WO2000033409A1 - Accumulateur au lithium - Google Patents
Accumulateur au lithium Download PDFInfo
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- WO2000033409A1 WO2000033409A1 PCT/JP1999/006668 JP9906668W WO0033409A1 WO 2000033409 A1 WO2000033409 A1 WO 2000033409A1 JP 9906668 W JP9906668 W JP 9906668W WO 0033409 A1 WO0033409 A1 WO 0033409A1
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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
- H01M10/056—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
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/187—Solid electrolyte characterised by the form
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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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
- 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
- H01M4/405—Alloys based on lithium
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/182—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte
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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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a high capacity, high safety lithium secondary battery.
- the present invention relates to a lithium secondary battery that can suppress a short circuit due to generation of dendrites from a negative electrode, has a high energy density, and has excellent charge / discharge cycle characteristics.
- Such lithium secondary batteries include an organic electrolyte type in which an organic electrolyte is impregnated in a porous polymer separator and a gel polymer type in which a gel polymer containing a large amount of an organic electrolyte is used.
- both the organic electrolyte type and the gel polymer type use a large amount of the organic electrolyte, and there is a problem caused by the organic electrolyte.
- these organic electrolytes are basically flammable substances, and there is a risk of explosion due to short-circuit due to temperature rise or impact due to any cause.
- increasing the energy density is a major technical issue for organic electrolyte and gel polymer batteries. At present, the limit is about 300Wh, and it is strongly desired to increase it to 400Wh / l or more.
- the use of lithium metal for the negative electrode is being studied as an effective means.
- lithium-containing material when a lithium-containing material is used as the negative electrode, lithium used for charging and discharging
- the thickness of the metal and the change in the shape of the negative electrode during charging and discharging have an effect on the electrolyte layer. In particular, this effect appears in high cycles of several hundred cycles or more.
- lithium metal easily reacts with moisture in the air, and a device for shutting off air in the film forming process is required.
- lithium dendritic metal grows on the surface of the lithium metal, which may cause an internal short circuit between the electrodes, which may cause an explosion or the like.
- a compound layer is formed by surface-treating lithium metal to be a negative electrode.
- the compound layer includes a polymer film, a fluoride film, a carbonate compound film, an oxide film, and the like.
- An all-solid-state battery that does not contain an organic electrolyte that may cause an explosion For example, an organic polymer, an inorganic crystal, or the like is used for the electrolyte.
- a main object of the present invention is to provide a lithium secondary battery that suppresses a short circuit due to generation of dendrites from a negative electrode, has a high energy density, and has excellent charge / discharge cycle characteristics. Disclosure of the invention
- the present invention achieves the above object by providing an electrolyte layer made of an inorganic solid electrolyte and a positive electrode containing an organic polymer. In other words, it prevents dendrite growth on lithium metal during charge and discharge, And suppresses the temperature rise inside the battery even during overcharge, thereby preventing explosion.
- an electrolyte layer made of an inorganic solid electrolyte and a positive electrode containing an organic polymer.
- FIG. 1 is an enlarged sectional view of a main part of a lithium secondary battery manufactured in Example 411.
- This battery is composed of a current collector 1, a positive electrode 2, a separator 3, a solid electrolyte thin film 4, a negative electrode 5, and a current collector 6.
- the electrolyte layer is an inorganic solid electrolyte.
- the inorganic solid electrolyte forms a graded compositional interface layer with lithium metal at the interface with lithium metal.
- the lithium metal and the organic polymer layer have a clear interface, whereas in the inorganic solid electrolyte, a layer in which the lithium metal and the lithium-containing inorganic compound are mixed is formed at the interface and peeled off.
- the inorganic solid electrolyte include sulfide-based, oxide-based, nitride-based, and oxynitride-based and oxysulfide-based mixed systems thereof.
- the sulfide include Li 2 S and a compound of Li 2 S and SiS 2 , GeS 2 , and Ga 2 S 3 .
- the oxynitride Li 3 P0 4 - x N 2X / 3, Li 4 Si0 4 _ x N 2 X / 3, Li 4 Ge0 4 _ x N 2X / 3 (0 rather X rather 4), 3 ⁇ 0 3 — x N 2x / 3 (0 ⁇ ⁇ 3).
- the inclusion of zeolite facilitates the formation of a graded composition layer on the surface of lithium metal.
- zeolite facilitates the formation of a graded composition layer on the surface of lithium metal.
- the lithium element content in these inorganic electrolyte layers is 30 atomic% or more and 65 atomic% or less. If it is less than 30 atomic%, the ionic conductivity becomes low and the resistance becomes high. In addition, the adhesion between the inorganic solid electrolyte layer and the lithium metal layer is reduced. On the other hand, when the composition exceeds 65 atomic%, the adhesion between the inorganic solid electrolyte layer and the lithium metal layer is improved, but the inorganic solid electrolyte layer is polycrystallized and becomes porous, so that the dense inorganic solid electrolyte layer has a high density. It becomes difficult to form a continuous film. In addition, it develops electronic conductivity, causing an internal short circuit when configuring the battery, and lowering the battery performance. Therefore, the electrolyte layer is preferably an amorphous body.
- components other than lithium include one or more elements selected from the group consisting of phosphorus, gay, boron, aluminum, germanium, and gallium (hereinafter, these elements are referred to as “additive elements”). It is preferable that it contains thiophene. It is effective that the inorganic solid electrolyte is an amorphous body, but the “additional element” can form a network structure via an iodide to form this amorphous skeleton. In addition, it is possible to supply sites that are optimal in size for lithium ions to conduct.
- the “additional element” can charge the terminal i-atom of the amorphous skeleton to a negative charge having an optimum intensity for capturing a positively charged lithium ion.
- the negatively-charged terminal zeo atoms capture the positively-charged lithium ions moderately and moderately, and serve to assist the conduction of lithium-ion without being unnecessarily firmly fixed.
- oxygen and nitrogen is mentioned in addition to the “element to be added” and ⁇ ⁇ ⁇ .
- oxygen or nitrogen it is possible to exhibit higher lithium ion conductivity. This means that it contains oxygen or nitrogen atoms. This is presumed to have the effect of widening the gap between the formed amorphous skeletons and reduce the hindrance of lithium ion migration.
- the inorganic solid electrolyte contains the “additional element”, it has the performance of further improving the affinity with lithium metal.
- the inclusion of lithium, zeolite, oxygen, and nitrogen improves the adhesion between the lithium metal and the inorganic solid electrolyte layer. However, it tends to inhibit the affinity between the inorganic solid electrolyte layer and the lithium metal, and tends to peel off.
- the ionic conductivity of the constituent material of the electrolyte layer is important. That is, in the traditional technique, I O emissions conductivity of the compound layer both formed on the surface of the lithium metal is extremely low than 1 0- 7 S / cm at room temperature. Therefore, through the inevitably pinholes or cracks are present, even if a thin film of about the compound layer number (nm), an organic electrolyte having a 1 0- 3 S / cm stand ions Den Shirubedo The liquid penetrates the interface between the lithium metal and the compound layer, and the flow of lithium ion leans toward the organic electrolyte having high ionic conductivity. Therefore, it was found that the interface between the lithium metal and the compound layer was eroded, so that the compound layer was easily peeled off, and the coating effect was thin.
- the flow of lithium ions is mainly passed through the electrolyte layer, and the above problem is solved.
- the lithium ion conductivity of such an electrolyte layer is preferably l (T 5 S / cm or more at 25 ° C. Even if pinholes or cracks exist in the electrolyte layer (thin film), Gas carbonate ions, oxygen gas, water molecules or fluorine ions, which are inevitably contained as impurities, react with lithium metal in pinholes and cracks, causing lithium carbonate, lithium oxide, and fluorine on the surface of the lithium metal.
- a layer with low ionic conductivity such as lithium fluoride is formed, so that pinholes and cracks are protected by the low ionic conductive layer and dendrite While suppressing the growth, lithium ions mainly pass through the electrolyte layer. More preferably, a 1 corresponds to more than 0% 5 X 1 0- 4 S / cm or more I on the conductivity of the organic electrolyte the ionic conductivity of the solid electrolyte layer (25 ° C). An even more preferable lithium ion conductivity (25 ° C.) is 1 xl O— 3 S / cm or more. It is also preferable to combine at least one of the following conditions in order to effectively form a low ion conductive compound with lithium metal.
- the inorganic solid electrolyte layer described above has a two-layer structure, so that its handling is further facilitated.
- a sulfide-containing lithium ion conductive compound has high lithium ion conductivity, but also has disadvantages of high hygroscopicity and hydrolyzability.
- lithium ion conductive compounds containing oxides have chemical stability to the atmosphere, but have low ion conductivity and compounds that are chemically unstable to the lithium metal of the negative electrode. Has become. Therefore, the electrolyte layer is composed of two layers, a negative electrode side layer and a positive electrode side layer.
- the negative electrode side layer is a thin film of a lithium ion conductive compound containing sulfides (lithium sulfide and gay sulfide), and the positive electrode side layer is oxidized.
- a thin film of a lithium ion conductive compound containing a substance it is possible to form an electrolyte layer that is stable to the atmosphere and has high ion conductivity.
- the positive electrode side layer functions as a protective film that prevents the reaction with moisture in the atmosphere, and dissolves in the organic electrolyte when the battery is configured.
- the dissolved constituent elements of the positive electrode side layer react with lithium metal in pinhole cracks in the electrolyte to form a low ion conductive layer, thereby suppressing the intensive growth of dendrite.
- the positive electrode side layer serving as the protective film is a lithium ion conductor containing phosphorus and further containing at least one of oxygen and nitrogen. That is, a phosphoric acid compound or a phosphate nitrogen compound is a suitable material.
- the Li component of the positive electrode side layer has a ratio of 30 atomic% or more and 50 atomic% or less. If it is less than 30 atomic%, the possibility of remaining undissolved during dissolution increases. On the other hand, if the composition exceeds 50 atomic%, hygroscopicity appears, and the composition does not function as a protective film.
- the thickness of the positive electrode side layer is preferably thin. However, if the thickness is too small, the effect of shielding the sulfide-containing negative electrode side layer from the atmosphere is reduced. Therefore, it is preferable that the thickness be 1 Onm or more or 1% or more of the thickness of the negative electrode side layer. Conversely, if the positive electrode side layer is too thick, it will be difficult to maintain high ionic conductivity or it will be difficult to dissolve. Therefore, the thickness is preferably 25 rn or less or 50% or less of the thickness of the negative electrode side layer.
- the thickness of the positive electrode side layer is 0. l ⁇ m or more and 2 / • im or less is preferable in terms of battery characteristics.
- the total thickness of the electrolyte layer is preferably 50 nm or more and 50 or less.
- the thickness exceeds 50 m, the coating effect is further enhanced, but the ionic conductivity is deteriorated and the battery performance is reduced.
- the time required to form the film is too high, making it impractical.
- the ion conduction resistance of the electrolyte layer is increased, which causes a problem that the output current cannot be increased.
- the thickness is less than 50, the electron conductive component becomes large, and a problem that self-discharge becomes easy occurs.
- a preferable total thickness of the electrolyte layer is 2 m or more. If the thickness is less than 2 m, pin the thin film electrolyte It becomes difficult to suppress the formation of holes and cracks. That is, when an anode containing an organic electrolyte is used, the electrolyte from the anode penetrates into the negative electrode surface through the pinholes and cracks, and reacts with the negative electrode to form dendrites through the pinholes and cracks. A short circuit occurs between the electrodes. In addition, the negative electrode undergoes a volume change during charging and discharging.
- the negative electrode cannot be fully piled up by the stress due to the strain at that time, and the electrolyte layer is easily broken.
- the thickness exceeds 22 m, the ionic conduction resistance of the electrolyte layer increases, and a problem arises in that the current density per unit area cannot be increased and efficiency is deteriorated.
- the material of the positive electrode those containing an active material in a binder of an organic polymer are preferable.
- the binder is selected from the group consisting of polyacrylonitrile-based polymers, polyethylene oxide-based polymers, and polyvinylidene fluoride-based polymers containing organic solvents such as ethylene carbonate, propylene carbonate, and dimethyl carbonate. At least one is preferred.
- the active material at least one L ix Co0 2, L ix Mn 2 0 4, L ix Ni 0 2 (0 ⁇ X ⁇ 1) is preferable. Further, it is desirable to mix a carbon powder for imparting electronic conductivity.
- the organic polymer in the positive electrode material may be a polyaniline-containing disulfide-based polymer or a polypyrrol-based polymer having both ionic conductivity and electron conductivity.
- a lithium ion conductive solid electrolyte powder is added to the positive electrode.
- the amount of the organic electrolyte component can be further reduced, and problems caused by the organic electrolyte can be reduced.
- the solid electrolyte is preferably a highly ionically conductive material which shows the above may be a material which has a higher ionic conductivity of 1 0- 3 SZ cm.
- an organic electrolyte solution is mainly contained around the active material in the positive electrode, an inorganic lithium ion conductive thin film is formed on the negative electrode using lithium metal as the negative electrode, and these are combined to achieve high performance. It is possible to use batteries.
- the advantages of this type of lithium secondary battery include the reduction of the amount of organic electrolyte, suppression of dendrite growth of metallic lithium on the negative electrode, suppression of contact with the positive electrode due to the effect of coating the negative electrode surface, and reduction of the electrolyte. There is reaction suppression.
- the content of the organic electrolyte can be reduced by using the battery configuration of the present invention when the organic electrolyte is contained. It can be greatly reduced to 10% or less. It was also found that even when the battery was left in a charged state, the phenomenon that the electrolytic solution was decomposed and deteriorated as in the past and the battery characteristics were greatly reduced was suppressed as much as possible.
- the ionic conductivity of the organic electrolyte is kept below that of the solid electrolyte thin film. This is because even if pinholes and cracks are present and the organic electrolyte penetrates into them, forming an ion conduction path, Li ions are mainly transmitted through the solid electrolyte thin film layer with high ion conductivity. Therefore, the supply of Li ions to the pinholes and cracks is suppressed, and the growth of lithium metal is suppressed.
- the ion conductivity of the organic electrolytic solution in the vicinity of the contact portion may be lower than the ionic conductivity of the inorganic solid electrolyte.
- reducing the ionic conductivity of the organic electrolyte For example, it is not possible to reduce the amount of solutes in the electrolyte component, or to increase the ionic conductivity due to high viscosity like sulfolane (Sulfolane; tetrahydrothiophene, dioxide) solvent. Solvents may be used.
- the organic solvent is polymerized by the catalytic action or polymerization initiating action of lithium metal to solidify or increase the viscosity, lowering the ionic conductivity, and generating lithium by the mechanical action of the polymer and the high viscosity substance. Suppress metal growth. Here, even if the solid electrolyte thin film is peeled off, the organic electrolyte leaches out, and these polymers and high-viscosity materials constantly cover the pinholes and cracks on the lithium metal surface. It is possible to construct a safe battery.
- an anion-polymerized monomer having an olefin bond such as styrenes, acrylonitriles, methyl acrylate, butadiene, and isoprene is used. Or use the one that contains it. It is also possible to use a solvent which solidifies and vitrifies by the action of lithium metal, like acetonitrile having a nitrile group, in part or in whole.
- the lithium-containing material used for the negative electrode is not only lithium metal itself but also lithium Alloys are also included.
- Specific examples of lithium alloys include alloys with In, Ti, Zn, Bi, Sn and the like.
- a metal thin film of a metal forming an alloy or an intermetallic compound with lithium for example, a metal thin film of Al, In, Bi, Zn, or Pb may be formed.
- the negative electrode composed of the metal thin film and the lithium-containing material By using the negative electrode composed of the metal thin film and the lithium-containing material, the movement of the lithium metal during charge and discharge is smooth, and the thickness of the lithium metal used is increased. In addition, the deformation of the negative electrode during charge and discharge becomes uniform, and distortion to the electrolyte layer can be reduced. This is thought to be because the interface in contact with the electrolyte layer was stabilized. The effect of smooth movement of lithium metal and reduction of strain to the electrolyte layer is exhibited when the negative electrode has a multilayer or inclined structure. Furthermore, Al, In, Bi, Zn, Pb, etc. are relatively stable to the atmosphere, and this covers the negative electrode, which serves as a substrate during the formation of the electrolyte layer. It can be simplified.
- the above-mentioned lithium-containing material may be used as it is without performing any pretreatment when forming the electrolyte layer.
- a thin oxide layer is often formed on the surface of a metal containing lithium, and it is more preferable to remove this oxide layer once and form a nitride layer or a sulfide layer.
- the electrolyte layer can be formed directly into a lithium alloy material, and the impedance between the lithium-containing metal and the solid electrolyte layer can be further reduced.
- a method for forming a nitride or a sulfide includes, but not limited to, exposing the surface of a lithium-containing material to high-frequency plasma in a nitrogen gas atmosphere or a hydrogen sulfide atmosphere. .
- exposing the surface of a lithium-containing material to high-frequency plasma in a nitrogen gas atmosphere or a hydrogen sulfide atmosphere is possible.
- the surface roughness (Rmax) of the negative electrode also has a significant effect on battery performance.
- Rmax value is preferably 0.01 or more and 5 or less.
- Rmax is less than 0.01 m, good bonding with the electrolyte layer cannot be obtained, and peeling tends to occur.
- Rmax exceeds 5 / m, it is difficult to form a dense electrolyte layer without pinholes, which is not preferable.
- the battery including the positive and negative electrodes and the electrolyte layer as described above has a stacked structure in which an electrolyte layer is sandwiched between a positive electrode and a negative electrode, and is stored in a battery case and sealed. More specifically, first, the negative electrode current collector and the negative electrode are joined, and an inorganic solid electrolyte thin film containing no organic electrolytic solution is formed on the lithium-containing material to be the negative electrode, and the joined body of the negative electrode and the electrolyte is formed. Make it. Further, a positive electrode material containing an organic polymer is formed on a positive electrode current collector (for example, copper or aluminum foil) to form a positive electrode. These junctions and the positive electrode are combined to produce a lithium secondary battery.
- a positive electrode current collector for example, copper or aluminum foil
- a negative electrode, an electrolyte layer, and a positive electrode may be stacked and wound into a cylindrical shape.
- a separator may be provided between the positive electrode and the solid electrolyte layer. Separation-For the material of the evening, use a material that has pores through which lithium ions can move, and is insoluble and stable in the organic electrolyte. For example, a nonwoven fabric or a porous material formed from polypropylene, polyethylene, fluororesin, polyamide resin, or the like can be used. In addition, a metal oxide film having pores may be used. It is not necessary to provide a lithium-containing material in the negative electrode from the beginning. Even if the negative electrode has a structure in which an inorganic solid electrolyte layer is formed directly on the current collector, the performance of the lithium secondary battery is sufficiently exhibited. . That is, the positive electrode contains a sufficient lithium component, and it is possible to store lithium metal between the negative electrode current collector and the inorganic solid electrolyte layer during charging. BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is an enlarged cross-sectional view of a main part of the lithium secondary battery prepared in Example 4-11. It is. BEST MODE FOR CARRYING OUT THE INVENTION
- This example shows a specific example of an inorganic solid electrolyte and a specific example of a positive electrode containing an organic polymer, and confirms the effects of the present invention.
- Lithium metal foil which is 50 / xm in thickness and the same size, was attached to a copper foil of 100 m thickness and 100 mm X 50 mm serving as a current collector.
- rolling may be performed by twin rolls.
- the surface accuracy of the roll needs to be smooth enough to achieve the target lithium surface roughness.
- good bonding can be obtained by raising the temperature to around the melting point of lithium metal.
- the RF magnetron sputtering evening method and a mixture of Li 2 S- SiS 2 -Li 4 Si0 4 to the target, in nitrogen gas atmosphere to form a solid electrolytic electrolyte thin film.
- the thickness is lO m
- the composition of the thin film is Li (0.42) ⁇ Si (0.13) • N (0.01) ⁇ 0 (0.01) ⁇ S (0.43) in molar ratio as a result of EPMA (Electron Probe Micro Analyzer) analysis. ).
- EPMA Electro Probe Micro Analyzer
- PAN polyacrylonitrile
- LiCoO 2 particles as an active material and carbon particles for imparting electron conductivity are mixed, and applied on a 100-thick aluminum foil to a thickness of 300 m to produce a positive electrode.
- the lithium metal on which the solid electrolyte membrane was formed and the above-mentioned positive electrode were joined to form a battery, and a lead wire was taken out and sealed in an aluminum laminate. Then, the charge and discharge characteristics were evaluated under the condition of a current value of 100 mA. As a result, the charge voltage was 4.2V and the capacity at the discharge voltage of 3.0V was 0.5Ah (ampere hour). The energy density was 490 Wh (watt hours) and 1 (liter).
- a polysulfide-containing disulfide-based polymer was used as the positive electrode material instead of the PAN-based material. Further, 10% by volume of fine particles having a particle diameter of 0.1 / im to 0.0 and having a composition of Li (0.42) .Si (0.13) .0.0 (0.01) ⁇ S (0.44) were mixed with the polymer material. The microparticles, Li 2 S- SiS 2 - the Li 4 Si0 4 mixed melt, dry nitrogen gas atmosphere was prepared by spray rapid solidification by an atomizing method. The thickness of the positive electrode was 350 m.
- Table 1 shows the results of evaluating the charge / discharge characteristics of the battery configuration shown in Example 1-1 by changing the thickness of the positive electrode, the electrolyte, and the negative electrode, respectively.
- the thickness of the positive electrode is 2 m or more and 1000 xm or less
- the thickness of the negative electrode is 1 / m or more and 200 ⁇ m or less
- the thickness of the electrolyte layer is 1 / im or more and 50 m or less.
- Table 2 shows the results of evaluating the charge and discharge characteristics of the battery configuration shown in Example 1-1 while changing the surface roughness of the negative electrode. It can be seen that the surface roughness affects the film quality of the upper electrolyte layer. In other words, when the surface roughness of the negative electrode exceeds 5 m, pinholes are formed in the electrolyte layer, and the charge and discharge cycle is short-circuited at 300 times. Table 2
- the surface of the lithium-indium alloy was nitrided in advance in place of the lithium metal foil of the negative electrode to form a nitride layer, and then a solid electrolyte membrane was similarly formed.
- a nitride layer was prepared.
- Observation and analysis of the nitride layer by TEM (Transmission Electron Microscope) and the like revealed that the composition was Li 3 N and the thickness was about 100 ⁇ .
- This nitride layer was obtained by exposing the surface with RF plasma in a nitrogen atmosphere before forming the solid electrolyte layer.
- This example shows the effect when the inorganic solid electrolyte is composed of two layers, a thin film of a lithium ion conductive compound containing a sulfide and a thin film of a lithium ion conductive compound containing an oxide. is there.
- a base material is a current collector made of 100 mm X 50 mm copper foil with a thickness of 20 im, and a lithium metal foil (negative electrode) with a thickness of 10 m and the same size bonded to a current collector.
- a thin film of a lithium ion conductive compound containing a sulfide is formed, and a thin film of a lithium ion conductive compound containing an oxide is further laminated to form a two-layer electrolyte layer.
- the electrolyte layer was formed by an in-line RF magnetron sputtering method.
- a solid electrolyte thin film was formed in an argon gas atmosphere using a mixture of Li 2 S—SiS 2 as a target.
- EPMA Electro Probe Micro Analyzer
- a thin film of a lithium ion conductive compound containing a sulfide is further placed on a thin film of [ ⁇ ( ⁇ in the evening, in a nitrogen atmosphere. It was formed, but its thickness was 1 m.
- the negative electrode and the electrolyte layer were left in the air for 6 hours, but no change was observed in the composition of the sulfide layer, which proved to be extremely stable.
- the ion conductivity showed good performance with almost no decrease in the high ion conductivity of the sulfide layer.
- the charge voltage was 4.2 V, and the capacity until the voltage dropped to 3.0 V by discharging 100 mA was 0.5 Ah (ampere hours).
- the energy density was 490 Wh (watt-hour) / 1 (liter).
- the deterioration of these characteristics was suppressed to 2%, and no trace of dendritic growth from the lithium metal of the negative electrode was observed.
- Example 2-1 the thickness of the thin film of the lithium ion conductive compound containing sulfide was 0.5 ⁇ m, and the thickness of the thin film of the lithium ion conductive compound containing oxide was 5 m.
- the oxide layer was too thick compared to the sulfide layer, and the ionic conductivity was extremely poor, so that a battery with the expected performance could not be obtained.
- Example 2-1 a thin film of a lithium ion conductive compound containing an oxide was formed as a lithium titanate-based amorphous with a thickness of 1.8 m.
- a battery with the same structure as that of 2-1 was fabricated and its performance was tested. Good results were obtained.
- Example 2-1 a battery was manufactured by changing the thickness of the sulfide layer and the oxide layer variously by changing the thin film of the lithium ion conductive compound containing an oxide to a lithium phosphate-based amorphous material and changing its performance.
- Table 3 shows the results of the tests.
- ⁇ means stable even over 1000 cycles
- ⁇ means stable even over 500 cycles
- X means 5% below 500 cycles The above performance degradation is shown.
- Rolling was performed by twin rolls to produce a negative electrode having a thickness of 50 x m and a thickness of indium metal foil laminated on a lithium metal foil.
- the interface between the two layers of metal was diffused with each other, and the composition was graded, but the surface was a single substance of the alloy.
- an electrolyte layer was formed by the method described in Example 1 to fabricate a battery, and a charge / discharge experiment was performed under the conditions of ImA / cm 2 (milliamps / square centimeter). Its current capacity was 20 mAh / cm 2 (milliampere.hour / square centimeter), and almost all lithium metal was used for charging and discharging, including the lithium ions present in the anode. Furthermore, the charge / discharge cycle was performed up to 1000 cycles under the same conditions, but the charge / discharge curve was stable with no significant change. No dendrites were found. (Example 3-1)
- the battery once fabricated was bent to generate a crack in the solid electrolyte layer, and the charge / discharge characteristics were examined.
- a lithium metal foil (negative electrode) of the same size with a thickness of lOm was attached to a ferrite stainless steel foil (negative electrode current collector) of 20 mm thick and 100 mm X 50 band. Rolling was performed using a roll as the bonding method.
- a mixture of vinylidene fluoride monomer, acetonitrile, LiPF 6 , LiCoO 2 particles, and conductive carbon particles, and a polymerization initiator (oxygenated triisobutyl boron) are mixed to form a 20 m thick aluminum foil (positive electrode).
- a current collector is applied to a thickness of 100 m and polymerized to produce a gelled positive electrode.
- Lithium ion conductivity of the organic electrolyte solution in the positive electrode was 5 X 10- 2 S / cm.
- the charge and discharge characteristics were evaluated and a crack test was performed.
- the crack test involves bending a battery once fabricated, causing cracks in the solid electrolyte layer, and observing changes in charge and discharge characteristics.
- LixMn 2 0 4 LixNi0 2
- LixMn 2 0 4 LixNi0 2
- good results were obtained when a polyethylene oxide polymer or a polyacrylonitrile polymer was used as the material in the positive electrode.
- LiBF 4, LiC10 4, LiCF 3 S0 good results in any of the 3 were obtained.
- N, N-dimethylformamide solvent (DMF) containing acrylonitrile was used instead of acetonitrile.
- the lithium ion conductivity of the organic electrolyte using this solvent was 2 ⁇ 10 12 S / cm.
- Example 3-1 an organic electrolytic solution was prepared in which the dissolved mass of the organic electrolytic solution was reduced to 25% of a normal amount, and a lithium battery was produced in the same manner as in Example 3-1.
- Example 3-1 In the battery configuration shown in Example 3-1, a separator was provided between the negative electrode and the positive electrode, and methylsulfolane was used instead of acetonitrile to similarly produce a lithium battery.
- the lithium ion conductivity of the organic electrolyte using this solvent during separation was 7 ⁇ 10 4 S / cm.
- Example 4 A lithium battery was manufactured in the same manner as in Example 3-1 except that methyl formate was used instead of acetonitrile. Lithium ion conductivity of the organic electrolyte solution using the solvent was 1 X10- 3 S / cm. As a result, the same good characteristics as in Example 3-1 were obtained, and the cycle characteristics also showed good results. (Example 4-1)
- FIG. 1 is an enlarged sectional view of a main part of the secondary battery obtained in this example.
- a 200-m-thick (micron meter) lithium metal 5 was laminated on a 1-inch-diameter current collector 6 made of nickel metal to form a negative electrode.
- the solid electrolyte membrane 4 was amorphous having a composition of 34 atom% of lithium, 14 atom% of phosphorus, 51 atom% of oxygen, and 1 atom% of oxygen.
- the thickness of this thin film was 800 nm (nanometer).
- the lithium ion conductivity of the amorphous thin film was 7 X10- 4 S / cm. Ion conductivity was measured by a complex impedance method by forming a comb-shaped gold electrode on a glass substrate containing no alkali ions, forming the same thin film on the electrode.
- LiCoO 2 particles as active material, carbon particles to impart electron conductivity, and poly Vinylidene fluoride was mixed with an organic solvent and applied on an aluminum foil to obtain a positive electrode I.
- the active material layer had a thickness of 80 m, a capacity density of 3.5 mAh (milliamp-hour) / cm 2 (square centimeter), and a total capacity of 17.2 mAh under an argon gas atmosphere with a dew point of less than 60 ° C.
- the negative electrode on which the solid electrolyte thin film is formed, the separator 3 (porous polymer film) and the positive electrode 2 are placed one on top of the other in a stainless steel sealed container, and a mixed solution of ethylene glycol and propylene carbonate is further added. was added dropwise to an organic electrolyte obtained by dissolving 1 mol% of L i PF 6 as an electrolytic salt, were prepared lithium secondary battery. At this time, the stainless steel becomes the current collector 1 on the positive electrode side.
- Example 4-1 Experiments were performed with the same configuration as in Example 4-1 and changing the composition and ionic conductivity of the inorganic solid electrolyte, and the cycle characteristics of this battery were investigated under the same conditions as in Example 4-1.
- the addition of nitrogen atoms to the inorganic solid electrolyte thin film and the adjustment of the content were performed by adjusting the nitrogen gas concentration in the introduced gas in the RF magnet opening method. The results are shown in Table 4.
- Comparative Example 4-1 As a comparative experiment, a charging / discharging experiment was performed in the same configuration as in Example 4-1 and using a lithium metal having no solid electrolyte layer as the negative electrode. The results are shown in Comparative Example 4-1 in Table 4. The current efficiency is low, in the order of 90% or more, from the beginning of charge / discharge, and after 78 cycles, a voltage drop that can be caused by a small internal short circuit has been observed, and the capacity has further decreased significantly did. In addition, similar experiments were conducted for batteries with different inorganic solid electrolyte compositions and ionic conduction characteristics, and the cycle characteristics of the batteries were investigated. Table 4 also shows the results. Comparative Examples 4-2 to 4-5 also show low cycle characteristics.
- the effect of the thickness of the inorganic solid electrolyte was investigated.In the same configuration as in Example 4-1 and in the inorganic solid electrolyte composition, only the thickness of the inorganic solid electrolyte thin film was changed. An experiment was conducted to investigate the cycle characteristics of the battery. Table 5 shows the results. The thickness of the solid electrolyte layer is 50nn! In any case in the range of up to 50 / im, no internal short circuit occurred even after 500 cycles, and no reduction in capacity was observed. Table 5 Battery performance depending on the thickness of the inorganic solid electrolyte thin film
- This example illustrates the effect of the composition of the layer on the positive electrode side of the inorganic solid electrolyte having a two-layer structure.
- Example 4-1 A similar experiment was performed with the same configuration as that of Example 4-1 except that the thickness of the inorganic solid electrolyte layer was changed from that of Examples 4-11 to 15 to investigate the cycle characteristics of the battery. Table 5 shows the results. When the thickness of Comparative Example 8 is 60 xm, From the beginning of the cycle, the current efficiency was insufficient at around 95%, but after 500 cycles the performance did not change.
- the stability of the inorganic solid electrolyte in air was investigated by changing the composition of the positive electrode side layer of the amorphous inorganic solid electrolyte layer into a two-layer inorganic solid electrolyte layer. Further, with the same configuration as the battery described in Example 4-1, the battery characteristics were also investigated.
- the composition of the inorganic solid electrolyte layer on the negative electrode side was the same as in Example 4-7.
- the thickness of each of the positive electrode side layer and the negative electrode side layer is 50 nm and 1 m. Table 6 shows the results. In each case, it shows extremely high stability.
- the battery characteristics also showed the expected battery performance. No internal short circuit occurred even after 500 cycles, and no reduction in capacity was observed. Table 6
- the inorganic solid electrolyte layer was made into a two-layer structure, and the composition of the positive electrode side layer in the amorphous inorganic solid electrolyte layer was changed from that of Examples 4-16 to 18 in the atmosphere of the inorganic solid electrolyte. Was investigated for its stability. Further, the battery characteristics were also investigated with the same configuration as the battery described in Example 4-1. The composition of the inorganic solid electrolyte on the negative electrode side was the same as in Example 4-7. Table 6 shows the results. In each of these cases, it became extremely unstable, and the battery characteristics were significantly reduced.
- Example 4-7 The stability of the inorganic solid electrolyte in air was investigated by changing the thickness of the solid electrolyte layer on the positive electrode side of the two inorganic solid electrolyte layers. Further, the battery characteristics of the same configuration as in Example 4-16 were investigated. The composition of the inorganic solid electrolyte on the negative electrode side was the same as that of Example 4-7. Table 7 shows the results. In each of these cases, extremely high stability was exhibited. The battery characteristics also showed the expected battery performance. No internal short circuit occurred even after 500 cycles, and no reduction in capacity was observed. (Comparative Example 4-1-1 to Comparative Example 4-1-2)
- the inorganic solid electrolyte layer was made to have a two-layer structure, and the thickness of the amorphous inorganic solid electrolyte layer on the positive electrode side was changed from that of Examples 4-1 9 to 20-20, so that the inorganic solid electrolyte was stable in air. Sex was investigated. Further, with the same configuration as in Example 4-16, the battery characteristics were also investigated. The composition of the inorganic solid electrolyte layer on the negative electrode side was the same as in Example 4-7. Table 7 shows the results. In each of these cases, it became extremely unstable and the battery performance was greatly reduced.
- Example 4-21 One Example examined the effect of pretreatment of lithium metal as a negative electrode.
- the lithium metal surface of the negative electrode was once subjected to press-passing in an argon gas atmosphere in an RF magnetron pass-through apparatus to remove an oxide layer unavoidable on the lithium metal surface. After that, an inorganic solid electrolyte thin film was formed on the surface.
- the composition of this electrolyte layer is as follows: Li: 39.4 atomic%, syrup: 0.3 atomic%, B: 16.0 atomic%, S: 3.3 atomic%, 0: 1.1 atomic%, and the film thickness is 2.5 m.
- a lithium secondary battery was manufactured in the same configuration as in Example 1, and the cycle characteristics of the battery were investigated. The cycle test was performed under a constant current condition of 17.2 mA. However, even after 500 cycles, no internal short circuit occurred and no capacity reduction was observed.
- the lithium metal surface of the negative electrode is once subjected to press-passing in an atmosphere containing H 2 S in an RF magnetron pass-through apparatus to remove an oxide layer inevitably existing on the surface, and at the same time, to remove lithium sulfide. A layer was formed. Thereafter, an inorganic solid electrolyte thin film was formed on the surface.
- the composition of this electrolyte layer is as follows: Li: 38.2 at%, P: 2.2 at%, S: 48.6 at%, 0: 1.0 at%, and film thickness: 10 // m.
- a lithium secondary battery was fabricated in the same configuration as in Example 4-1, and the cycle characteristics of the battery were investigated. The cycle test was performed under a constant current condition of 17.2 mA. Even after 500 cycles, no internal short-circuit occurred and no reduction in capacity was observed. (Example 4-23)
- the lithium metal surface of the negative electrode was once pre-sputtered in an N 2 atmosphere in an RF magnetron sputtering apparatus to remove the oxide layer inevitably existing on the surface and form a lithium nitride layer at the same time. .
- an inorganic solid electrolyte thin film was formed on the surface.
- the composition of this electrolyte layer is Li: 42.3 atoms %, P: 0.3 at%, Si: 11.8 at%, S: 44.3 at%, 0: 1.3 at%, and film thickness is lim.
- a lithium secondary battery was fabricated in the same configuration as in Example 4-1 and the cycle characteristics of the battery were investigated. The cycle test was performed under a constant current condition of ⁇ .2 mA. However, even after 500 cycles, no internal short circuit occurred and no reduction in capacity was observed. Industrial applicability
- the present invention it is possible to suppress a short circuit due to generation of dendrites from a lithium metal negative electrode, to provide a high energy density, excellent stability in charge / discharge cycle characteristics, and to provide a highly safe lithium secondary battery. A battery is obtained.
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US09/601,498 US6365300B1 (en) | 1998-12-03 | 1999-11-29 | Lithium secondary battery |
CA002319460A CA2319460C (en) | 1998-12-03 | 1999-11-29 | Lithium storage battery |
EP99973180A EP1052718B1 (en) | 1998-12-03 | 1999-11-29 | Lithium storage battery |
DE69936706T DE69936706T2 (de) | 1998-12-03 | 1999-11-29 | Lithiumspeicherbatterie |
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JP10/344593 | 1998-12-03 | ||
JP34459398 | 1998-12-03 | ||
JP773699 | 1999-01-14 | ||
JP11/7736 | 1999-01-14 | ||
JP7873399 | 1999-03-24 | ||
JP11/78733 | 1999-03-24 |
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WO2000033409A1 true WO2000033409A1 (fr) | 2000-06-08 |
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PCT/JP1999/006668 WO2000033409A1 (fr) | 1998-12-03 | 1999-11-29 | Accumulateur au lithium |
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US (1) | US6365300B1 (ja) |
EP (1) | EP1052718B1 (ja) |
CA (1) | CA2319460C (ja) |
DE (1) | DE69936706T2 (ja) |
WO (1) | WO2000033409A1 (ja) |
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JP6729796B2 (ja) * | 2017-04-04 | 2020-07-22 | 株式会社村田製作所 | 全固体電池、電子機器、電子カード、ウェアラブル機器および電動車両 |
KR102281373B1 (ko) | 2018-04-26 | 2021-07-22 | 주식회사 엘지에너지솔루션 | 고체 전해질 전지용 양극 및 그를 포함하는 고체 전해질 전지 |
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- 1999-11-29 DE DE69936706T patent/DE69936706T2/de not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
CA2319460A1 (en) | 2000-06-08 |
DE69936706T2 (de) | 2008-04-30 |
CA2319460C (en) | 2010-02-02 |
EP1052718A1 (en) | 2000-11-15 |
EP1052718A4 (en) | 2005-03-30 |
DE69936706D1 (de) | 2007-09-13 |
EP1052718B1 (en) | 2007-08-01 |
US6365300B1 (en) | 2002-04-02 |
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