electrode active material was formed on a current collector 9 similar to Sample 1 using an electrolytic plating method.
- a plating bath having the composition shown in (Table 1) was used, and metallic tin was used for the anode of the counter electrode.
- the negative electrode 1 on which the active material layer 10 was formed was vacuum-treated and heat-treated at 200 ° C. for 10 hours.
- sample 8 50 wt.% By rf sputtering method on current collector 9 similar to sample 1.
- sample 9 50 wt% Sn was applied to current collector 9 similar to sample 1 by rf sputtering.
- Samples 7 to 9 were analyzed by XPS and AES in the vicinity of the interface between current collector 9 and active material layer 10, and active material layer 10 and current collector 9 had less interfaces. It was confirmed that some parts were alloyed and joined.
- an inorganic compound layer 11 having a thickness of 500 nm and made of Li PTO was formed on the active material layer 10 by rf sputtering.
- Li PO with a diameter of 4 inches and a transition metal element as shown in Table 2 were used as targets.
- the composition of the formed inorganic compound layer 11 is such that platinum is placed beside the current collector 9 on which the active material layer 10 was formed when the inorganic compound layer 11 was formed.
- the sample was prepared by installing the plate and analyzed by ICP spectroscopy. According to this method, the composition of the composition was Li PTO.
- Sample 1 ⁇ In order to compare the characteristics of LO with the conventional structure, a comparative sample in which a layer that also has a lithium phosphate (LIPON) force instead of the inorganic compound layer 11 of Sample 1 was formed. 1 to 5 were produced. The active material layers 10 of Comparative Samples 1 to 5 were the same as Samples 1, 7, 8, 9, and 10, respectively. In forming the LIPON layer, a mixed gas of argon and nitrogen gas was used as the discharge gas, and Li PO was used as the target. The thickness of the LIPON layer is about 0
- Table 2 shows the configurations of Sampu Nore 1 to 10 and Comparative Sampu Nore 1 to 5.
- the positive electrode 2 using LiCoO as an active material is used as shown in FIG.
- a coin-type secondary battery was produced.
- the positive electrode 2 was produced as follows. First, the positive electrode active material LiCoO and the conductive agent
- Tylene black and poly (vinylidene fluoride) as a binder were mixed at a weight ratio of 90: 5: 5. This mixture was dispersed in N-methylpyrrolidone to prepare a positive electrode paste. Next, this positive electrode paste was applied onto a positive electrode current collector 7 made of an aluminum foil by a doctor blade method, heated and dried, and then pressed to form an active material layer 8. Next, positive current collector 7 A case 6 to be a positive electrode terminal was attached to the.
- the electrolyte 3 was prepared by dissolving 1 mol / L of LiPF in a mixed solvent of ethylene carbonate and ethylmethyl carbonate mixed at a volume ratio of 1: 1. Using this solution as a separator
- a coin-type battery having a diameter of 20 mm and a height of 1.6 mm was manufactured using the above-described components. At that time, the case 5 enclosing the positive electrode 2 was covered with the lid 5 enclosing the negative electrode 1, and force squeezed and sealed through the gasket 4. The battery was designed so that the charge / discharge capacity of the positive electrode 2 was twice the charge / discharge capacity of the negative electrode 1, and the battery was configured with negative electrode capacity restrictions.
- each battery was housed in a constant temperature bath at a temperature of 20 ° C., and a charge / discharge cycle test was performed.
- the battery was charged at a constant current until the battery voltage reached 4.2 V at a current value at which the design capacity was discharged in 5 hours, that is, at a 5-hour rate. Then, it switched to 4.2V constant voltage charge and charged until the current value dropped to 5% of the constant current charge value.
- constant current discharging was performed until the battery voltage reached 2.5 V at the same current value as during constant current charging, and the discharge capacity was measured. In this way, the ratio of the discharge capacity during the cycle to the initial discharge capacity, that is, the change in the capacity maintenance ratio was examined. In addition, the capacity retention after 100 cycles was compared as necessary.
- the battery was disassembled after charging and the negative electrode 1 was examined, it was confirmed that lithium was occluded in the active material layer 10.
- FIG. 2 shows the relationship between the capacity retention ratio and the number of cycles (cycle characteristics) between the battery of sample 1 and the battery of comparative sample 1.
- the capacity retention rate of the comparative sample 1 in which LIPON was formed as a conventional ionic conductor in the inorganic compound layer was reduced early.
- the sample 1 battery in which tungsten W was selected as the component T and the inorganic compound layer 11 made of a compound having a chemical composition represented by the general formula Li PTO was formed was markedly different from the comparative sample 1. The cycle characteristics were improved.
- Table 2 shows the results of comparing the capacity retention rates after 100 cycles.
- the capacity retention rate is about 40%.
- the batteries of Samples 1 to 10 in which the inorganic compound layer 11 of the present invention was formed were 100 Even after the cycle has elapsed, the capacity retention rate of approximately 60% or more is maintained, and excellent cycle characteristics are exhibited.
- Samples 1A to 1H were prepared.
- an inorganic compound layer 11 made of a compound having a chemical composition represented by Li PW O in which WZP, which is the molar ratio of W and P, is changed by changing the sputtering rf power in the configuration of Sample 1 is used.
- WZP corresponds to y in the composition formula.
- Other conditions were the same as for sample 1.
- WZP was 0.005, 0.01, 0.05, 0.1, 0.2, 0.5, 0.6, and 0.8 for samples 1A to LH, respectively.
- Negative electrode 1 was formed in the same manner as Sample 1, except that the transition metal oxide shown in Table 4 was used as the sputtering target. Using the obtained negative electrodes 1 of samples 1J to 6J, batteries were produced. The composition of the inorganic compound layer 11 in Samples 1J to 6J is shown in (Table 4). The capacity retention rate after 100 cycles, which is the result of evaluating the obtained battery under the same conditions as described above, is shown in (Table 4).
- the comparative sample 1 had a capacity retention rate of 43.4%, whereas the inorganic compound layer also had a compound force having a chemical composition represented by Li PTO.
- the batteries of samples 1J to 11 that formed 11 showed a capacity retention rate of 60% or more even after 100 cycles, and showed excellent cycle characteristics.
- the cycle characteristics were improved even when transition metal oxides were used as raw materials in addition to the transition metal alone.
- transition metal oxides shown in (Table 4) pentanoic acid vanadium (V O), triacidic chromium (Cr O), diacid
- Niobium pentoxide (Nb 2 O 3) and acid silver (Ag 2 O) can be used to achieve the same effect.
- Negative electrode 1 was formed in the same manner as Sample 1, except that the lithium-containing transition metal oxide shown in (Table 5) was used as the sputtering target. Using the obtained samples 1K to 4K, negative electrode 1 of 6 mm, a battery was produced. The composition of the inorganic compound layer 11 in Samples 1 to 4 and 6 is shown in (Table 5). (Table 5) shows the capacity retention rate after 100 cycles, which is the result of evaluating the obtained battery under the same conditions. As can be seen from (Table 5), the capacity retention rate of Comparative Sample 1 was 43.4%, while Li PT
- a sample 1K to 4K, 6mm battery with an inorganic compound layer 11 having a chemical composition represented by 0 has a capacity retention rate of 60% or more even after 100 cycles, and excellent cycle characteristics showed that.
- the cycle characteristics are improved.
- FIG. 4 shows the capacity retention rate and the WZP after 100 cycles when a battery using the negative electrode 1 formed by forming Li PWO with different WZP in the inorganic compound layer 11 was used. Shows the relationship. As is clear from FIG. 4, the capacity retention ratio was 0.01 or more and 1.0 or less when the capacity retention ratio was 60% or more, indicating good characteristics.
- Discoloration is seen when That is, it can be seen that even when WZP is greater than 0.5 and less than or equal to 1.0, the reactivity between the inorganic compound layer 11 and metallic lithium is low. Since lithium ions are reduced at the negative electrode 1 during discharge, a similar reaction occurs, and it is assumed that this is the result.
- the y value which is the molar ratio of the component T to P has an appropriate range.
- the appropriate range of X and z values depends on the y value.
- Each is automatically determined. This is because the valence of each atom is determined as described above. That is, if the target is a transition metal, 2.0 ⁇ x ⁇ 3.0, 0.01 ⁇ y ⁇ 0.5, 3.5 ⁇ z ⁇ 4.0. If the target is a transition metal oxide, then 2.0 ⁇ x ⁇ 3.0, 0.01 ⁇ y ⁇ l. 0, 3.5 ⁇ z ⁇ 7.0. In the case of target force lithium oxyacid salt, 2. 0 ⁇ x ⁇ 7.0, 0. 01 ⁇ y ⁇ l. 0, 3.5 ⁇ z ⁇ 8.0.
- the conceptual diagram showing the basic structure in the second embodiment of the present invention is the same as FIG.
- the inorganic compound layer 11 in the negative electrode 1 according to this embodiment is made of a compound having a chemical composition represented by LiMON.
- M is an element consisting of the element symbols Si, B, Ge, Al, C, Ga and S, and is at least one element selected from the group force.
- the compound LiMON is also a material with excellent lithium ion conductivity and moisture resistance discovered by the present inventors, and is disclosed in JP-A-2005-38844.
- the bond between component element M and oxygen in LiMON is more thermodynamically stable than the bond between phosphorus and oxygen in lithium nitride phosphate. For this reason, this composition maintains the structure of the solid electrolyte stably even when it comes into contact with water molecules, and suppresses a decrease in ionic conductivity in a humid environment. Further, due to the stability of the inorganic compound layer 11, strong protection of the active material layer 10 that has occluded lithium ions is achieved.
- the bond between component M and oxygen serves to form a more stable bond than the bond between phosphorus and oxygen in lithium nitride phosphate even in a wet environment.
- Li MO N is required to exhibit favorable ionic conductivity.
- lithium oxyacid salt is LiBO, LiAlO or LiGaO
- component M is B, A or Ga
- the lithium oxalate is Li SiO, Li GeO or Li CO, i.e. in the above general formula
- Lithium oxyacid salt is Li AIO
- X and y can be changed according to the amount and type of lithium oxyacid salt used as a raw material, and z can be changed according to the amount and pressure of nitrogen when forming the inorganic compound layer 11.
- the range of z is particularly important. If it is less than 0.01, there will be a problem with ionic conductivity. Conversely, if z> 0.5, the skeletal structure is likely to be destroyed. Impairs ionic conductivity.
- the inorganic compound layer 11 consisting of a compound having a chemical composition represented by Li MO N, a lithium phosphate compound and Li SiO, LiBO, LiA are used as a target.
- a method using lithium oxyacid salt is preferred.
- N it is preferable to apply a sputtering method using nitrogen gas or a vapor deposition method in a nitrogen atmosphere to replace some of the oxygen atoms with nitrogen atoms.
- a sputtering method using nitrogen gas or a vapor deposition method in a nitrogen atmosphere to replace some of the oxygen atoms with nitrogen atoms.
- Target oxides of component elements M such as O, Al 2 O, and Ga 2 O or a mixture of these
- the valences of lithium atom and oxygen atom are +1 and 2 respectively.
- the nitrogen atom is trivalent.
- Element M is the same as the valence in the compound used as the target.
- the ratio of the element M is set to 1.
- calculate the ratio of oxygen atoms and nitrogen atoms to element M by using a method such as nitrogen oxygen analysis (inactive gas impulse heating and melting method).
- X is calculated using the above valence, assuming that the overall valence is zero.
- the formation method of the active material layer 10, the form of the current collector 9, the formation method and thickness of the inorganic compound layer 11 are the same as those in Embodiment 1. Further, as in the first embodiment, when the active material layer 10 contains a metal, it is preferable that this metal and at least a part of the current collector 9 form an alloy. [0079]
- the durability of the negative electrode 1 with respect to moisture can be increased, and deterioration of cycle characteristics of a battery using the negative electrode 1 can be suppressed.
- Such negative electrode 1 can be applied to all lithium batteries that absorb and release lithium ions and use S or Sn as a single element, compound, or alloy as a negative electrode, and its storage characteristics are charge / discharge cycle characteristics. improves.
- the inorganic compound layer 11 faces the electrolyte 3 and serves as a migration path of lithium ions onto the substrate 10 isolated from the electrolyte 3. In this configuration, even if the electrolyte 3 contains moisture, the inorganic compound layer 11 can continue to play the role of an ion transfer path that is not affected by the moisture of the electrolyte 3.
- Embodiment 2 according to the present invention will be described below with specific examples.
- an active material layer 10 made of Si is formed on a current collector 9 made of Cu in the same manner as Sample 1 in Embodiment 1, and a compound having a chemical composition represented by LiMON is formed thereon.
- An inorganic compound layer 11 was formed.
- lithium oxyacid salts shown in (Table 7) were used as targets, respectively, rf magnetron sputtering was used, and sputtering was performed using nitrogen gas.
- the sputtering conditions were an internal pressure of 2.7 Pa, a gas flow rate of 10 sccm, a high frequency irradiation power of 200 W, and a sputtering time of 20 minutes.
- the thickness of the obtained inorganic compound layer 11 was approximately 0.15 m.
- the composition of the inorganic compound layer 11 of each sample is shown in (Table 7).
- the inorganic compound layer 11 is formed using a mixture of two types of transition metal lithium-containing transition metal oxides as a sputtering target.
- the lithium oxyacid salt nitride was formed under the same conditions as Samples 21 to 28, except that the lithium oxyacid salt mixture shown in Table 8 (molar ratio 1: 1) was used to form the inorganic compound layer 11.
- Samples 31 to 43 of the negative electrode 1 on which the inorganic compound layer 11 made of was formed were produced. Except for this, a battery was fabricated under the same conditions as in Embodiment 1, and the cycle characteristics were evaluated. Table 8 shows the composition of the inorganic compound layer 11 and the capacity retention rate after 100 cycles of charge and discharge, which is the evaluation result.
- the batteries of Samples 31 to 43 also showed a capacity retention rate of 60% or more even after 100 cycles, and exhibited excellent cycle characteristics.
- the component M may be composed of a plurality of elemental forces.
- the component T in the first embodiment may be composed of a plurality of elements in the same manner.
- FIG. 5 shows the capacity retention rate and NZSi after 100 cycles when a battery using a negative electrode composed of Li SiO N with different NZSi formed on the inorganic compound layer 11 was charged and discharged. Shows the relationship.
- the capacity retention ratio greatly depends on NZ Si, and an improvement effect was observed at 0.01 or higher.
- the capacity retention rate increased with the increase of NZSi, and a high value from 0.3 to 0.5 was stably obtained.
- NZSi is the most preferred range of force 0.3 or more and 0.5 or less.
- the present invention is not limited to the shape of such a battery.
- the negative electrode for a battery according to the present invention is provided with a negative electrode active material layer that reversibly occludes and releases lithium and contains silicon (Si) or tin (Sn) as a simple substance, a compound, or an alloy, and a negative electrode active material layer thereon.
- a lithium ion conductive inorganic compound layer In this negative electrode, the stability of the negative electrode active material layer itself with respect to moisture can be improved, and the cycle characteristics can be greatly improved in a battery using an electrolyte that may be mixed with a minute amount of moisture.
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Abstract
Description
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EP05793190.9A EP1677375B1 (en) | 2004-10-21 | 2005-10-14 | Negative electrode for battery and battery using same |
JP2006522820A JP4444287B2 (ja) | 2004-10-21 | 2005-10-14 | 電池用負極とこれを用いた電池 |
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- 2005-10-14 CN CNB2005800010765A patent/CN100454613C/zh active Active
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CN1860628A (zh) | 2006-11-08 |
EP1677375A4 (en) | 2013-03-13 |
KR100728441B1 (ko) | 2007-06-13 |
US20070020520A1 (en) | 2007-01-25 |
KR20060085625A (ko) | 2006-07-27 |
JP4444287B2 (ja) | 2010-03-31 |
EP1677375A1 (en) | 2006-07-05 |
JPWO2006043470A1 (ja) | 2008-05-22 |
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US7632607B2 (en) | 2009-12-15 |
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