WO2012157120A1 - 硫化物系固体電池モジュール - Google Patents
硫化物系固体電池モジュール Download PDFInfo
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- WO2012157120A1 WO2012157120A1 PCT/JP2011/061565 JP2011061565W WO2012157120A1 WO 2012157120 A1 WO2012157120 A1 WO 2012157120A1 JP 2011061565 W JP2011061565 W JP 2011061565W WO 2012157120 A1 WO2012157120 A1 WO 2012157120A1
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- sulfide
- based solid
- positive electrode
- negative electrode
- battery
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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
- H01M10/04—Construction or manufacture in general
- H01M10/0463—Cells or batteries with horizontal or inclined 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
- H01M10/05—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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
Definitions
- the present invention relates to a sulfide-based solid battery module that can suppress rapid deterioration of some unit cells due to hydrogen sulfide.
- the secondary battery can convert the decrease in chemical energy associated with the chemical reaction into electrical energy and perform discharge.
- the secondary battery converts electrical energy into chemical energy by flowing current in the opposite direction to that during discharge.
- the battery can be stored (charged).
- lithium secondary batteries are widely used as power sources for notebook personal computers, mobile phones, and the like because of their high energy density.
- lithium cobaltate Li 1-x CoO 2
- Li 1-x CoO 2 + xLi + + xe ⁇ ⁇ LiCoO 2 (II) (In the above formula (II), 0 ⁇ x ⁇ 1.)
- reverse reactions of the above formulas (I) and (II) proceed in the negative electrode and the positive electrode, respectively, and in the negative electrode, graphite (Li x C) containing lithium by graphite intercalation is Since lithium cobaltate (Li 1-x CoO 2 ) is regenerated, re-discharge is possible.
- a lithium secondary battery in which the electrolyte is a solid electrolyte and the battery is completely solid does not use a flammable organic solvent in the battery. It is considered to be excellent in productivity.
- a sulfide-based solid electrolyte is known as a solid electrolyte material used for such a solid electrolyte.
- sulfide-based solid electrolyte materials easily generate hydrogen sulfide by reacting with moisture, batteries using sulfide-based solid electrolyte materials are liable to deteriorate due to the generation of hydrogen sulfide, and the life of the battery There was a problem of short.
- Patent Document 1 includes a first composite material layer containing sulfide glass ceramics and a positive electrode active material, a second composite material layer containing sulfide glass ceramics and a negative electrode active material, and the first composite material layer and the second composite material layer.
- a solid battery including a solid electrolyte layer containing sulfide glass ceramics positioned between the composite layers, a storage case for storing the solid battery, a load sensor provided on the storage case, and the storage case And the technique of the battery unit provided with the clamping member which pinches
- FIG. 3 of Patent Document 1 describes a schematic cross-sectional view of the solid state battery of the invention disclosed in the document.
- hydrogen sulfide is generated by the reaction between the moisture and sulfide glass ceramics.
- the generated hydrogen sulfide accumulates in some specific solid state batteries, and only the solid state battery deteriorates. As a result, the entire battery unit may be overcharged.
- the present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a sulfide-based solid battery module that can suppress abrupt deterioration of some unit cells due to hydrogen sulfide.
- the sulfide-based solid battery module of the present invention includes a unit battery in which at least a positive electrode, an electrolyte layer, and a negative electrode are stacked in this order, and at least one of the positive electrode, the electrolyte layer, and the negative electrode includes a sulfide-based solid material.
- a sulfide-based solid battery module comprising a unit battery stack in which two or more unit batteries are further stacked along the stacking direction of the unit batteries, wherein the stacking direction of the unit battery stacks is 45 ° to the vertical direction. It is tilted at an angle of 90 °.
- the sulfide-based solid material is preferably a sulfide-based solid electrolyte.
- the stacking direction of the unit cell stack is substantially perpendicular to the vertical direction.
- each unit cell included in the unit cell stack is similarly deteriorated from the end portion where the hydrogen sulfide is accumulated. Therefore, the deterioration rates of the unit cells can be made substantially equal, and abrupt deterioration of some unit cells can be prevented.
- the sulfide-based solid battery module of the present invention includes a unit battery in which at least a positive electrode, an electrolyte layer, and a negative electrode are stacked in this order, and at least one of the positive electrode, the electrolyte layer, and the negative electrode includes a sulfide-based solid material.
- a sulfide-based solid battery module comprising a unit battery stack in which two or more unit batteries are further stacked along the stacking direction of the unit batteries, wherein the stacking direction of the unit battery stacks is 45 ° to the vertical direction. It is tilted at an angle of 90 °.
- the battery may be deteriorated by a gas such as hydrogen sulfide generated in the battery.
- a gas such as hydrogen sulfide generated in the battery.
- the case where the stacking direction of the stacked body is arranged so as to be substantially parallel to the vertical direction is considered.
- the specific gravity of the generated gas is heavy, the generated gas is biased in the lower part of the stack in the vertical direction, and only a specific unit cell near the lowermost part of the stacked unit cells is contaminated.
- the inventors of the present invention have arranged a stacked body in which a plurality of unit cells are stacked at a predetermined angle with respect to the vertical direction, and preferably, the stacked direction of the stacked body is substantially perpendicular to the vertical direction.
- the material contained in the sulfide-based solid battery is contained or permeated through the exterior resin part that covers the sulfide-based solid battery and mixed from outside air. May react with the sulfide-based solid material to generate hydrogen sulfide (H 2 S).
- H 2 S hydrogen sulfide
- the specific gravity of hydrogen sulfide is heavy with respect to the atmosphere (such as dry air) that fills the sulfide-based solid battery. Therefore, when a plurality of the sulfide-based solid batteries are stacked, the generated hydrogen sulfide stagnates at the bottom of the stacked body.
- the battery member such as the positive electrode active material is subjected to physical and chemical losses due to hydrogen sulfide, and the electrical resistance of the entire laminate increases.
- the stacking direction of the stacked body is arranged so as to be substantially parallel to the vertical direction, the specific sulfide-based solid battery at the bottom of the stacked body connected in series deteriorates and the resistance increases. Therefore, it leads to the overcharge and the life shortening of the whole laminated body.
- the deterioration state of each solid battery in the stacked body becomes uniform, and overcharging and shortening of the life of the entire stacked body can be avoided.
- FIG. 2 is a schematic cross-sectional view showing the relationship between the stacking direction and the vertical direction of the unit battery stack included in the present invention.
- a double wavy line means omission of the figure.
- the unit battery 5 includes a positive electrode including the positive electrode active material layer 2 and the current collector 4, a negative electrode including the negative electrode active material layer 3 and the current collector 4, and the electrolyte layer 1 sandwiched between the positive electrode and the negative electrode. Since the battery shown in FIG. 2 has a bipolar structure, the positive electrode and the negative electrode of the unit batteries 5 adjacent to each other share a current collector. Two or more unit cells 5 are stacked to form a unit cell stack 6. As shown in FIG.
- the stacking direction 7 a of each unit battery substantially coincides with the stacking direction 7 of the unit battery stack.
- the stacking direction is a direction in which the layers are stacked, and is a direction substantially perpendicular to the plane direction of the layers.
- the stacking direction 7 of the unit cell stack 6 is inclined at an angle ⁇ of 45 ° to 90 ° with respect to the vertical direction 10.
- the angle ⁇ in the stacking direction of the unit cell stack with respect to the vertical direction is defined as an acute angle formed by the stacking direction 7 of the unit cell stack and the vertical direction 10 as shown in FIG.
- the angle ⁇ is less than 45 °, a predetermined amount of gas expected in the unit cell stack When this occurs, almost all of a specific unit cell may be affected by the gas.
- the angle ⁇ of the unit cell stack in the stacking direction with respect to the vertical direction is preferably 70 ° to 90 °, and more preferably 90 °.
- a mechanism in which the inclination of the entire sulfide-based solid battery module does not directly affect the inclination of the unit battery stack for example, the inclination of the unit battery stack is controlled.
- An inclination control method for controlling the inclination of the unit cell stack or the like can be provided.
- the tilt control method for example, a method of manually adjusting the position of the unit cell stack so as to obtain an optimal tilt as appropriate can be cited.
- the tilt control device include, for example, a unit cell stack that automatically controls the tilt of the unit cell stack by placing a weight such as a ballast, or a device that can check the tilt, such as a level. And a device for controlling the inclination of the.
- FIG. 1 is a diagram showing a typical example of a laminated structure of a sulfide-based solid battery module according to the present invention, and is a diagram schematically showing a cross section cut in a laminating direction.
- the sulfide-based solid battery module according to the present invention is not necessarily limited to this example.
- a double wavy line means omission of the figure.
- the unit battery 5 includes the positive electrode including the positive electrode active material layer 2 and the current collector 4, the negative electrode including the negative electrode active material layer 3 and the current collector 4, and the electrolyte sandwiched between the positive electrode and the negative electrode.
- Two or more unit cells 5 are stacked to form a unit cell stack 6.
- the positive electrode lead 8a and the negative electrode lead 8b are respectively connected to the outermost current collector set among the layers constituting the unit battery stack 6. Further, the entire unit battery stack 6 is housed in a battery case 9 with the ends of the positive electrode lead 8 a and the negative electrode lead 8 b remaining.
- the angle ⁇ of the unit cell stack 6 in the stacking direction 7 with respect to the vertical direction 10 is 90 °. By setting such an angle, only the specific unit cell is not immersed in the generated gas, and the deterioration rates of all the unit cells can be made substantially equal.
- a method / device for controlling the inclination of the entire sulfide-based solid battery module of this typical example may be used in combination.
- a method and apparatus for controlling the inclination of the entire sulfide-based solid battery module the same apparatus and method as those described above can be used.
- the other components such as the positive electrode and the negative electrode, the electrolyte layer, and the separator used in the sulfide-based solid battery module of the present invention will be described separately.
- at least one of the positive electrode, the electrolyte layer, and the negative electrode contains a sulfide solid material.
- the positive electrode used in the present invention preferably includes a positive electrode current collector, and more preferably includes a positive electrode active material layer containing a positive electrode active material. As shown in FIG. 1, a positive electrode lead may be connected to the positive electrode current collector.
- the negative electrode used in the present invention preferably includes a negative electrode current collector, and more preferably includes a negative electrode active material layer containing a negative electrode active material. As shown in FIG. 1, a negative electrode lead may be connected to the negative electrode current collector.
- the positive electrode active material used in the present invention include LiCoO 2 , LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNiPO 4 , LiMnPO 4 , LiNiO 2 , LiMn 2 O 4 , LiCoMnO 4. , Li 2 NiMn 3 O 8 , Li 3 Fe 2 (PO 4 ) 3 and Li 3 V 2 (PO 4 ) 3 .
- LiNbO 3 or the like may be coated on the positive electrode active material.
- LiCoO 2 is preferably used as the positive electrode active material.
- the thickness of the positive electrode active material layer used in the present invention varies depending on the intended use of the sulfide-based solid battery module, but is preferably in the range of 5 to 250 ⁇ m, and in the range of 20 to 200 ⁇ m. Is particularly preferable, and most preferably in the range of 30 to 150 ⁇ m.
- the average particle diameter of the positive electrode active material is, for example, preferably in the range of 1 to 50 ⁇ m, more preferably in the range of 1 to 20 ⁇ m, and particularly preferably in the range of 3 to 5 ⁇ m. If the average particle size of the positive electrode active material is too small, the handleability may be deteriorated. If the average particle size of the positive electrode active material is too large, it may be difficult to obtain a flat positive electrode active material layer. Because.
- the average particle diameter of the positive electrode active material can be determined by measuring and averaging the particle diameter of the active material carrier observed with, for example, a scanning electron microscope (SEM).
- the positive electrode active material layer may contain a conductive material, a binder, and the like as necessary.
- the conductive material included in the positive electrode active material layer used in the present invention is not particularly limited as long as the conductivity of the positive electrode active material layer can be improved.
- the content of the conductive material in the positive electrode active material layer varies depending on the type of the conductive material, but is usually in the range of 1 to 10% by mass.
- binding material of the positive electrode active material layer used in the present invention examples include synthetic rubbers such as styrene-butadiene rubber, ethylene-propylene rubber, styrene-ethylene-butadiene rubber; polyvinylidene fluoride (PVDF), polytetra A fluoropolymer such as fluoroethylene (PTFE) can be given.
- the content of the binder in the positive electrode active material layer may be an amount that can fix the positive electrode active material or the like, and is preferably smaller. The content of the binder is usually in the range of 1 to 10% by mass. After the positive electrode active material layer is formed, the positive electrode active material layer may be pressed in order to improve the electrode density.
- the positive electrode current collector used in the present invention is not particularly limited as long as it has a function of collecting the positive electrode active material layer.
- Examples of the material for the positive electrode current collector include aluminum, SUS, nickel, iron, and titanium. Among these, aluminum and SUS are preferable.
- As a shape of a positive electrode electrical power collector foil shape, plate shape, mesh shape etc. can be mentioned, for example, Foil shape is preferable.
- the negative electrode active material used for the negative electrode active material layer is not particularly limited as long as it can absorb and release metal ions.
- metal materials such as lithium metal, lithium alloy, metal oxide, metal sulfide, metal nitride, and graphite can be used.
- the negative electrode active material may be in the form of a powder or a thin film.
- the negative electrode active material layer may contain a conductive material, a binder, and the like as necessary. What was mentioned above can be used for the binder and the said electrically conductive material which can be used in a negative electrode active material layer. Moreover, it is preferable to select the usage-amount of a binder and a electrically conductive material suitably according to the use etc. of a sulfide type solid battery module. Further, the film thickness of the negative electrode active material layer is not particularly limited, but is preferably in the range of, for example, 5 to 150 ⁇ m, and more preferably in the range of 10 to 80 ⁇ m.
- the same materials and shapes as those of the positive electrode current collector described above can be employed.
- a manufacturing method of the negative electrode used in the present invention a method similar to the manufacturing method of the positive electrode as described above can be adopted.
- the manufacturing method of the unit cell stack is not necessarily limited to this method.
- the positive electrode and / or negative electrode used in the present invention may contain a sulfide-based solid material.
- the sulfide solid material is not particularly limited as long as it is a solid material containing sulfur element as a main component.
- Specific examples of the sulfide-based solid material include a sulfide-based solid electrolyte and a sulfide-based solid electrode active material.
- Specific examples of the sulfide-based solid electrolyte used in the present invention include Li 2 S—P 2 S 5 , Li 2 S—P 2 S 3 , Li 2 S—P 2 S 3 —P 2 S 5 , Li 2 S—SiS 2 , LiI—Li 2 S—P 2 S 5 , LiI—Li 2 S—SiS 2 —P 2 S 5 , Li 2 S—SiS 2 —Li 4 SiO 4 , Li 2 S—SiS 2 -Li 3 PO 4 , Li 3 PS 4 -Li 4 GeS 4 , Li 3.4 P 0.6 Si 0.4 S 4 , Li 3.25 P 0.25 Ge 0.76 S 4 , Li 4-x Examples thereof include Ge 1-x P x S 4 .
- Specific examples of the sulfide-based solid electrode active material used in the present invention include TiS 2 .
- the electrolyte layer used in the present invention is preferably a layer containing an ion exchange solid electrolyte that performs ion exchange between the positive electrode active material and the negative electrode active material described above.
- Specific examples of the solid electrolyte include oxide-based solid electrolytes, polymer electrolytes, gel electrolytes and the like in addition to the sulfide-based solid electrolytes described above.
- LiPON lithium phosphate oxynitride
- La 0.51 Li 0.34 TiO Examples include 0.74 , Li 3 PO 4 , Li 2 SiO 2 , Li 2 SiO 4 and the like.
- the polymer electrolyte contains a lithium salt and a polymer.
- the lithium salt is not particularly limited as long as it is a lithium salt used in a general lithium secondary battery.
- LiPF 6 , LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiCF 3 SO 3 examples include LiC 4 F 9 SO 3 , LiC (CF 3 SO 2 ) 3, and LiClO 4 .
- the polymer is not particularly limited as long as it forms a complex with a lithium salt, and examples thereof include polyethylene oxide.
- the gel electrolyte contains a lithium salt, a polymer, and a nonaqueous solvent.
- the lithium salt described above can be used as the lithium salt.
- the non-aqueous solvent is not particularly limited as long as it can dissolve the lithium salt.
- non-aqueous solvents may be used alone or in combination of two or more.
- room temperature molten salt can also be used as a non-aqueous electrolyte.
- the polymer is not particularly limited as long as it can be gelled, and examples thereof include polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride (PVDF), polyurethane, polyacrylate, cellulose and the like. Can be mentioned.
- Examples of the method for producing the electrolyte layer include a method of pressing the solid electrolyte.
- the electrolyte layer may be produced by applying a slurry obtained by mixing the solid electrolyte and the solvent to a desired location such as a positive electrode or a negative electrode.
- a separator can be used in the present invention.
- the separator is disposed between the positive electrode current collector and the negative electrode current collector described above, and usually has a function of preventing the contact between the positive electrode active material layer and the negative electrode active material layer and holding the electrolyte layer.
- the material for the separator include resins such as polyethylene (PE), polypropylene (PP), polyester, cellulose, and polyamide. Among these, polyethylene and polypropylene are preferable.
- the separator may have a single layer structure or a multilayer structure.
- the separator having a multilayer structure examples include a separator having a two-layer structure of PE / PP and a separator having a three-layer structure of PP / PE / PP.
- the separator may be a nonwoven fabric such as a resin nonwoven fabric or a glass fiber nonwoven fabric.
- the film thickness of the said separator is not specifically limited, It is the same as that of the separator used for a general sulfide type solid battery.
- the battery case which accommodates a sulfide type solid battery module can also be used as another component.
- the shape of the battery case is not particularly limited as long as it can accommodate the above-described positive electrode, negative electrode, electrolyte layer, and the like. Specifically, a cylindrical shape, a square shape, a coin shape, a laminate shape, etc. Can be mentioned.
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Abstract
Description
LixC→C+xLi++xe- (I)
(上記式(I)中、0<x<1である。)
式(I)の反応で生じる電子は、外部回路を経由し、外部の負荷で仕事をした後、正極に到達する。そして、式(I)の反応で生じたリチウムイオン(Li+)は、負極と正極に挟持された電解質内を、負極側から正極側に電気浸透により移動する。
Li1-xCoO2+xLi++xe-→LiCoO2 (II)
(上記式(II)中、0<x<1である。)
充電時においては、負極及び正極において、それぞれ上記式(I)及び式(II)の逆反応が進行し、負極においてはグラファイトインターカレーションによりリチウムが入り込んだグラファイト(LixC)が、正極においてはコバルト酸リチウム(Li1-xCoO2)が再生するため、再放電が可能となる。
しかしながら、硫化物系固体電解質材料は、水分と反応し硫化水素を発生しやすい性質を持つため、硫化物系固体電解質材料を用いた電池においては硫化水素の発生による劣化が起こりやすく、電池の寿命が短いという課題があった。
本発明は、上記実状を鑑みて成し遂げられたものであり、硫化水素による一部の単位電池の急激な劣化を抑制できる硫化物系固体電池モジュールを提供することを目的とする。
ここで、硫化物系固体材料を含む単位電池が複数積層した積層体を設置する際に、当該積層体の積層方向が、鉛直方向に対して略平行となるように配置される場合について検討する。発生ガスの比重が重い場合には、積層体の鉛直方向下部に発生ガスが偏り、複数積層した単位電池の内、最下部付近の特定の単位電池のみが汚染される。一方、発生ガスの比重が軽い場合には、積層体の鉛直方向上部に発生ガスが偏り、複数積層した単位電池の内、最上部付近の特定の単位電池のみが汚染される。このように、当該積層体の積層方向が、鉛直方向に対して略平行に配置される場合には、特定の単位電池のみの汚染が進行することにより、積層体全体の過充電や、短寿命化につながるおそれがある。
特にバイポーラ構造の場合、積層体の積層方向が鉛直方向に対して略平行となるように配置されると、直列接続した積層体下部の特定の硫化物系固体電池が劣化し、高抵抗化するため、積層体全体の過充電や短寿命化に繋がる。積層体の積層方向を鉛直方向に対して所定の角度に傾けて配置することにより、積層体中の各固体電池の劣化状態が均等となり、積層体全体の過充電や短寿命化を回避できる。
単位電池5は、正極活物質層2及び集電体4を備える正極と、負極活物質層3及び集電体4を備える負極と、当該正極及び当該負極に挟持される電解質層1を備える。なお、図2に示した電池はバイポーラ構造であるため、互いに隣り合う単位電池5の正極と負極は、集電体を共有する。
単位電池5が2以上積層して、単位電池積層体6を構成する。図2に示すように、各単位電池の積層方向7aは、単位電池積層体の積層方向7と略一致する。なお、本発明における積層方向とは、層が積み重なる方向のことであり、層の平面方向と略垂直な方向のことである。
単位電池積層体の厚さや、単位電池積層体を構成する各層の厚さ及び面積にもよるが、角度θが45°未満であるとすると、単位電池積層体内に、予想される所定量のガスが発生した場合に、ある特定の単位電池のほぼ全体が当該ガスに侵されるおそれがある。このように特定の単位電池のみが発生ガスに侵されると、単位電池間の劣化速度を略等しくし、一部の単位電池の急激な劣化を防ぐという、本発明の効果が十分に発揮されないおそれがある。
鉛直方向に対する、単位電池積層体の積層方向の角度θは、70°~90°であることが好ましく、90°であることがより好ましい。
なお、本発明の硫化物系固体電池モジュール全体の傾きと、本発明に用いられる単位電池積層体の傾きとは、必ずしも一致しない。例えば、本発明の硫化物系固体電池モジュール内に、硫化物系固体電池モジュール全体の傾きが単位電池積層体の傾きに直接影響を及ぼさないような機構、例えば、単位電池積層体の傾きを制御する傾き制御方法を用いたり、単位電池積層体の傾きを制御する傾き制御装置等を設けたりすることもできる。傾き制御方法の例としては、例えば、適宜最適な傾きとなるように手動で単位電池積層体の位置を調節する方法等を挙げることができる。傾き制御装置の例としては、例えば、バラスト等の重りを配置することにより単位電池積層体の傾きを制御する装置や、水準器等の傾斜を確認できる機器と連動して自動で単位電池積層体の傾きを制御する装置等を挙げることができる。
上述したように、単位電池5は、正極活物質層2及び集電体4を備える正極と、負極活物質層3及び集電体4を備える負極と、当該正極及び当該負極に挟持される電解質層1を備え、さらに、互いに隣り合う単位電池の正極と負極は、集電体を共有する。単位電池5が2以上積層して、単位電池積層体6を構成する。
単位電池積層体6を構成する層のうち、最も外側に位置する集電体一組について、それぞれ正極リード8a、負極リード8bが接続されている。さらに、正極リード8a、及び負極リード8bの端部を残し、単位電池積層体6全体は電池ケース9に収納されている。
本典型例においては、鉛直方向10に対する、単位電池積層体6の積層方向7の角度θは90°である。このような角度とすることにより、特定の単位電池のみが発生ガスに浸されることがなく、全ての単位電池の劣化速度を略等しくすることができる。
なお、図には示していないが、本典型例の硫化物系固体電池モジュール全体の傾きを制御する方法・装置を併用してもよい。硫化物系固体電池モジュール全体の傾きを制御する方法・装置としては、上述した傾き制御方法・装置等と同様のものを使用できる。
本発明に用いられる正極は、好ましくは正極集電体を備え、さらに好ましくは正極活物質を含有する正極活物質層を備える。図1に示したように、正極集電体には、正極リードが接続されていてもよい。
本発明に用いられる負極は、好ましくは負極集電体を備え、さらに好ましくは負極活物質を含有する負極活物質層を備える。図1に示したように、負極集電体には、負極リードが接続されていてもよい。
これらの中でも、本発明においては、LiCoO2を正極活物質として用いることが好ましい。
本発明において用いられる正極活物質層が有する導電化材としては、正極活物質層の導電性を向上させることができれば特に限定されるものではないが、例えばアセチレンブラック、ケッチェンブラック、VGCF等のカーボンブラック等を挙げることができる。また、正極活物質層における導電化材の含有量は、導電化材の種類によって異なるものであるが、通常1~10質量%の範囲内である。
正極活物質層を形成した後は、電極密度を向上させるために、正極活物質層をプレスしても良い。
負極活物質層中に用いることができる結着材及び上記導電化材は、上述したものを用いることができる。また、結着材及び導電化材の使用量は、硫化物系固体電池モジュールの用途等に応じて、適宜選択することが好ましい。また、負極活物質層の膜厚としては、特に限定されるものではないが、例えば5~150μmの範囲内、中でも10~80μmの範囲内であることが好ましい。
本発明に用いられる負極の製造方法としては、上述したような正極の製造方法と同様の方法を採用することができる。
図1に示した様な単位電池積層体を形成する場合には、集電体の一方の面に正極活物質層を、他方の面に負極活物質層を形成し、当該正極活物質層-集電体-負極活物質層の積層体を、図1に示したような積層の順序となるように、後述する電解質層と共に積層させるという方法を採用することができる。ただし、単位電池積層体の製造方法は、必ずしもこの方法に限られるものではない。
硫化物系固体材料としては、硫黄元素を主要成分として含む固体材料であれば、特に限定されない。硫化物系固体材料としては、具体的には、硫化物系固体電解質、硫化物系固体電極活物質が挙げられる。
本発明に用いられる硫化物系固体電解質としては、具体的には、Li2S-P2S5、Li2S-P2S3、Li2S-P2S3-P2S5、Li2S-SiS2、LiI-Li2S-P2S5、LiI-Li2S-SiS2-P2S5、Li2S-SiS2-Li4SiO4、Li2S-SiS2-Li3PO4、Li3PS4-Li4GeS4、Li3.4P0.6Si0.4S4、Li3.25P0.25Ge0.76S4、Li4-xGe1-xPxS4等を例示することができる。
本発明に用いられる硫化物系固体電極活物質としては、具体的には、TiS2が挙げられる。
本発明に用いられる電解質層は、好ましくは、上述した正極活物質及び負極活物質の間でイオン交換を行う、イオン交換固体電解質を含む層である。固体電解質としては、具体的には、上述した硫化物系固体電解質の他にも、酸化物系固体電解質、ポリマー電解質、ゲル電解質等を例示することができる。
リチウム塩としては、上述したリチウム塩を用いることができる。
非水溶媒としては、上記リチウム塩を溶解できるものであれば特に限定されるものではなく、例えば、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート、1,2-ジメトキシエタン、1,2-ジエトキシエタン、アセトニトリル、プロピオニトリル、テトラヒドロフラン、2-メチルテトラヒドロフラン、ジオキサン、1,3-ジオキソラン、ニトロメタン、N,N-ジメチルホルムアミド、ジメチルスルホキシド、スルホラン、γ-ブチロラクトン等が挙げられる。これらの非水溶媒は、1種のみ用いてもよく、2種以上を混合して用いても良い。また、非水電解液として、常温溶融塩を用いることもできる。
ポリマーとしては、ゲル化が可能なものであれば特に限定されるものではなく、例えば、ポリエチレンオキシド、ポリプロプレンオキシド、ポリアクリルニトリル、ポリビニリデンフロライド(PVDF)、ポリウレタン、ポリアクリレート、セルロース等が挙げられる。
その他の構成要素として、セパレータを本発明に用いることができる。セパレータは、上述した正極集電体及び上記負極集電体の間に配置されるものであり、通常、正極活物質層と負極活物質層との接触を防止し、電解質層を保持する機能を有する。上記セパレータの材料としては、例えばポリエチレン(PE)、ポリプロピレン(PP)、ポリエステル、セルロース及びポリアミド等の樹脂を挙げることができ、中でもポリエチレン及びポリプロピレンが好ましい。また、上記セパレータは、単層構造であっても良く、複層構造であっても良い。複層構造のセパレータとしては、例えばPE/PPの2層構造のセパレータ、PP/PE/PPの3層構造のセパレータ等を挙げることができる。さらに、本発明においては、上記セパレータが、樹脂不織布、ガラス繊維不織布等の不織布等であっても良い。また、上記セパレータの膜厚は、特に限定されるものではなく、一般的な硫化物系固体電池に用いられるセパレータの膜厚と同様である。
また、その他の構成要素として、硫化物系固体電池モジュールを収納する電池ケースを用いることもできる。電池ケースの形状としては、上述した正極、負極、電解質層等を収納できるものであれば特に限定されるものではないが、具体的には、円筒型、角型、コイン型、ラミネート型等を挙げることができる。
2 正極活物質層
3 負極活物質層
4 集電体
5 単位電池
6 単位電池積層体
7 単位電池積層体の積層方向を示す両矢印
7a 単位電池の積層方向を示す両矢印
8a 正極リード
8b 負極リード
9 電池ケース
10 鉛直方向を示す矢印
θ 鉛直方向に対する、単位電池積層体の積層方向の角度
100 硫化物系固体電池モジュール
Claims (3)
- 少なくとも正極、電解質層、及び負極がこの順に積層し、且つ、当該正極、電解質層、及び負極の少なくともいずれか1つが硫化物系固体材料を含む単位電池が、当該単位電池の積層方向に沿ってさらに2以上積層した単位電池積層体を備える硫化物系固体電池モジュールであって、
前記単位電池積層体の積層方向が、鉛直方向に対して45°~90°の角度で傾いていることを特徴とする、硫化物系固体電池モジュール。 - 前記硫化物系固体材料が硫化物系固体電解質である、請求の範囲第1項に記載の硫化物系固体電池モジュール。
- 前記単位電池積層体の積層方向が、鉛直方向に対して略垂直である、請求の範囲第1項又は第2項に記載の硫化物系固体電池モジュール。
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US13/386,912 US20140205885A1 (en) | 2011-05-19 | 2011-05-19 | Sulfide-based solid cell module |
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