WO2015098551A1 - リチウム固体電池、リチウム固体電池モジュール、およびリチウム固体電池の製造方法 - Google Patents
リチウム固体電池、リチウム固体電池モジュール、およびリチウム固体電池の製造方法 Download PDFInfo
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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
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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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
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0436—Small-sized flat cells or batteries for portable equipment
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M2300/008—Halides
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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 lithium solid state battery in which occurrence of a short circuit due to dendrite is suppressed.
- lithium batteries Since currently marketed lithium batteries use an electrolyte containing a flammable organic solvent, it is necessary to install a safety device that suppresses the temperature rise during a short circuit and a structure for preventing a short circuit.
- a lithium battery in which the electrolyte is changed to a solid electrolyte layer to make the battery completely solid does not use a flammable organic solvent in the battery, so the safety device can be simplified, and manufacturing costs and productivity can be reduced. It is considered excellent.
- Patent Document 1 discloses a Li 2 S—P 2 S 5 —LiI-based sulfide solid electrolyte material.
- This invention is made
- a sulfide glass having an ionic conductor containing Li element, P element and S element is contained, and the average pore radius determined by mercury porosimetry is 0.0057 ⁇ m or less.
- a lithium solid state battery comprising a solid electrolyte layer is provided.
- a lithium solid state battery including a solid electrolyte layer having a specific sulfide glass and having an average pore radius of the solid electrolyte layer equal to or less than a predetermined value, and suppressing occurrence of a short circuit due to dendrite. It can be.
- the sulfide glass has the above ion conductor, and LiI
- the ion conductor has a PS 4 3- structure, the PS 4 with respect to the total anion structure of the ion conductor 3- It is preferable that the structure ratio is 50 mol% or more and the LiI ratio is in the range of 20 mol% to 30 mol%.
- the solid electrolyte layer preferably has an average pore area of 7.30 ⁇ m 2 or less with respect to a plane of 100 ⁇ m 2 perpendicular to the thickness direction.
- the solid electrolyte layer preferably has a pore breaking distance of 3 ⁇ m or more.
- the solid electrolyte layer preferably has a pore connection length in the thickness direction of 3.7 ⁇ m or less.
- the lithium solid state battery is formed between the positive electrode active material layer containing the positive electrode active material, the negative electrode active material layer containing the negative electrode active material, and the positive electrode active material layer and the negative electrode active material layer. It is preferable to provide the solid electrolyte layer.
- the lithium solid state battery includes the negative electrode current collector, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector in this order, and the solid electrolyte layer is provided on the surface of the negative electrode current collector. It is preferable to provide.
- the lithium solid state battery includes the negative electrode current collector, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector in this order, and is deposited on the surface of the negative electrode current collector on the solid electrolyte layer side. It is preferable to provide a negative electrode active material layer made of Li metal.
- the present invention provides a lithium solid state battery module comprising the above-described lithium solid state battery and a restraining member that applies a restraining pressure in the thickness direction to the lithium solid state battery.
- the present invention by using the above-described lithium solid state battery, it is possible to obtain a lithium solid state battery module in which occurrence of a short circuit due to dendrite is suppressed.
- this invention has a solid electrolyte layer formation process which presses the sulfide glass which has an ion conductor which has Li element, P element, and S element, and forms a solid electrolyte layer, and is calculated
- An average pore radius of the solid electrolyte layer is 0.0057 ⁇ m or less, and a method for producing a lithium solid state battery is provided.
- a solid electrolyte layer is formed using a specific sulfide glass, and the average pore radius is set to a predetermined value or less, whereby a lithium solid state battery that suppresses the occurrence of short circuits caused by dendrites is obtained. Obtainable.
- the lithium solid state battery of the present invention has the effect of suppressing the occurrence of short circuits due to dendrites.
- FIG. 3 is a result of charge / discharge measurement of evaluation batteries obtained in Examples 1 and 2 and Comparative Examples 1 to 4.
- FIG. FIG. 10 is an enlarged view of FIG. 9. It is explanatory drawing explaining the observation area
- lithium solid state battery the lithium solid state battery module, and the method for producing the lithium solid state battery of the present invention will be described in detail.
- FIG. 1 is a schematic cross-sectional view showing an example of a lithium solid state battery of the present invention.
- a lithium solid battery 10 in FIG. 1 is formed between a positive electrode active material layer 1 containing a positive electrode active material, a negative electrode active material layer 2 containing a negative electrode active material, and a positive electrode active material layer 1 and a negative electrode active material layer 2.
- the solid electrolyte layer 3 contains a specific sulfide glass, and the average pore diameter of the solid electrolyte layer 3 is not more than a specific value.
- Cited Document 1 discloses a method for manufacturing a nonaqueous electrolyte battery for the purpose of preventing a short circuit.
- a battery using an electrolytic solution and a battery using a solid electrolyte layer are used for dendrite growth and suppression. The mechanism is completely different. Specifically, as shown in FIG.
- the average pore radius defined in the present invention is very small, and greatly exceeds the level that can be easily obtained by pressing a high pressure on any sulfide glass. That is, in order to obtain a desired average pore radius in the present invention, not only the pressing conditions but also the characteristics as a material of sulfide glass are important. Conventionally, knowledge about moldability (easiness of crushing of pores, degree of plastic deformation) of sulfide glass is not known, and there is no index. Moreover, if the moldability of sulfide glass is poor, it is difficult to obtain a desired average pore radius no matter how high the pressure is pressed.
- the sulfide glass containing Li element, P element and S element has good moldability, and further, by setting the average pore radius to a predetermined value or less.
- the occurrence of short circuits due to dendrites is considered to be because the pore size of the solid electrolyte layer is smaller than the size of the tip portion of the dendrite.
- the lithium solid state battery of the present invention will be described for each configuration.
- the solid electrolyte layer in this invention is formed between a positive electrode active material layer and a negative electrode active material layer, and has specific sulfide glass.
- the average pore radius of the solid electrolyte layer obtained by the mercury intrusion method is usually 0.0057 ⁇ m or less, preferably 0.0054 ⁇ m or less, and more preferably 0.0051 ⁇ m or less. preferable.
- the average pore radius of the solid electrolyte layer is determined by a mercury intrusion method. Specifically, as described in Examples described later, the average pore radius can be obtained from the pore distribution curve by using a pore distribution measuring device.
- the sulfide glass in the present invention is one of sulfide solid electrolyte materials, and has an ion conductor having a Li element, a P element, and an S element.
- the sulfide glass in the present invention means an amorphous body in a broad sense. Therefore, as a result of amorphization, for example, even a material in which a part of the raw material (for example, LiI described later) remains and a peak is observed in X-ray diffraction is included in the sulfide glass in the present invention. It is. Among them, the sulfide glass in the present invention preferably has no peak observed in X-ray diffraction.
- the ionic conductor in the present invention is usually composed of a Li cation and an anion structure containing P and S.
- the ionic conductor in the present invention preferably contains the PS 4 3- structure as a main component (50 mol% or more) of the anion structure.
- the ratio of the PS 4 3- structure is preferably 60 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more with respect to the total anion structure of the ionic conductor. 90 mol% or more is particularly preferable.
- the proportion of PS 4 3- structure can be determined by Raman spectroscopy, NMR, XPS, or the like.
- the sulfide glass in the present invention usually has the above ionic conductor as a main component.
- the ratio of the ionic conductor in the sulfide glass is preferably 65 mol% or more, more preferably 70 mol% or more, and further preferably 75 mol% or more.
- the sulfide glass may be composed only of the above ionic conductor, and may contain other components. Examples of other components include LiI. Since the sulfide glass has the ionic conductor and LiI, the moldability of the sulfide glass (easy to collapse the pores) is improved, and a solid electrolyte layer having a smaller average pore radius can be obtained. .
- LiI is usually present in a state incorporated into the structure of the ionic conductor. More specifically, it is considered that it is dispersed microscopically (in a state where it cannot be physically separated) around the anion structure (for example, PS 4 3 ⁇ ) of the ionic conductor.
- the ratio of LiI is, for example, 5 mol% or more, preferably 10 mol% or more, and more preferably 20 mol% or more. On the other hand, the ratio of LiI is, for example, 35 mol% or less, and preferably 30 mol% or less.
- the sulfide glass is xLiI ⁇ (100 ⁇ x) (yLi 2 S ⁇ (1-y) P 2 S 5 ) (20 ⁇ x ⁇ 30, 0.7 ⁇ y ⁇ 0.8).
- y is 0.72 or more, and it is more preferable that it is 0.74 or more.
- y is preferably 0.78 or less, and more preferably 0.76 or less.
- the sulfide glass in the present invention does not substantially contain crosslinking sulfur. It is because it can be set as the sulfide glass with little hydrogen sulfide generation amount.
- “Bridged sulfur” refers to bridged sulfur in a compound formed by the reaction of Li 2 S and a sulfide of P. For example, it corresponds to a sulfur bridge having an S 3 P—S—PS 3 structure formed by reaction of Li 2 S and P 2 S 5 . Such bridging sulfur easily reacts with water and easily generates hydrogen sulfide. Furthermore, “substantially free of bridging sulfur” can be confirmed by measurement of a Raman spectrum.
- the peak of the S 3 P—S—PS 3 structure usually appears at 402 cm ⁇ 1 . Therefore, it is preferable that this peak is not detected. Further, the peak of the PS 4 3 ⁇ structure usually appears at 417 cm ⁇ 1 .
- the intensity I 402 at 402 cm -1 is preferably smaller than the intensity I 417 at 417 cm -1. More specifically, the strength I 402 is preferably 70% or less, more preferably 50% or less, and even more preferably 35% or less with respect to the strength I 417 .
- the sulfide glass in the present invention is preferably formed by amorphizing a raw material composition containing Li 2 S, a sulfide of P (phosphorus), and LiI.
- Li 2 S preferably has few impurities. This is because side reactions can be suppressed.
- examples of the sulfide of P (phosphorus) include P 2 S 3 and P 2 S 5 .
- simple substance P and simple substance S may be used in place of the sulfide of P (phosphorus).
- Examples of the method for making amorphous include a mechanical milling method and a melt quenching method. Examples of the mechanical milling include a ball mill, a vibration mill, a turbo mill, a mechanofusion, and a disk mill. Mechanical milling may be performed dry or wet, but the latter is preferred. This is because a highly uniform sulfide glass can be obtained.
- ortho generally refers to one having the highest degree of hydration among oxo acids obtained by hydrating the same oxide.
- the crystal composition in which Li 2 S is added most in the sulfide is called the ortho composition.
- Li 3 PS 4 corresponds to the ortho composition.
- Feedstock composition if containing Li 2 S and P 2 S 5, the proportion of Li 2 S to the total of Li 2 S and P 2 S 5 is preferably in the range of 70 mol% ⁇ 80 mol%, It is more preferably in the range of 72 mol% to 78 mol%, and still more preferably in the range of 74 mol% to 76 mol%.
- the sulfide glass in the present invention preferably has a glass transition point. This is because Li ion conductivity is further improved by increasing the amorphousness to such an extent that it has a glass transition point. The presence or absence of a glass transition point can be confirmed by differential thermal analysis (DTA).
- DTA differential thermal analysis
- Examples of the shape of the sulfide glass in the present invention include particles.
- the average particle diameter (D 50 ) of the sulfide glass is, for example, 0.01 ⁇ m or more, and preferably 0.1 ⁇ m or more.
- the average particle diameter (D 50 ) of the sulfide glass is, for example, 50 ⁇ m or less, and preferably 30 ⁇ m or less.
- the sulfide glass in the present invention preferably has high Li ion conductivity, and the Li ion conductivity at room temperature (25 ° C.) is preferably 1 ⁇ 10 ⁇ 4 S / cm or more, for example, 1 ⁇ More preferably, it is 10 ⁇ 3 S / cm or more.
- the solid electrolyte layer in the present invention is characterized in that the average pore radius determined by the mercury intrusion method is in the above-described range.
- the pore distribution of the solid electrolyte layer in the present invention can also be evaluated by cross-sectional observation using a FIB-SEM (focused ion beam / scanning electron microscope). Specifically, the following average pore area, pore breakage distance, and pore connection length can be determined.
- the solid electrolyte layer in the present invention preferably has a small average pore area with respect to a plane of 100 ⁇ m 2 perpendicular to the thickness direction. It is because generation
- the average pore area is, for example, preferably less than 7.61Myuemu 2, and more preferably 7.30Myuemu 2 or less. In particular, the average pore area is preferably in the above range in the observation region having the surface on the negative electrode active material layer side of the solid electrolyte layer as the end face.
- the solid electrolyte layer in the present invention preferably has a large pore breaking distance. It is because generation
- a region where the pore area ratio is 0.05% or less is defined as a pore breakage region, and the length of the pore breakage region in the thickness direction is defined as a pore breakage distance.
- the pore breaking distance is preferably greater than 2 ⁇ m, for example, and more preferably 3 ⁇ m or more.
- the pore breaking distance starting from the surface of the solid electrolyte layer on the negative electrode active material layer side is preferably in the above range.
- the solid electrolyte layer in the present invention preferably has a short pore connection length in the thickness direction. It is because generation
- the pore connection length is preferably less than 6.8 ⁇ m, and more preferably 3.7 ⁇ m or less.
- the pore connection length starting from the surface of the solid electrolyte layer on the negative electrode active material layer side is preferably within the above range.
- the total number of pores in a plane 100 ⁇ m 2 perpendicular to the thickness direction is preferably 100 or less on the surface of the solid electrolyte layer on the negative electrode active material layer side.
- the solid electrolyte layer in the present invention may be composed only of the above-described sulfide glass, and may contain other components. Examples of other components include a binder described later.
- the ratio of the sulfide glass contained in the solid electrolyte layer is, for example, 50% by volume or more, preferably 60% by volume or more, more preferably 70% by volume or more, and 80% by volume or more. Is more preferable, and 90% by volume or more is particularly preferable.
- the thickness of the solid electrolyte layer is, for example, in the range of 0.1 ⁇ m to 1000 ⁇ m, and preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
- Negative electrode active material layer is a layer containing at least a negative electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good.
- the negative electrode active material is not particularly limited as long as dendrite can be generated during charging. On the other hand, whether or not dendrite is actually generated is greatly influenced by the current density during charging. For example, if the current density during charging is extremely increased, dendrites are generated in many cases. For example, when the Li insertion potential of the negative electrode active material is low, dendrites are likely to occur during charging.
- the Li insertion potential of the negative electrode active material is preferably 1.5 V (vs Li / Li + ) or less, and more preferably 0.5 V (vs Li / Li + ) or less. Note that the Li insertion potential of the negative electrode active material can be determined by, for example, cyclic voltammetry.
- the negative electrode active material examples include metal lithium; lithium alloys such as lithium aluminum alloy, lithium tin alloy, lithium lead alloy, and lithium silicon alloy; tin oxide, silicon oxide, lithium titanium oxide, niobium oxide, and tungsten oxide.
- Metal sulfides such as tin sulfide, metal sulfides such as tin sulfide and titanium sulfide; metal nitrides such as lithium cobalt nitride, lithium iron nitride and lithium manganese nitride; and carbon materials such as graphite it can.
- the negative electrode active material layer may contain a solid electrolyte material.
- the solid electrolyte material By using the solid electrolyte material, the ion conductivity of the negative electrode active material layer can be improved.
- the kind of solid electrolyte material is not specifically limited, For example, a sulfide solid electrolyte material can be mentioned.
- the sulfide solid electrolyte material include Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —LiI, Li 2 S—P 2 S 5 —LiCl, and Li 2 S—P 2 S 5 —.
- LiBr Li 2 S—P 2 S 5 —Li 2 O, Li 2 S—P 2 S 5 —Li 2 O—LiI, Li 2 S—SiS 2 , Li 2 S—SiS 2 —LiI, Li 2 S— SiS 2 —LiBr, Li 2 S—SiS 2 —LiCl, Li 2 S—SiS 2 —B 2 S 3 —LiI, Li 2 S—SiS 2 —P 2 S 5 —LiI, Li 2 S—B 2 S 3 , Li 2 S-P 2 S 5 -Z m S n ( however, m, n is the number of positive .Z is, Ge, Zn, one of Ga.), Li 2 S- GeS 2, Li 2 S- SiS 2 -Li 3 PO 4, Li 2 S-SiS 2 -Li x MO (However, x, y is a positive number .M is, P, Si, Ge, B , Al, Ga, either an
- the negative electrode active material layer may further contain a conductive material.
- a conductive material By adding a conductive material, the conductivity of the negative electrode active material layer can be improved.
- the conductive material include acetylene black, ketjen black, and carbon fiber.
- the negative electrode active material layer may contain a binder. Examples of the type of binder include fluorine-containing binders such as polyvinylidene fluoride (PVDF).
- PVDF polyvinylidene fluoride
- the thickness of the negative electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the positive electrode active material layer in the present invention is a layer containing at least a positive electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good.
- a positive electrode active material for example, an oxide active material can be exemplified, and specifically, LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2, etc.
- Rock salt layered active material spinel type active material such as LiMn 2 O 4 , Li (Ni 0.5 Mn 1.5 ) O 4 , olivine type active material such as LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCuPO 4, etc.
- Si-containing oxides such as Li 2 FeSiO 4 and Li 2 MnSiO 4 may be used as the positive electrode active material.
- the surface of the positive electrode active material may be covered with a coat layer. This is because the reaction between the positive electrode active material and the solid electrolyte material can be suppressed.
- the material for the coating layer include Li ion conductive oxides such as LiNbO 3 .
- the solid electrolyte material, the conductive material, and the binder used for the positive electrode active material layer are the same as those in the negative electrode active material layer described above.
- the thickness of the positive electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the lithium solid state battery of the present invention has at least the solid electrolyte layer, the negative electrode active material layer, and the positive electrode active material layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material layer.
- the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon.
- examples of the material for the negative electrode current collector include SUS, copper, nickel, and carbon.
- the thickness, shape, and the like of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the battery.
- the battery case of a general battery can be used for the battery case used for this invention. Examples of the battery case include a SUS battery case.
- the lithium solid state battery of the present invention may be a primary battery or a secondary battery, and among them, a secondary battery is preferable. This is because it can be repeatedly charged and discharged and is useful, for example, as an in-vehicle battery.
- Examples of the shape of the lithium solid state battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type.
- the lithium solid state battery of the present invention can suppress the occurrence of a short circuit due to dendrites, it is suitable for high rate charging.
- the lithium solid state battery of the present invention may have a charge control unit that controls the charge rate.
- the charge rate is, for example, preferably 1C or more, more preferably 3C or more, and further preferably 5C or more.
- the lithium solid state battery of the present invention is not particularly limited as long as it has the above-described solid electrolyte layer.
- As the configuration of the lithium solid battery for example, as shown in FIG. 1 described above, a positive electrode active material layer 1 containing a positive electrode active material, a negative electrode active material layer 2 containing a negative electrode active material, and a positive electrode active material layer 1 And a configuration including a solid electrolyte layer 3 formed between the negative electrode active material layer 2.
- the lithium solid state battery of the present invention may be a battery that does not provide a negative electrode active material layer during assembly and deposits Li metal as a negative electrode active material by subsequent charging.
- a negative electrode current collector 5 As a configuration of such a lithium solid state battery, for example, as shown in FIG. 3, a negative electrode current collector 5, a solid electrolyte layer 3, a positive electrode active material layer 1, and a positive electrode current collector 4 are provided in this order.
- the structure provided with the solid electrolyte layer 3 on the surface of the body 5 can be mentioned. As shown in FIG.
- a lithium solid battery that does not have a negative electrode active material layer at the time of assembly has a specific problem that a short circuit due to dendrite is more likely to occur than a lithium solid battery that has a negative electrode active material layer at the time of assembly.
- Li is inserted into the negative electrode active material (for example, carbon), and therefore usually Li deposition does not immediately occur on the surface of the negative electrode active material.
- the negative electrode active material layer is not provided at the time of assembly, Li deposition occurs on the surface of the negative electrode current collector at the time of charging, so that a short circuit due to dendrite tends to occur remarkably.
- such a lithium solid state battery does not have a negative electrode active material layer at the stage before charging (when the battery is assembled), and is a negative electrode active material using Li contained in the positive electrode active material layer at the time of charging. Li metal is deposited and self-formed. Therefore, it is advantageous in terms of volume and weight as compared with the case where the negative electrode active material layer is provided in advance, and has an advantage that the energy density of the battery can be increased. In addition, there is an advantage that the amount of Li metal used in the battery can be minimized.
- the configuration of the lithium solid state battery of the present invention includes, as shown in FIG. 4, for example, a negative electrode current collector 5, a solid electrolyte layer 3, a positive electrode active material layer 1, and a positive electrode current collector 4 in this order.
- the structure provided with the negative electrode active material layer 2 which is the Li metal deposited on the surface of the solid electrolyte layer 3 side of the electric body 5 may be used.
- the lithium solid state battery shown in FIG. 4 corresponds to a state in which the lithium solid state battery having the configuration shown in FIG. 3 is charged.
- Li metal is deposited on the surface of the negative electrode current collector can be confirmed by observing the interface between the two.
- a field emission scanning electron microscope FE-SEM
- FE-SEM field emission scanning electron microscope
- Li metal when Li metal is arranged in advance, the Li metal exists uniformly in a dense state.
- Li metal when Li metal is deposited, the Li metal is present in a slightly sparse state following the surface shape of the solid electrolyte layer.
- the surface of the deposited Li metal may be fibrous (about 100 nm in diameter).
- the thickness of the Li metal deposited on the surface of the negative electrode current collector is not particularly limited, but varies depending on the state of charge (State-of-Charge).
- the maximum thickness of the Li metal is, for example, 50 ⁇ m or less, preferably 30 ⁇ m or less, and more preferably 20 ⁇ m or less. Note that the maximum thickness of the Li metal can be calculated as an average thickness in a state in which charging is most advanced.
- the amount of Li in the entire battery usually matches the amount of Li in the positive electrode active material layer and the solid electrolyte layer. Further, when an electrochemical redox decomposition reaction or the like does not occur in the solid electrolyte layer, the amount of Li in the solid electrolyte layer is constant, so that the amount of Li decreased from the positive electrode active material layer during charging and the negative electrode during charging This corresponds to the amount of Li deposited on the current collector. Further, in a state where the charging is completely advanced, the positive electrode active material may not contain Li.
- FIG. 5 is a schematic cross-sectional view showing an example of the lithium solid state battery module of the present invention.
- a lithium solid state battery module 30 in FIG. 5 includes a lithium solid state battery 10 and a restraining member 20 that applies a restraining pressure in the thickness direction DT to the lithium solid state battery 10.
- the restraining member 20 is connected to the plate-like portion 12 sandwiching both surfaces of the lithium solid battery 10, the rod-like portion 11 that couples the two plate-like portions 12, and the rod-like portion 11, and restrains pressure by a screw structure or the like.
- an adjustment unit 13 for adjustment.
- the insulation process required for a restraint member may be given so that a positive / negative electrode may not short-circuit.
- the present invention by using the above-described lithium solid state battery, it is possible to obtain a lithium solid state battery module in which occurrence of a short circuit due to dendrite is suppressed.
- the restraining member in the present invention is not particularly limited as long as the restraining pressure in the thickness direction can be applied to the lithium solid state battery, and a general restraining member can be used.
- the restraint pressure (surface pressure) in this invention is not specifically limited, For example, it is 0.1 MPa or more, and it is preferable that it is 1 MPa or more. By increasing the restraint pressure, there is an advantage that it is easy to maintain contact between particles such as contact between active material particles and electrolyte particles.
- the restraint pressure (surface pressure) is, for example, 100 MPa or less, and preferably 50 MPa or less. This is because if the restraint pressure is too large, the restraint member is required to have high rigidity, and the module may be increased in size.
- FIG. 6 is a schematic cross-sectional view showing an example of a method for producing a lithium solid state battery of the present invention.
- sulfide glass having a composition of 30LiI ⁇ 70 (0.75Li 2 S ⁇ 0.25P 2 S 5 ) is pressed to form the solid electrolyte layer 3 (FIG. 6A).
- the positive electrode active material layer 1 is formed by arranging and pressing a positive electrode material containing a positive electrode active material on one surface of the solid electrolyte layer 3 (FIG. 6B).
- a negative electrode material containing a negative electrode active material is disposed on the other surface of the solid electrolyte layer 3 and pressed to form the negative electrode active material layer 2 (FIG. 6C).
- the positive electrode current collector 4 and the negative electrode current collector 5 are respectively disposed on the surfaces of the positive electrode active material layer 1 and the negative electrode active material layer 2 (FIG. 6D).
- a lithium solid state battery is obtained by storing the obtained laminate in a battery case (not shown).
- the average pore radius of the solid electrolyte layer determined by the mercury intrusion method is set to a predetermined value or less.
- the number of times of pressing may be one time or a plurality of times, but it is usually a plurality of times.
- the average pore radius of the solid electrolyte layer is set to a predetermined value or less by the plurality of presses.
- a solid electrolyte layer is formed using a specific sulfide glass, and the average pore radius is set to a predetermined value or less, whereby a lithium solid state battery that suppresses the occurrence of short circuits caused by dendrites is obtained. Obtainable.
- the manufacturing method of the lithium solid battery of this invention is demonstrated for every process.
- Solid electrolyte layer forming step is a step of pressing the sulfide glass having an ionic conductor containing Li element, P element and S element to form the solid electrolyte layer.
- the sulfide glass and the solid electrolyte layer obtained in this step are the same as the contents described in the above “A. Lithium solid battery”, so description thereof is omitted here.
- the method to press is not specifically limited, For example, a flat plate press, a roll press, etc. can be mentioned.
- the maximum pressure applied to the solid electrolyte layer is, for example, greater than 588 MPa, preferably 600 MPa or more, more preferably 650 MPa or more, further preferably 700 MPa or more, and 750 MPa. The above is particularly preferable.
- the maximum pressure applied to the solid electrolyte layer is, for example, 1000 MPa or less, and preferably 800 MPa or less.
- the “maximum pressure applied to the solid electrolyte layer” is not only the pressure applied in the solid electrolyte layer forming step, but also the highest pressure applied to the solid electrolyte layer in each step described later. Say things.
- a positive electrode active material layer forming step of forming a positive electrode active material layer using a positive electrode material containing a positive electrode active material, a negative electrode material containing a negative electrode active material You may have the negative electrode active material layer formation process which forms a negative electrode active material layer using.
- a positive electrode material and a negative electrode material will not be specifically limited if a desired active material layer can be obtained, For example, a compound material, a thin film, a sintered compact etc. can be mentioned.
- the order of the solid electrolyte layer forming step, the positive electrode active material layer forming step, and the negative electrode active material layer forming step is not particularly limited as long as a desired lithium solid state battery can be obtained, and any order may be adopted. Can do. Further, the solid electrolyte layer forming step and the positive electrode active material layer forming step may be performed simultaneously, or the solid electrolyte layer forming step and the negative electrode active material layer forming step may be performed simultaneously. Furthermore, the solid electrolyte layer forming step, the positive electrode active material layer forming step, and the negative electrode active material layer forming step may be performed simultaneously. Moreover, you may press in the state which has arrange
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
- Example 1 Synthesis of sulfide glass
- lithium sulfide Li 2 S, purity 99.9%, manufactured by Nippon Chemical Industry Co., Ltd.
- diphosphorus pentasulfide P 2 S 5 , purity 99.9%, manufactured by Aldrich
- lithium iodide LiI, purity 99.9%, manufactured by Aldrich
- This sulfide glass is referred to as sulfide glass A.
- This sulfide glass is referred to as sulfide glass B.
- a coating layer (average thickness: 10 nm) composed of LiNbO 3 was formed on the surface of this positive electrode active material using a tumbling fluidized coating apparatus (manufactured by POWREC).
- Example 2 For evaluation in the same manner as in Example 1 except that the sulfide glass used for the solid electrolyte layer was changed to sulfide glass B (30LiI ⁇ 70 (0.75Li 2 S ⁇ 0.25P 2 S 5 )). A battery was obtained.
- Example 1 A sulfide glass (75Li 2 S ⁇ 25P 2 S 5 ) was obtained in the same manner as in Example 1 except that LiI was not used. This sulfide glass is referred to as sulfide glass C. An evaluation battery was obtained in the same manner as in Example 1 except that the sulfide glass used for the solid electrolyte layer was changed to sulfide glass C (75Li 2 S ⁇ 25P 2 S 5 ).
- Example 2 An evaluation battery was obtained in the same manner as in Example 2 except that the pressure at the time of forming the positive electrode active material layer was changed to 588 MPa.
- FIG. 10 is an enlarged view of FIG.
- Comparative Examples 1 to 4 a rapid voltage drop was confirmed during charging, suggesting that a short circuit occurred due to dendrites.
- FIG. 9 in Examples 1 and 2, a short circuit did not occur during charging, and a charge specific capacity of about 150 mAh / g and a discharge specific capacity of about 130 mAh / g were obtained.
- the discharge specific capacity was smaller than in Examples 1 and 2.
- Table 1 in Examples 1 and 2 high Coulomb efficiency of 85% or more was shown.
- the pore area ratio in the thickness direction of the solid electrolyte layer obtained from the image analysis result is shown in FIG. As shown in FIG. 12, it was confirmed that the larger the molding pressure, the smaller the pore area ratio, and the shorter the short circuit.
- Table 2 shows the average pore area with respect to a plane of 100 ⁇ m 2 perpendicular to the thickness direction. As shown in Table 2, when the average pore area with respect to the plane 100 [mu] m 2 is 7.3 .mu.m 2 or less, and it is possible to suppress the generation of short-circuit due to dendrite.
- a region where the pore area ratio is 0.05% or less is defined as a pore breakage region, and the length of the pore breakage region in the thickness direction is defined as a pore breakage distance, as shown in Table 2
- the pore breakage distance is 3 ⁇ m or more, the occurrence of a short circuit due to dendrites can be suppressed.
- FIG. 13 is a cross-sectional view and a perspective view showing connected pores.
- 13 (a-1) and (a-2) are the results of Example 2
- FIGS. 13 (b-1) and (b-2) are the results of Comparative Example 2
- FIG. (C-1) and (c-2) are the results of Comparative Example 3.
- 14 and 15 are graphs showing the ratio of the connected pores to the total pores. From these results, the pore connection length in the thickness direction was calculated. The results are shown in FIG.
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Abstract
Description
まず、本発明のリチウム固体電池について説明する。図1は、本発明のリチウム固体電池の一例を示す概略断面図である。図1におけるリチウム固体電池10は、正極活物質を含有する正極活物質層1と、負極活物質を含有する負極活物質層2と、正極活物質層1および負極活物質層2の間に形成された固体電解質層3と、正極活物質層1の集電を行う正極集電体4と、負極活物質層2の集電を行う負極集電体5と、これらの部材を収納する電池ケース6とを有する。本発明においては、固体電解質層3が特定の硫化物ガラスを含有し、さらに、固体電解質層3の平均細孔径が特定の値以下であることを大きな特徴とする。
以下、本発明のリチウム固体電池について、構成ごとに説明する。
本発明における固体電解質層は、正極活物質層および負極活物質層の間に形成され、特定の硫化物ガラスを有する。また、本発明において、水銀圧入法により求められる固体電解質層の平均細孔半径は、通常、0.0057μm以下であり、0.0054μm以下であることが好ましく、0.0051μm以下であることがより好ましい。固体電解質層の平均細孔半径は、水銀圧入法により求める。具体的には、後述する実施例に記載するように、細孔分布測定装置を用いることによって、細孔分布曲線から平均細孔半径を求めることができる。
本発明における硫化物ガラスは、硫化物固体電解質材料の一つであり、Li元素、P元素およびS元素を有するイオン伝導体を有する。また、本発明における硫化物ガラスは、広義の非晶質体を意味する。そのため、非晶質化した結果、例えば原料の一部(例えば、後述するLiI)が残存し、X線回折においてピークが観測されるような材料であっても、本発明における硫化物ガラスに含まれる。中でも、本発明における硫化物ガラスは、X線回折においてピークが観測されないことが好ましい。
本発明における固体電解質層は、水銀圧入法により求められる平均細孔半径が上述した範囲内にあることを特徴とする。一方、本発明における固体電解質層の細孔分布は、FIB-SEM(集束イオンビーム/走査型電子顕微鏡)を用いた断面観察でも評価することができる。具体的には、以下の平均細孔面積、細孔断絶距離、細孔連結長を求めることができる。
本発明における負極活物質層は、少なくとも負極活物質を含有する層であり、必要に応じて、固体電解質材料、導電化材および結着材の少なくとも一つを含有していても良い。
本発明における正極活物質層は、少なくとも正極活物質を含有する層であり、必要に応じて、固体電解質材料、導電化材および結着材の少なくとも一つを含有していても良い。正極活物質としては、例えば酸化物活物質を挙げることができ、具体的には、LiCoO2、LiMnO2、LiNiO2、LiVO2、LiNi1/3Co1/3Mn1/3O2等の岩塩層状型活物質、LiMn2O4、Li(Ni0.5Mn1.5)O4等のスピネル型活物質、LiFePO4、LiMnPO4、LiNiPO4、LiCuPO4等のオリビン型活物質等を挙げることができる。また、Li2FeSiO4、Li2MnSiO4等のSi含有酸化物を正極活物質として用いても良い。また、正極活物質の表面は、コート層で被覆されていても良い。正極活物質と固体電解質材料との反応を抑制できるからである。コート層の材料としては、例えば、LiNbO3等のLiイオン伝導性酸化物を挙げることができる。
本発明のリチウム固体電池は、上述した固体電解質層、負極活物質層および正極活物質層を少なくとも有する。さらに通常は、正極活物質層の集電を行う正極集電体、および負極活物質層の集電を行う負極集電体を有する。正極集電体の材料としては、例えばSUS、アルミニウム、ニッケル、鉄、チタンおよびカーボン等を挙げることができる。一方、負極集電体の材料としては、例えばSUS、銅、ニッケルおよびカーボン等を挙げることができる。正極集電体および負極集電体の厚さや形状等については、電池の用途等に応じて適宜選択することが好ましい。また、本発明に用いられる電池ケースには、一般的な電池の電池ケースを用いることができる。電池ケースとしては、例えばSUS製電池ケース等を挙げることができる。
本発明のリチウム固体電池は、一次電池であっても良く、二次電池であっても良いが、中でも二次電池であることが好ましい。繰り返し充放電でき、例えば車載用電池として有用だからである。本発明のリチウム固体電池の形状としては、例えば、コイン型、ラミネート型、円筒型および角型等を挙げることができる。また、本発明のリチウム固体電池は、デンドライトに起因する短絡の発生を抑制できるため、ハイレート充電に適している。本発明のリチウム固体電池は、充電レートを制御する充電制御部を有していても良い。充電レートは、例えば1C以上であることが好ましく、3C以上であることがより好ましく、5C以上であることがさらに好ましい。
次に、本発明のリチウム固体電池モジュールについて説明する。図5は、本発明のリチウム固体電池モジュールの一例を示す概略断面図である。図5におけるリチウム固体電池モジュール30は、リチウム固体電池10と、リチウム固体電池10に厚さ方向DTの拘束圧を付与する拘束部材20とを有する。また、拘束部材20は、リチウム固体電池10の両表面を挟む板状部12と、2つの板状部12を連結する棒状部11と、棒状部11に連結され、ネジ構造等により拘束圧を調整する調整部13とを有する。なお、正負極が短絡しないように、拘束部材に必要な絶縁処理が施されていても良い。
次に、本発明のリチウム固体電池の製造方法について説明する。図6は、本発明のリチウム固体電池の製造方法の一例を示す概略断面図である。図6においては、まず、30LiI・70(0.75Li2S・0.25P2S5)の組成を有する硫化物ガラスをプレスし、固体電解質層3を形成する(図6(a))。次に、固体電解質層3の一方の表面に、正極活物質を含有する正極材を配置し、プレスすることで、正極活物質層1を形成する(図6(b))。次に、固体電解質層3の他方の表面に、負極活物質を含有する負極材を配置し、プレスすることで、負極活物質層2を形成する(図6(c))。次に、正極活物質層1および負極活物質層2の表面に、それぞれ、正極集電体4および負極集電体5を配置する(図6(d))。得られた積層体を電池ケース(図示せず)に収納することで、リチウム固体電池が得られる。本発明においては、水銀圧入法により求められる固体電解質層の平均細孔半径を所定の値以下とする。リチウム固体電池の製造に際し、プレスする回数は、一回でも良く、複数回でも良いが、通常は、複数回である。その複数回のプレスによって、固体電解質層の平均細孔半径を所定の値以下とする。
以下、本発明のリチウム固体電池の製造方法について、工程ごとに説明する。
本発明における固体電解質層形成工程は、Li元素、P元素およびS元素を有するイオン伝導体を有する硫化物ガラスをプレスし、上記固体電解質層を形成する工程である。
本発明においては、固体電解質層形成工程の他に、正極活物質を含有する正極材を用いて正極活物質層を形成する正極活物質層形成工程、負極活物質を含有する負極材を用いて負極活物質層を形成する負極活物質層形成工程を有していても良い。正極材および負極材の形態は、所望の活物質層を得ることができれば特に限定されるものではないが、例えば、合材、薄膜、焼結体等を挙げることができる。
(硫化物ガラスの合成)
出発原料として、硫化リチウム(Li2S、純度99.9%、日本化学工業社製)と、五硫化二リン(P2S5、純度99.9%、アルドリッチ社製)と、ヨウ化リチウム(LiI、純度99.9%、アルドリッチ社製)とを用いた。次に、Ar雰囲気下(露点-70℃)のグローブボックス内で、Li2S、P2S5およびLiIを、20LiI・80(0.75Li2S・0.25P2S5)の組成比で混合した。この混合物2gを、遊星型ボールミルの容器(45cc、ZrO2製)に投入し、脱水ヘプタン(水分量30ppm以下、4g)を投入し、さらにZrO2ボール(φ=5mm、53g)を投入し、容器を完全に密閉した(Ar雰囲気)。この容器を遊星型ボールミル機(フリッチュ製P7)に取り付け、台盤回転数500rpmで、1時間処理および15分休止のメカニカルミリングを40回行った。その後、得られた試料を、ホットプレート上でヘプタンを除去するように乾燥させ、硫化物ガラス(20LiI・80(0.75Li2S・0.25P2S5)、D50=25μm)を得た。この硫化物ガラスを、硫化物ガラスAとする。また、同様の方法により、硫化物ガラス(30LiI・70(0.75Li2S・0.25P2S5)、D50=25μm)を得た。この硫化物ガラスを、硫化物ガラスBとする
まず、正極活物質(LiNi1/3Co1/3Mn1/3O2、三元系層状活物質、D50=4μm~6μm、日亜化学工業社製)を用意した。この正極活物質の表面に、転動流動コーティング装置(パウレック社製)を用いて、LiNbO3から構成されるコート層(平均厚さ10nm)を形成した。コート層を形成した正極活物質と、硫化物ガラスBと、導電化材(VGCF)とを、正極活物質:硫化物ガラスB:導電化材=73:24:3の重量比で混合し、正極合材を得た。
固体電解質層に用いられる硫化物ガラスを、硫化物ガラスB(30LiI・70(0.75Li2S・0.25P2S5))に変更したこと以外は、実施例1と同様にして評価用電池を得た。
LiIを用いなかったこと以外は、実施例1と同様にして硫化物ガラス(75Li2S・25P2S5)を得た。この硫化物ガラスを、硫化物ガラスCとする。固体電解質層に用いられる硫化物ガラスを、硫化物ガラスC(75Li2S・25P2S5)に変更したこと以外は、実施例1と同様にして評価用電池を得た。
正極活物質層を形成する際の圧力を、588MPaに変更したこと以外は、実施例2と同様にして評価用電池を得た。
正極活物質層を形成する際の圧力を、392MPaに変更したこと以外は、実施例2と同様にして評価用電池を得た。
正極活物質層を形成する際の圧力を、196MPaに変更したこと以外は、実施例2と同様にして評価用電池を得た。
(水銀圧入法による細孔分布測定)
硫化物ガラスA~Cを、それぞれプレスして固体電解質層を成型し、水銀圧入法により、固体電解質層の細孔分布を測定した。なお、成型圧力は、実施例1、2および比較例1~4において付与した最大圧力と同一とした。測定には、細孔分布測定装置(micromeritics社製オートポアIV9520)を用い、乾燥Ar雰囲気に置換した簡易グローブバッグ内で行った。細孔径はWashburnの式を用いて算出し、得られた細孔分布曲線から平均細孔半径を求めた。
Washburnの式:PD=-4σcоsθ
(P:圧力、D:細孔直径、σ:水銀の表面張力、θ:水銀と試料との接触角)
実施例1、2および比較例1~4で得られた評価用電池を用いて、充放電測定を行った。測定条件は、25℃、電流密度0.2mAh/cm2(0.1Cに相当)、3.0V~4.1V、CC充放電とした。内部短絡が起きた場合には、充電が終了しないため、その場合は20時間で充電を終了させ、放電させた。なお、内部短絡の有無は、充電時の急激な電圧低下の有無により判断した。また、充放電容量について、クーロン効率を算出した。
硫化物ガラスBを、それぞれプレスして固体電解質層を成型し、FIB-SEMを用いた断面観察により、固体電解質層の細孔分布を測定した。なお、成型圧力は、実施例2および比較例2~4において印加した最大圧力と同一とした。測定には、集束イオン/電子ビーム加工観察装置(日立ハイテクノロジーズ社製nanoDUE’T NB5000)を用いた。まず、乾燥Ar雰囲気で、試料表面に保護膜(タングステン蒸着膜)を堆積させ、次に、図11に示すような観察領域(一辺が約10μmの立方体)周辺の領域をFIB加工により除去した。その後、自動加工モードで観察した。具体的には、立方体を奥行き方向(固体電解質層の厚さ方向)に沿って100枚にスライスし、それぞれの表面の画像解析を行った。なお、解像度は1nm程度である。
2 … 負極活物質層
3 … 固体電解質層
4 … 正極集電体
5 … 負極集電体
6 … 電池ケース
10 … リチウム固体電池
20 … 拘束部材
30 … リチウム固体電池モジュール
Claims (10)
- Li元素、P元素およびS元素を有するイオン伝導体を有する硫化物ガラスを含有し、水銀圧入法により求められる平均細孔半径が0.0057μm以下である固体電解質層を備えることを特徴とするリチウム固体電池。
- 前記硫化物ガラスは、前記イオン伝導体と、LiIとを有し、
前記イオン伝導体はPS4 3-構造を有し、前記イオン伝導体の全アニオン構造に対する前記PS4 3-構造の割合が50mol%以上であり、
前記LiIの割合が20mol%~30mol%の範囲内であることを特徴とする請求項1に記載のリチウム固体電池。 - 前記固体電解質層は、厚さ方向に垂直な平面100μm2に対する平均細孔面積が7.30μm2以下であることを特徴とする請求項1または請求項2に記載のリチウム固体電池。
- 前記固体電解質層は、細孔断絶距離が3μm以上であることを特徴とする請求項1から請求項3までのいずれかの請求項に記載のリチウム固体電池。
- 前記固体電解質層は、厚さ方向における細孔連結長が3.7μm以下であることを特徴とする請求項1から請求項4までのいずれかの請求項に記載のリチウム固体電池。
- 正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、前記正極活物質層および前記負極活物質層の間に形成された前記固体電解質層とを備えることを特徴とする請求項1から請求項4までのいずれかの請求項に記載のリチウム固体電池。
- 負極集電体、前記固体電解質層、正極活物質層および正極集電体をこの順で備え、
前記負極集電体の表面上に、前記固体電解質層を備えることを特徴とする請求項1から請求項4までのいずれかの請求項に記載のリチウム固体電池。 - 負極集電体、前記固体電解質層、正極活物質層および正極集電体をこの順で備え、
前記負極集電体の前記固体電解質層側の表面に析出したLi金属である負極活物質層を備えることを特徴とする請求項1から請求項4までのいずれかの請求項に記載のリチウム固体電池。 - 請求項1から請求項8までのいずれかの請求項に記載のリチウム固体電池と、前記リチウム固体電池に厚さ方向の拘束圧を付与する拘束部材とを有することを特徴とするリチウム固体電池モジュール。
- Li元素、P元素およびS元素を有するイオン伝導体を有する硫化物ガラスをプレスし、固体電解質層を形成する固体電解質層形成工程を有し、
水銀圧入法により求められる前記固体電解質層の平均細孔半径を、0.0057μm以下とすることを特徴とするリチウム固体電池の製造方法。
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