WO2013161310A1 - 固体電解質及び二次電池 - Google Patents
固体電解質及び二次電池 Download PDFInfo
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Definitions
- the present invention relates to a solid electrolyte and a secondary battery using the same.
- a lithium secondary battery using lithium metal for the negative electrode theoretically has a large battery capacity per mass and a high potential.
- no conductive auxiliary agent or current collector is required, the time and effort for coating can be reduced, and the cost can be reduced.
- the all solid secondary battery it has been proposed to use a solid electrolyte made of an oxide sintered body. Since the oxide sintered body is hard, penetration of the solid electrolyte by dendrite can be prevented. However, the solid electrolyte has high interface resistance with the electrode material and low battery performance. The reason for the high interfacial resistance between the solid electrolyte and the electrode material is that the two are solid, so that the contact between the two becomes a point contact and there are few ion conduction paths.
- the solid electrolyte in JP 2010-218686 A and JP 2009-23839 A, is made of an oxide sintered body, and the surface portion is made porous.
- the solid electrolyte is also used in an electrolyte secondary battery using an aqueous or non-aqueous electrolyte solution.
- the solid electrolyte is used as a separator that separates the electrodes.
- a solid electrolyte used as a separator in an electrolytic solution secondary battery as disclosed in JP-A-2010-108809, one formed of a hard oxide sintered body and having irregularities formed on the surface was developed. ing.
- dendrite of the electrode component grows by repetition of charge and discharge.
- the hard solid electrolyte as a separator disclosed in Japanese Patent Application Laid-Open No. 2010-108809 can also suppress penetration of dendrite.
- the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a solid electrolyte which can prevent penetration of dendrites of electrode components and has high ion conductivity, and a secondary battery using the same.
- the solid electrolyte of the present invention is a sheet-like solid electrolyte made of an oxide sintered body, and the solid electrolyte is a layered dense portion having a sintered density of 90% or more, and the solid electrolyte It is characterized in that it comprises a porous portion formed continuously with at least one surface of the dense portion on the surface side, and a porous portion having a porosity of 50% or more.
- the secondary battery of the present invention is characterized by having the above-described solid electrolyte, and a positive electrode and a negative electrode which are disposed at opposite positions with the solid electrolyte interposed therebetween.
- a secondary battery according to the present invention comprises a separator comprising the solid electrolyte described above, a positive electrode and a negative electrode disposed at opposite positions sandwiching the separator, and a positive electrode disposed the positive electrode sandwiching the separator. It is characterized by having an electrolytic solution with which at least one side by the side and the negative electrode side which arranged the above-mentioned negative electrode was filled.
- the solid electrolyte of the present invention is made of an oxide sintered body, the dense portion has the above-mentioned predetermined sintered density, and the porous portion has the above-mentioned predetermined porosity. For this reason, penetration of the dendrite of an electrode component can be prevented, and a solid electrolyte with high ion conductivity and a secondary battery using the same can be provided.
- FIG. 6 is a cross-sectional explanatory view of the solid electrolyte of Example 2;
- FIG. 10 is a cross-sectional explanatory view of the solid electrolyte of Example 3;
- FIG. 14 is a cross-sectional explanatory view of the solid electrolyte of Example 4;
- FIG. 14 is a cross-sectional explanatory view of the solid electrolyte of Example 5;
- FIG. 16 is a cross-sectional explanatory view of the solid electrolyte of Example 6.
- FIG. 2 is a cross-sectional explanatory view of the battery 1;
- FIG. 2 is a cross-sectional explanatory view of a comparative battery 1;
- FIG. 2 is a cross-sectional explanatory view of a battery 3;
- Solid electrolyte Since the solid electrolyte is solid and has ion conductivity, it is disposed between the positive electrode and the negative electrode, and exhibits ion conductivity between the positive and negative electrodes.
- the solid electrolyte is made of an oxide sintered body.
- the oxide sintered body is harder than a solid electrolyte made of an organic polymer material. For this reason, even if the electrode component dendrite grows, penetration of dendrite into the solid electrolyte can be prevented. Therefore, there is no fear of a short circuit.
- the oxide sintered body since the oxide sintered body has high water resistance, it can also be used as a separator of a water-based electrolyte solution. Since the oxide sintered body has high heat resistance, it is hard to burn and safe. It can be used stably even under harsh environments.
- the solid electrolyte has a dense portion, and a porous portion formed continuously with at least one surface of the dense portion on the surface side of the solid electrolyte.
- the dense portion extends in the direction perpendicular to the movement direction of the ions, and blocks the dendrite of the electrode component from penetrating the dense portion.
- the cross section of the dense portion may have a planar shape, or may have a shape in which unevenness is repeated. It is preferable to present a shape in which the unevenness is repeated while holding the same thickness, for example, a shape in which zigzag unevenness is repeated in the planar direction on both the front and back while holding the same thickness, both on the front and back There is a shape in which the wavy unevenness is repeated in the planar direction.
- the sintered density of the dense portion is 90% or more. Therefore, the compact portion can block the mass transfer between the front and back while having ion conductivity.
- the solid electrolyte is disposed between the positive electrode and the negative electrode, the movement of substances other than ions can be blocked between the positive and negative electrodes, and a short circuit can be prevented. In addition, penetration of dendrite of the electrode component into the solid electrolyte can be prevented.
- the sintered density of the dense portion is less than 90%, substances other than ions may pass through the dense portion, and the barrier property of mass transfer in the dense portion may be reduced.
- the lower limit of the sintered density of the dense portion is preferably 95%, and more preferably 97%. In this case, the blocking property of the dense portion is further improved.
- the upper limit of the sintered density of the dense part is preferably closer to 100% from the viewpoint of barrier property, but is preferably 95% from the viewpoint of mass productivity.
- the sintered density of the dense portion refers to the ratio (percentage) of the density of the dense portion to the true density of the dense portion.
- the open porosity of the dense portion is preferably 5% or less, and more preferably 3% or less. In this case, mass transfer other than ions between the front and back of the dense part can be effectively suppressed.
- the open porosity of the dense portion refers to the ratio (percentage) of the volume of open pores in the dense portion to the total volume of the dense portion.
- the open pore in the dense portion is a hole formed in the dense portion and refers to a hole communicating with the outside of the dense portion.
- the thickness of the dense portion is preferably 1 ⁇ m to 1000 ⁇ m, and more preferably 10 ⁇ m to 100 ⁇ m. In this case, the ion conduction speed can be increased while preventing penetration of the dendrite of the electrode component, and the battery capacity can be increased.
- the ratio of the thickness of the dense portion to the total thickness of the solid electrolyte is preferably 5% to 95%, and more preferably 10% to 90%. In this case, the thickness of the dense portion can be reduced while maintaining the thickness of the porous portion sufficiently. Therefore, the ion conduction speed can be increased, and the battery output is increased.
- the porous portion may be formed on one of the surface and the back surface of the dense portion.
- the porous portion may be formed on both the front and back sides of the dense portion.
- the thickness of the porous portion may be different on the front and back sides.
- a large number of pores are formed in the porous portion.
- the porosity of the porous portion is 50% or more.
- the pores of the porous portion can be ion conduction paths.
- the porosity of the porous portion is 50% or more, a large number of holes are formed in the porous portion, and the number of ion conduction paths is increased. Therefore, the battery capacity is increased.
- the porosity of the porous portion is less than 50%, the battery capacity may be reduced.
- the lower limit of the porosity of the porous portion is preferably 70%, and more preferably 80%. In this case, the number of ion conduction paths is further increased, and the battery capacity is further increased.
- the upper limit of the porosity of the porous portion is preferably 95%, and more preferably 90%, from the viewpoint of maintaining the strength of the porous portion.
- the porosity of the porous portion refers to the ratio of the volume of all the pores formed in the porous portion to the total volume of the porous portion. All the pores include not only open pores open to the outside of the porous part but also closed air bubbles sealed inside the porous part and not open to the outside.
- the porous portion preferably has open pores open to the outside of the porous portion.
- the open porosity of the porous portion is preferably 50% or more.
- the open porosity of the porous portion refers to the ratio of the volume of open pores open to the outside of the porous portion to the total volume of the porous portion.
- the lower limit of the open porosity of the porous portion is preferably 60%, and more preferably 70%. In this case, the battery capacity is further increased.
- the upper limit of the open porosity of the porous portion is preferably 95%, and more preferably 90%, from the viewpoint of maintaining the strength of the porous portion.
- the ratio of the open porosity to the porosity of the porous portion is preferably 60% to 100%, and more preferably 70% to 100%, and 80% to 100%. In this case, most of the pores formed in the porous portion become open pores. For this reason, when the electrode active material is coated on the surface of the porous portion, the electrode active material easily enters the porous portion, and the contact area between the electrode material and the solid electrolyte is further increased. In addition, in the electrolytic solution secondary battery, the electrolytic solution easily intrudes into the porous portion, and it becomes easy to insert and extract ions. Therefore, the battery capacity is further increased.
- the average depth L (see FIG. 1) of the open pores of the porous portion is preferably 0.1 ⁇ m to 500 ⁇ m, and more preferably 1 ⁇ m to 100 ⁇ m.
- the average depth L refers to the average value of the length in the thickness direction from the open end of the open pore opened to the outside of the porous portion to the bottom.
- the average opening diameter D (see FIG. 1) of the open pores of the porous portion is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 50 ⁇ m.
- the average opening diameter D of the open pores of the porous portion refers to the average value of the diameters of the largest perfect circles that fit in the open ends of the open pores opened to the outside of the porous portion.
- the electrode active material when the electrode active material is coated on the surface of the porous portion, the electrode active material can easily enter the inside of the porous portion, and the contact area between the electrode material and the solid electrolyte can be increased.
- the penetration speed of the electrolyte into the porous portion is increased.
- the porosity of the porous portion may be constant in the thickness direction, but may be changed in the thickness direction.
- the porosity of the surface layer portion of the porous portion may be larger than the porosity of the inner portion of the porous portion.
- the surface layer portion of the porous portion is the surface layer portion opposite to the dense portion in the porous portion, and the inner portion of the porous portion is the dense portion side in the porous portion.
- the open porosity of the porous portion may be constant in the thickness direction, but may be changed in the thickness direction.
- the open porosity of the surface layer part of the porous part may be larger than the open porosity of the inner part of the porous part.
- the electrode active material easily enters from the surface layer portion of the porous portion, and the contact area between the electrode material and the solid electrolyte further increases.
- the electrolyte can easily permeate into the porous portion.
- the thickness of the porous portion is preferably 0.1 ⁇ m or more and 500 ⁇ m or less, and more preferably 1 ⁇ m or more and 100 ⁇ m or less.
- the contact area between the solid electrolyte and the electrode active material can be sufficiently increased while the thickness of the solid electrolyte is reduced, and the contact resistance between the solid electrolyte and the electrode active material is significantly reduced.
- the chance of contact between the electrolyte and the solid electrolyte is increased, and the storage and release of ions are facilitated.
- the ratio of the thickness of the porous portion to the thickness of the dense portion preferably exceeds 0.1 and does not exceed 5. In this case, the balance between the thickness of the dense portion and the thickness of the porous portion is good.
- the penetration of the dendrite of the electrode component is surely prevented in the dense portion, and many ion conduction paths can be formed in the porous portion, whereby the battery capacity can be increased and the output can be increased.
- the thickness of the porous portion means the thickness of the porous portion formed on one side, and the porous portion is formed on both the front and back sides of the dense portion. When a part is formed, the thickness of each porous part is said.
- the total thickness of the solid electrolyte is preferably 2000 ⁇ m or less, more preferably 1000 ⁇ m or less, still more preferably 400 ⁇ m or less, and most preferably 100 ⁇ m or less. In this case, the battery can be miniaturized.
- the lower limit of the total thickness of the solid electrolyte is preferably 50 ⁇ m, more preferably 20 ⁇ m, and still more preferably 10 ⁇ m. In this case, many ion conduction paths can be secured in the porous portion, and penetration of dendrite can be effectively prevented in the dense portion. If the total thickness of the solid electrolyte is less than 10 ⁇ m, the handling (handling property) becomes difficult, and the amount by which the porous portion can be filled with the active material is small, and the capacity may be reduced.
- the oxide sintered body constituting the solid electrolyte has, for example, a crystal structure of garnet type, perovskite type, NASICON type, ⁇ ′ ′-Al 2 O 3 type, ⁇ ′ ′-Al 2 O 3 type. Among these, it is particularly preferable to have a garnet-type crystal structure.
- the crystal structure of the oxide sintered body is, for example, garnet-type Li 7 La 3 Zr 2 O 12 (LLZ), garnet-type Li 5 La 3 (Nb, Ta) 2 O 12 , garnet-type Li 6 BaLa 2 Ta 2 O 12 , Perovskite-type Li x La 2-x / 3 TiO 3 (0 ⁇ x ⁇ 0.5) (LTT), NASICON-type Li 1 + x + y (Al, Ga) x (Ti, Ge, Zr) 2- x Si y P 3-y O 12 (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3) Ti-based one is LATP, Ge-based one LAGP), ⁇ ′ ′-Al 2 O 3 type Li 2 O ⁇ It is preferable to use 5 Al 2 O 3 , ⁇ ′-Al 2 O 3 type Li 2 O ⁇ 11 Al 2 O 3 , Li 4 SiO 4 .
- LAGP garnet-type LLZ
- garnet-type Li 5 La 3 (Nb, Ta) 2 O 12 garnet-type Li 6 BaLa 2 Ta 2 O 12 are preferable. They have high ion conductivity at room temperature, for example, they do not react at the potential of Li and have high electrochemical stability.
- a method of manufacturing a solid electrolyte will be described.
- a solid electrolyte powder consisting of a solid electrolyte is synthesized by, for example, a solid phase method, a coprecipitation method, a hydrothermal method, a glass crystallization method, a sol gel method, or the like.
- the solid electrolyte powder is used to form a compact portion and a porous portion.
- (1-1) Slurry the solid electrolyte powder with an organic solvent or water. If necessary, a binder may be further added to the solid electrolyte powder.
- the slurry is formed into a desired shape by using a doctor blade or a roll coater, screen printing or cast molding. After shaping, the shaped body is dried and sintered.
- the compact may be sintered after being pressed by CIP (cold isostatic pressing), WIP (hot water isostatic pressing), hot press or the like. In sintering the formed body, it is preferable to carry out HIP (hot isostatic pressing) or to sinter under vacuum conditions. Thereby, the sintered density of the dense part can be increased, and the porosity of the dense part can be reduced.
- the solid electrolyte powder is formed into a pellet or sheet shape by a hand press or the like. If necessary, a binder may be added to the solid electrolyte powder. Sinter the compact.
- the compact may be sintered after CIP, WIP or hot pressing. At the time of sintering, it is preferable to sandwich and sinter with a setter such as quartz glass, perform HIP or SPS (discharge plasma sintering), or sinter under vacuum conditions. Thereby, the sintered density of the dense part becomes high.
- the shape of the dense portion is a flat surface by making the surface of the mold, the press die, and the coated substrate the shape of the dense portion. , And a desired shape such as an uneven surface.
- the porous portion is formed on one side or both sides of the dense portion, for example, by any of the following methods (2-1) to (2-13) Form
- the slurry may be mixed with a binder.
- the slurry is cast in the interstices of the beads using the beads made of a polymer material as a template. This is fired to remove pores, thereby forming pores and sintering the solid electrolyte.
- Foaming is performed by mixing solid electrolyte powder with a precursor of an organic material that solidifies in a foamed shape, such as foamed polystyrene such as expanded polystyrene, foamed urethane, carmage, and solidified in that shape, and heats it. Let The foam is then fired to remove organics. As a result, holes are formed and the solid electrolyte is sintered.
- foamed polystyrene such as expanded polystyrene, foamed urethane, carmage
- the slurry may be mixed with a binder.
- the slurry is shaped and freeze dried. By lyophilization, the liquids in the slurry become frozen in a state of being aggregated with one another. By drying the frozen body, a hole is formed at the place where the frozen body was present. In this method, longitudinal open pores extending in the thickness direction of the porous portion are easily formed. After drying, it is fired to sinter the solid electrolyte.
- the porosity gradient in the thickness direction of the porous portion is made by adjusting the conditions of lyophilization of the formed body, it is possible to make the porosity gradient in the thickness direction of the porous portion or maintain the porosity at a constant porosity in the thickness direction.
- a porous portion having a constant porosity is formed in the thickness direction.
- the porosity of the surface layer of the porous part is large, and the porosity inside the porous part is small.
- a solid electrolyte is prepared by a sol-gel method, and micron-sized pores are formed by hydrolysis with a basic substance. Thereafter, the solid electrolyte is dried to remove by-product water and organic solvents, and sintered.
- Water or an organic solvent is added to the solid electrolyte powder to make a slurry.
- the slurry may be mixed with a binder.
- the slurry is impregnated into a porous resin body used for a sponge or a battery separator, dried and sintered. Thereby, the porous resin body is removed, and pores are formed between the solid electrolytes.
- the diameter of the pores is often slightly larger than several tens of ⁇ m.
- a thick film of a solid electrolyte is formed by a sol-gel method. It is preferable to perform film formation by dip or spin. Further, instead of performing heat treatment every film formation, film formation may be repeated to form a thick film and then heat treatment may be performed to form a thick film. The formed gel is freeze-dried and then sintered.
- the porosity gradient in the thickness direction of the porous portion is made by adjusting the conditions of lyophilization of the formed body, it is possible to make the porosity gradient in the thickness direction of the porous portion or maintain the porosity at a constant porosity in the thickness direction.
- a porous portion having a constant porosity is formed in the thickness direction.
- the porosity of the surface layer of the porous part is large, and the porosity inside the porous part is small.
- the kneaded product obtained by mixing and solidifying the solid electrolyte and the ultraviolet curing resin is formed into a sheet on the surface of the dense portion.
- drawing and etching are performed on the sheet-like kneaded material by lithography, only the irradiation part irradiated with light by lithography remains. Thereafter, the solid electrolyte is sintered.
- the porous portion is formed by mixing solid electrolyte powder particles and an electrode active material, applying the mixture on the surface of the dense portion, and baking it.
- the solid electrolyte powder particles are dispersed among the electrode active materials. Between the respective particles, it is preferable to form a substantially porous solid electrolyte layer by leaving a predetermined interval and containing an electrode active material therebetween.
- the plurality of solid electrolyte powder particles may be deposited in the thickness direction of the solid electrolyte.
- the diameter M (see FIG. 5) of the solid electrolyte powder particles is preferably 0.1 ⁇ m or more and 20 ⁇ m or less.
- the average opening diameter D of the gaps between the solid electrolyte powder particles is preferably 1 ⁇ m or more and 25 ⁇ m or less.
- the solid electrolyte by forming the dense portion and the porous portion, respectively, and stacking and sintering the two.
- a press, a doctor blade, a roll coater, screen printing or the like is performed.
- adhesion may be enhanced by various presses, CIP, WIP, hot press or the like, or an adhesive such as a binder may be used.
- Water or an organic solvent is added to the solid electrolyte powder to make a slurry.
- the slurry may be mixed with a binder.
- the slurry is molded in a porous mold.
- the shaped body is dried through the pores of the mold. At this time, the drying conditions are adjusted so that the moisture content of the green dry molded body is graded in the thickness direction. It cools from the one where water content is large, and lyophilizes. Thereby, the porosity of the molded body is graded in the thickness direction.
- the compact is then sintered to form a porous section with graded porosity.
- the slurry of the solid electrolyte powder is molded with a compact mold. Only one side of the shaped body is dried and the moisture content is graded. Cooling from a high water content and freeze-drying forms a gradient in the porosity of the shaped body. The compact is sintered to form a porous portion with graded porosity.
- Polymer microbeads are mixed with a slurry of solid electrolyte, shaped by doctor blade, roll coater, screen printing or the like, and dried. When the mixing ratio of microbeads and the particle size are changed and coating is repeated, a gradient is formed in the porosity of the compact. Thereafter, when the compact is sintered, porous portions with graded porosity are formed.
- the porosity can be determined, for example, by observing a cross section (a fracture surface, a CP processed surface, etc.) with a SEM (scanning electron microscope) or the like, and the open porosity is, for example, a bulk density and a sintered density obtained by Archimedes method or the like. It can be calculated from
- the ion conductor of the secondary battery using the above-mentioned solid electrolyte is, for example, lithium ion.
- the lithium ion is an ion conductor
- the secondary battery is, for example, a lithium secondary battery in which the negative electrode is lithium, a Li / Air battery in which the negative electrode is lithium, an oxygen in positive electrode, a lithium water battery in which the negative electrode is lithium and the positive electrode is water.
- lithium dendrite is easily generated on the negative electrode surface.
- a lithium negative electrode but also in the case of using a negative electrode made of a carbon material, a lithium-containing compound, tin or silicon and an alloy thereof, dendrite may be formed due to the balance of positive and negative electrodes or overdischarge.
- the secondary battery includes the solid electrolyte, and a positive electrode and a negative electrode disposed at opposite positions with the solid electrolyte interposed therebetween.
- This secondary battery is an all solid secondary battery. All solid secondary batteries have a large capacity. In addition, the safety is high because the organic electrolytic solution is not used.
- the positive electrode is made of a positive electrode material.
- the positive electrode material is made of, for example, a metal plate such as copper, silver, gold, iron, nickel or the like.
- the positive electrode material may be composed of an electrode active material for the positive electrode and a current collector coated with the electrode active material for the positive electrode.
- an electrode active material for the positive electrode for example, a metal complex oxide of lithium and a transition metal such as lithium-manganese complex oxide, lithium-cobalt complex oxide, lithium-nickel complex oxide, etc. is used. Specifically, LiCoO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , Li 2 MnO 3 and the like can be mentioned.
- the electrode active material for the positive electrode it is also possible to use elemental sulfur, a sulfur-modified compound, oxygen, water and the like.
- the current collector for the positive electrode may be any one generally used for a positive electrode of a lithium ion secondary battery, such as aluminum, nickel, stainless steel, etc., and may have various shapes such as mesh or metal foil.
- the negative electrode is made of a negative electrode material.
- the negative electrode material is made of, for example, a metal plate of lithium, tin, magnesium, calcium, aluminum, indium or the like.
- the negative electrode material may be composed of an electrode active material for the negative electrode and a current collector coated with the electrode active material for the negative electrode.
- the electrode active material for the negative electrode is made of an element material which is capable of absorbing and desorbing lithium ions and which is an element capable of alloying reaction with lithium and / or an element compound having an element capable of alloying reaction with lithium.
- the electrode active material for the negative electrode may contain a carbon material together with the element material or the element compound. Alternatively, in place of the elemental material or the elemental compound, a carbon material may be included.
- a carbon material as an electrode active material for a positive electrode for example, graphite such as natural graphite or artificial graphite, or carbon nanotube may be used.
- the elemental materials are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn, Pb, Sb It is preferable that the material is at least one selected from the group consisting of and Bi. Among them, silicon (Si) or tin (Sn) is preferable.
- the elemental compound may be a compound having the material. Among them, silicon compounds or tin compounds are preferable.
- the silicon compound may be SiO x (0.5 ⁇ x ⁇ 1.5). Examples of tin compounds include tin alloys (Cu-Sn alloy, Co-Sn alloy, etc.).
- any electrode active material for positive electrode and negative electrode may be applied to the surface of the current collector, it is preferable to apply to the porous portion of the solid electrolyte. This is because the electrode active material enters the porous portion, the contact area between the solid electrolyte and the electrode active material is increased, and the separation of the electrode active material from the solid electrolyte can be prevented.
- the secondary battery includes a separator made of a solid electrolyte, a positive electrode and a negative electrode disposed at opposite positions sandwiching the separator, and a positive electrode side and the negative electrode disposed the positive electrode sandwiching the separator. And an electrolytic solution filled in at least one of the arranged negative electrode sides.
- This secondary battery is an electrolytic solution secondary battery.
- the negative electrode material used for the negative electrode is, for example, a metal plate.
- a material of the metal plate as the negative electrode material for example, lithium (Li), sodium (Na), magnesium (Mg), calcium (Ca), aluminum (Al), potassium (K), strontium (Sr), barium ( Metals or alloys such as Ba) can be used.
- the positive electrode material used for the positive electrode is, for example, a metal plate.
- the metal plate as a positive electrode material can use metals or alloys, such as copper, iron, nickel, silver, gold
- the negative electrode material may be composed of a current collector for the negative electrode and an electrode active material for the negative electrode covering the surface of the current collector.
- the positive electrode material may be composed of a current collector plate for the positive electrode and an electrode active material for the positive electrode covering the surface of the current collector.
- the electrode active material for the negative electrode and the negative electrode may be, for example, the electrode active material for the negative electrode and the positive electrode described in the above (1).
- an electrode active material may be apply
- An electrolytic solution is filled in at least one of the positive electrode side and the negative electrode side across the separator.
- the electrolytic solution may be filled on the positive electrode side, may be filled on the negative electrode side, or may be filled on both the positive electrode side and the negative electrode side.
- an electrolytic solution for the negative electrode and an electrolytic solution for the positive electrode any of an organic electrolytic solution, an aqueous solution of water and an electrolytic solution of an ionic liquid can be used. Which electrolyte is used depends on the types of negative electrode material and positive electrode material.
- the electrolyte may be an organic electrolyte or an ionic liquid.
- the organic electrolyte refers to an electrolyte comprising an electrolyte and an organic solvent.
- both the front and back sides of the solid electrolyte may be porous portions. Since the surface area of the porous portion is large, the absorption and release of ions can be efficiently performed, and high output can be achieved.
- these electrode active materials may be filled in the pores of the porous portion of the solid electrolyte .
- the contact area between the electrode active material and the solid electrolyte can be increased, and the contact resistance between the electrode active material and the solid electrolyte can be lowered.
- the electrode active material since the electrode active material is in the porous portion, the electrode active material does not peel off from the solid electrolyte.
- the shape of the secondary battery is not particularly limited, and various shapes such as cylindrical, laminated, coin, and laminate types can be adopted.
- the secondary battery may be mounted on a vehicle. By driving the traveling motor with the above secondary battery, it can be used with a large capacity and a large output.
- the vehicle may be a vehicle using electric energy from a secondary battery in all or part of its power source, and may be, for example, an electric vehicle or a hybrid vehicle.
- a secondary battery When a secondary battery is mounted on a vehicle, a plurality of secondary batteries may be connected in series to form a battery pack.
- various household appliances driven by batteries such as personal computers and mobile communication devices, office devices, and industrial devices can be mentioned.
- the solid electrolyte 3 of the present example comprises a dense portion 1 and a porous portion 2 formed continuously on the surface side of the solid electrolyte 3 with one surface of the dense portion 1.
- the dense portion 1 has a planar shape.
- the sintered density of the dense part 1 is 98%.
- the open porosity of the dense portion 1 is less than 1%.
- the thickness of the dense portion 1 is about 50 ⁇ m.
- the ratio of the thickness of the dense portion 1 to the total thickness of the solid electrolyte 3 is 25%.
- the porosity of the porous portion 2 is 80%, and the open porosity of the porous portion 2 is 75%.
- the ratio of the open porosity of the porous portion 2 to the porosity of the porous portion 2 is 94%.
- the average opening diameter D of the open pores 20 opened on the surface of the porous portion 1 is 50 ⁇ m.
- the average depth L of the open pores 20 is 48 ⁇ m.
- the thickness of the porous portion 2 is about 100 ⁇ m.
- the ratio of the thickness of the porous portion 2 to the thickness of the dense portion 1 is 2.
- the oxide sintered body constituting the solid electrolyte is a lithium ion conductor.
- the dense portion 1 is a garnet-type Li 7 La 3 Zr 2 O 12 (LLZ).
- the dense portion 1 is formed.
- a solid electrolyte powder (diameter 1 ⁇ m) made of LLZ is formed by a solid phase method. Water is added to the powder to form a slurry, which is formed into a sheet by a doctor blade method. The shaped body is dried and calcined at 1150 ° C.
- the porous portion 2 is formed on the surface of the dense portion 1.
- water is added to the solid electrolyte powder consisting of LLZ used in the dense part 1 to form a slurry.
- the slurry is applied to one side of the dense part 1 to form a porous formed part. Lyophilization is carried out while maintaining the planar direction of the porous formed part in the horizontal direction. The freezing temperature was -40.degree. Liquid nitrogen was used in the cold trap (freeze collection). After lyophilization, it is calcined at 1100 ° C.
- Example 2 In the solid electrolyte 3 of this example, as shown in FIG. 2, the porous portion 2 is formed on both the front and back sides of the dense portion 1.
- the thickness of the dense portion 1 is 50 ⁇ m, and the thickness of each porous portion 2 is 100 ⁇ m.
- the ratio of the thickness of the dense portion 1 to the total thickness of the solid electrolyte 3 is 20%.
- a slurry of a solid electrolyte is applied to both the front and back sides of the dense portion 1, freeze-dried, and fired. Others are the same as in the first embodiment.
- the porosity of the porous portion 2 has a gradient in the thickness direction.
- the porosity of the porous portion 2 is 80% in the surface layer portion 2a and gradually decreases toward the inside, and the porosity in the inside 2b near the dense portion 1 in the porous portion 2 is approximately 0%.
- a slurry of a solid electrolyte is applied to the surface of the dense portion 1 as in FIG. 1, freeze-dried and fired.
- a cooling medium was placed on the top of the molded body, and the molded body was cooled with a temperature gradient. Others are the same as in the first embodiment.
- the thickness (50 ⁇ m) of the porous portion 2 ′ formed on the surface of the dense portion 1 is the thickness of the porous portion 2 ′ ′ formed on the back surface of the dense portion 1.
- the thickness of the dense portion 1 is 50 ⁇ m, and the ratio of the thickness of the dense portion 1 to the total thickness of the solid electrolyte 3 is 25%.
- the porosity of the thick porous portion 2 ' is larger in the surface portion than in the inside, as in the porous portion 2 of the third embodiment.
- the porosity of the thin porous portion 2 ′ ′ is substantially the same in the thickness direction as in the porous portion of the first embodiment. The other respects are the same as those of the second embodiment.
- Example 5 In the solid electrolyte 3 of this example, as shown in FIG. 5, the porous portion 2 is formed only on the surface of the dense portion 1.
- the porous portion 2 is composed of secondary particles 22 of solid electrolyte powder and gaps 23 formed between the secondary particles 22.
- the diameter M of the secondary particles 22 is 10 ⁇ m.
- the average opening diameter D of the gap 23 between the secondary particles 22 is 25 ⁇ m.
- the dense portion 1 is formed in the same manner as in Example 1, particles made of LLZ are synthesized by a solid phase method, and this is pulverized using a ball mill at 300 rpm to form secondary particles 22 with uniform particle diameter.
- natural graphite powder (diameter 5 ⁇ m) is prepared as an active material powder for a negative electrode. Secondary particles 22 of LLZ and natural graphite powder are mixed in an amount of 3: 1 (volume ratio), water is added to this to form a slurry. The slurry is applied to the surface of the dense part 1, dried and fired. Thereby, the porous portion 2 is formed on the surface of the dense portion 1.
- Example 6 In the solid electrolyte of the present example, as shown in FIG. 6, the dense portion 1 spreads in the planar direction while repeating unevenness in a zigzag manner in the thickness direction of the solid electrolyte.
- the porous portion 2 is formed on both the front and back sides of the dense portion 1.
- the porous portion 2 is formed not only on the peak portion 1 a but also on the front surface of the valley portion 1 b and the slope portion 1 c on both the front and back sides of the dense portion 1.
- the surface of the porous portion 2 has irregularities along the shape of the dense portion 1.
- the unevenness difference of the dense portion 1 is 20 ⁇ m, the thickness of the dense portion 1 is 50 ⁇ m, and the pitch of the unevenness is 25 ⁇ m.
- the sintered density of the dense portion 1 is 98%, and the open porosity of the dense portion 1 is 1%.
- the open porosity here is the ratio of open pores on the surface of the uneven surface formed by the mold.
- the porosity of the porous portion 2 is 83%.
- the open porosity of the porous portion 2 is 80%.
- the thickness of the porous portion 2 is 100 ⁇ m.
- the slurry of the LLZ powder is shaped by pressing it with a press die having a zigzag surface, and is then dried and fired.
- the formation of the porous part 2 is the same as in Example 1.
- the solid electrolyte 3 of the present reference example includes only the dense portion 1 in which the unevenness is repeated in a zigzag in the thickness direction of the solid electrolyte. Due to the unevenness of the dense portion 1, the hole 11 is formed between the dense portion 1.
- the overall shape of the solid electrolyte 3 is such that the hole 11 is formed between the dense portions 1.
- the unevenness difference of the dense portion 1 is 20 ⁇ m, the thickness of the dense portion 1 is 50 ⁇ m, and the pitch of the unevenness is 25 ⁇ m.
- the sintered density of the dense portion 1 is 98%, and the open porosity of the dense portion 1 is 98%.
- the open porosity of the porous portion 2 is 50%.
- the dense portion 1 is formed in the same manner as the dense portion 1 of the sixth embodiment.
- the solid electrolyte of this comparative example consists only of a planar dense portion.
- the solid electrolyte has the same configuration as that of the dense part of Example 1.
- the thickness of the solid electrolyte is 50 ⁇ m.
- Electrode active material 41 for the positive electrode is coated on the surface of the porous portion 2 of the solid electrolyte 3 of Example 1 with a doctor blade.
- the slurry of the electrode active material 41 for the positive electrode contains a powder (diameter 5 ⁇ m) of LiCoO 2 , a conductive additive, and a binder.
- the electrode active material 41 penetrates into the open pores 20 of the porous portion 2 and the peeling from the solid electrolyte 3 is prevented. After coating, the electrode active material is dried and sintered.
- the current collector 40 for the positive electrode is made to face the surface of the porous part 2 of the solid electrolyte 3, and the metal plate 5 for the negative electrode is made to face the surface of the dense part 1 of the solid electrolyte 3.
- the current collector 40 for the positive electrode is a metal sputtered film made of Pt, and the metal plate 5 for the negative electrode is made of Li. These are housed in a case and sealed.
- the solid electrolyte 3 of Example 1 is an oxide sintered body made of LLZ, and thus is harder than a solid electrolyte made of an organic polymer material. Therefore, penetration of dendrite can be prevented even if lithium dendrite is generated by repetition of charge and discharge. Therefore, there is no risk of battery short circuit. Since the oxide sintered body has high heat resistance, it is hard to burn and safe. It can be used stably even under harsh environments.
- the sintered density of the dense portion 1 is very high, the movement of substances other than lithium ions is blocked. Therefore, a battery short circuit can be suppressed.
- the porosity of the porous part 2 is high, the surface area of the porous part 2 becomes high, and lithium ions can be efficiently stored and released.
- the porous portion 2 has a high porosity. Therefore, the number of ion conduction paths is increased. Further, the electrode active material 41 enters the porous portion 2, the contact area between the solid electrolyte 3 and the electrode active material 41 is large, and the contact resistance between the solid electrolyte 3 and the electrode active material 41 can be reduced. In addition, peeling of the electrode active material 41 from the solid electrolyte 3 can be prevented. Thus, the capacity of the battery is increased.
- Comparative battery 1 An all solid secondary battery is manufactured using the solid electrolyte of the comparative example. As shown in FIG. 9, a slurry of the electrode active material 41 for the positive electrode is applied to one surface of the solid electrolyte 3 with a doctor blade. Since the electrode active material 41 is formed only of the flat portion 1, the electrode active material 41 is coated in a layer on one surface of the solid electrolyte 3. Thereafter, the current collector 40 for the positive electrode is disposed on the side to which the electrode active material 41 of the solid electrolyte 3 is applied, and the metal plate 5 for the negative electrode is disposed on the opposite side. Others are the same as the battery 1.
- the solid electrolyte of the comparative example is composed of only a planar dense portion. For this reason, penetration of dendrite of lithium ion can be prevented.
- the solid electrolyte 3 of the comparative example is formed of only the flat portion 1, the contact area between the electrode active material 41 and the solid electrolyte 3 is small, and the battery capacity is small.
- This battery is an electrolytic solution secondary battery using the solid electrolyte of Example 1.
- an electrolytic solution on the positive electrode side was added to the configuration of the battery 1 shown in FIG.
- the electrolytic solution on the positive electrode side permeates the porous portion 2 of the solid electrolyte 3. In the porous portion 2 having a large porosity, the contact between the electrolytic solution and the solid electrolyte is frequent, and the absorption and release of ions are actively performed. Therefore, the output of the battery is high.
- the present comparative battery is an electrolytic solution secondary battery using the solid electrolyte of the comparative example as a separator.
- an electrolytic solution is added to the positive electrode side in the configuration of the comparative battery 1 shown in FIG.
- the electrolytic solution is similar to that of the battery 2.
- the solid electrolyte since the solid electrolyte consists only of the planar dense portion 1, the surface area of the solid electrolyte is smaller and the lithium ion absorption and release are smaller compared to the solid electrolyte of Example 1 having the porous portion. Therefore, the battery output is also small.
- An electrolyte secondary battery (Li / Air battery) is manufactured using the solid electrolyte of Example 1.
- a metal plate 5 made of lithium metal is disposed on the surface of the dense portion 1 of the solid electrolyte 3 of Example 1 as a negative electrode.
- a carbon nanotube 43 is supported as a positive electrode active material, and a metal plate 44 is disposed as a current collector.
- the metal plate 44 is a metal mesh. These are placed in a case with a hole in the positive electrode side, and sealed so that Li does not touch the air.
- the solid electrolyte 3 is formed of a hard oxide sintered body, penetration of lithium dendrite can be prevented.
- the sintered density of the dense portion 1 is very high, it is possible to block the transfer of substances other than lithium ions.
- the porous part 2 has a high porosity, the reaction area is large, the performance decrease due to the precipitation of the reaction product Li 2 O 2 is small, the lithium ion is easily absorbed and released, and the lithium ion conduction path Will increase. Therefore, the battery capacity is increased, and the output of the battery can be increased.
- the solid electrolyte 3 of Example 5 can be manufactured by a simple method and is excellent in mass productivity.
- the dense portion 1 since the dense portion 1 exhibits a zigzag uneven shape, it can form a larger number of ion conduction paths as compared with the dense portion 1 which spreads like a flat like other solid electrolytes. it can. Therefore, the proportion of the active material in the battery configuration can be increased, the capacity is large, and a high output can be exhibited.
- the electrode active material is filled in the porous portion 2 or the electrolyte is allowed to permeate. It is good to It is good for the side of the dense part 1 to face a metal plate as an electrode. In particular, it is preferable that a metal plate made of lithium metal in which dendrite growth is remarkable be made to face the side of the dense portion 1. Penetration of dendrite can be reliably cut off by the dense portion 1.
- the porous portions 2 are formed on both the front and back sides of the dense portion 1 as in Examples 2, 4 and 6, it is preferable to fill the porous portions 2 on both sides with the electrode active material.
- the electrode active material gets into the large number of pores formed in the porous portion 2, so that the contact resistance can be reduced and the peeling of the electrode active material can be prevented.
- the porous portions 2 formed on both the front and back sides of the dense portion 1 as in Examples 2, 4 and 6 the porous portions 2 formed on the front and back sides of the dense portion 1 are used for the positive electrode. And an electrolyte for the negative electrode may be permeated. As a result, the contact opportunity between the electrolyte solution in the electrolyte solution and the solid electrolyte is increased, and the absorption and release of ions are actively performed, the capacity is increased, and a high output can be exhibited.
- the solid electrolyte of the reference example is formed only from the dense part where the uneven shape is repeated. Therefore, the surface area of the solid electrolyte is increased, and the ion conduction path is increased. Therefore, high output of the battery can be achieved.
- the solid electrolyte of the reference example is also made of the oxide sintered body, penetration of lithium dendrite can be prevented.
- Lithium used as the negative electrode material of the above-mentioned secondary battery can be replaced with, for example, sodium, magnesium, calcium, aluminum or the like to make a battery.
Abstract
Description
固体電解質は固体でイオン伝導性を有するため、正極と負極の間に配置されて、正負極間でイオン伝導性を発揮する。
上記固体電解質を用いた二次電池のイオン伝導体は、例えば、リチウムイオンである。リチウムイオンがイオン伝導体である二次電池において、負極がリチウム金属又はリチウム合金からなる場合はリチウム二次電池といわれ、負極がそれ以外の負極材料からなる場合はリチウムイオン二次電池といわれる。
本例の固体電解質3は、図1に示すように、緻密部1と、固体電解質3の表面側に緻密部1の一方の表面と連続して形成された多孔質部2とからなる。緻密部1は、平面形状である。緻密部1の焼結密度は98%である。緻密部1の開気孔率は1%未満である。緻密部1の厚みは、約50μmである。固体電解質3の全体厚みに対する緻密部1の厚みの比率は25%である。
本例の固体電解質3では、図2に示すように、緻密部1の表裏両面に多孔質部2が形成されている。緻密部1の厚みは50μmであり、それぞれの多孔質部2の厚みは100μmである。固体電解質3の全体の厚みに対する緻密部1の厚みの比率は、20%である。緻密部1を形成した後に、固体電解質のスラリーを緻密部1の表裏両面に塗布し、凍結乾燥させ、焼成する。その他は実施例1と同様である。
本例の固体電解質3では、図3に示すように、多孔質部2の気孔率が厚み方向に勾配がある。多孔質部2の気孔率は、表層部2aで、80%であり、内部に向かって徐々に小さくなり、多孔質部2における緻密部1付近の内部2bで気孔率はほぼ0%である。多孔質部2を形成するに当たっては、図1と同様に固体電解質のスラリーを緻密部1の表面に塗布し、凍結乾燥させ、焼成する。凍結乾燥の条件は、成形体上部に冷却媒体を設置し、成形体に温度勾配をつけながら冷却した。その他は、実施例1と同様である。
本例の固体電解質3では、図4に示すように、緻密部1の表面に形成した多孔質部2’の厚み(50μm)が、緻密部1の裏面に形成した多孔質部2”の厚み(100μm)よりも大きい。緻密部1の厚みは50μmとする。固体電解質3の全体の厚みに対する緻密部1の厚みの比率は25%である。
本例の固体電解質3では、図5に示すように、緻密部1の表面にのみ多孔質部2が形成されている。多孔質部2は、固体電解質粉末の二次粒子22と、二次粒子22の間に形成された隙間23とから構成されている。二次粒子22の直径Mは10μmである。二次粒子22間の隙間23の平均開口直径Dは25μmである。
本例の固体電解質では、図6に示すように、緻密部1が固体電解質の厚み方向にジグザグ状に凹凸を繰り返しながら平面方向に広がっている。緻密部1の表裏両面には、多孔質部2が形成されている。多孔質部2は、緻密部1の表裏両面において山部1aだけでなく、谷部1b及び傾斜部1cの前面にも形成されている。多孔質部2の表面は、緻密部1の形状に沿って凹凸を有する。
本参考例の固体電解質3は、図7に示すように、固体電解質の厚み方向にジグザグ状に凹凸を繰り返す緻密部1のみからなる。緻密部1の凹凸により、緻密部1の間に穴部11が形成される。固体電解質3の全体形状は、緻密部1の間に穴部11が形成された形状となる。
本比較例の固体電解質は、平面状の緻密部のみからなる。固体電解質は、実施例1の緻密部と同様の構成である。固体電解質の厚みは50μmである。
上記実施例1の固体電解質を用いて全固体二次電池を製造する。
図8に示すように、上記実施例1の固体電解質3の多孔質部2の表面に、正極用の電極活物質41のスラリーをドクターブレードにより塗工する。正極用の電極活物質41のスラリーは、LiCoO2からなる粉末(直径5μm)と、導電助剤と、バインダとを含む。電極活物質41は、多孔質部2の開放気孔20中に入り込み、固体電解質3からの剥離が防止される。塗工後に、電極活物質を乾燥、焼結させる。
比較例の固体電解質を用いて全固体二次電池を製造する。図9に示すように、固体電解質3の一方の面に、ドクターブレードにより正極用の電極活物質41のスラリーを塗布する。電極活物質41は、平面状の緻密部1のみからなるため、電極活物質41は固体電解質3の一方の面に層状に塗工される。その後、固体電解質3の電極活物質41を塗工した側には正極用の集電体40を配置し、反対側には負極用の金属板5を配置する。その他は、電池1と同様である。
本電池は、実施例1の固体電解質を用いた電解液二次電池である。本電池では、図8に示した上記電池1の構成に、正極側の電解液を追加した。正極側の電解液は、LiPF6からなる電解質と、EC/DEC=1:1(vol)からなる溶媒とからなる。正極側の電解液は、固体電解質3の多孔質部2に浸透させる。気孔率の大きな多孔質部2では電解液と固体電解質との接触機会が多く、イオンの吸蔵及び放出が活発に行われる。ゆえに、電池の出力が高くなる。
本比較電池は、比較例の固体電解質をセパレータとして用いた電解液二次電池である。本比較例電池は、図9に示した比較電池1の構成に、正極側に電解液を追加している。電解液は、電池2と同様である。本比較電池では、固体電解質が平面状の緻密部1のみからなるため、多孔質部を有する実施例1の固体電解質に比べて、固体電解質の表面積が小さく、リチウムイオンの吸蔵及び放出が少ない。ゆえに、電池出力も少ない。
実施例1の固体電解質を用いて電解質二次電池(Li/Air電池)を製造する。図10に示すように、実施例1の固体電解質3の緻密部1の表面に、負極としてリチウム金属からなる金属板5を配置する。実施例1の固体電解質3の多孔質部2の表面には、正極活物質としてカーボンナノチューブ43を担持させ、集電体として金属板44を配置する。本実施例において金属板44は金属メッシュである。これらを正極側に穴を開けたケースに入れ、Liが大気に触れないようシールする。
実施例2~6の固体電解質を用いて上記電池1~2を製造した場合にも、実施例1と同様に、リチウムのデンドライトの貫通を防止でき、且つ高い電池容量を発揮できた。
Claims (16)
- 酸化物焼結体よりなるシート状の固体電解質であって、
前記固体電解質は、焼結密度が90%以上である層状の緻密部と、前記固体電解質の表面側に前記緻密部の少なくとも一方の表面と連続して形成された気孔率が50%以上の多孔質部とからなることを特徴とする固体電解質。 - 前記多孔質部の開気孔率は、50%以上である請求項1記載の固体電解質。
- 前記緻密部の開気孔率は5%以下である請求項1又は2に記載の固体電解質。
- 前記緻密部の厚みは、1μm以上1000μm以下である請求項1~3のいずれか1項に記載の固体電解質。
- 前記固体電解質の全体の厚みに対する前記緻密部の厚みの比率は5%以上95%以下である請求項1~4のいずれか1項に記載の固体電解質。
- 前記多孔質部の厚みは0.1μm以上500μm以下である請求項1~5のいずれか1項に記載の固体電解質。
- 前記酸化物焼結体は、リチウムイオン伝導体である請求項1~6のいずれか1項に記載の固体電解質。
- 前記酸化物焼結体の結晶構造はガーネット型である請求項1~7のいずれか1項に記載の固体電解質。
- 前記多孔質部の表層部の気孔率は、前記多孔質部の内部の気孔率よりも大きい請求項1~8のいずれか1項に記載の固体電解質。
- 前記多孔質部は、固体電解質粉末粒子と電極活物質とを混合し、前記緻密部表面に塗布し、焼成させることにより形成され、前記固体電解質粉末粒子が前記電極活物質間で分散してなる請求項1~9のいずれか1項に記載の固体電解質。
- 前記緻密部の断面が凹凸を繰り返す形状である請求項1~10のいずれか1項に記載の固体電解質。
- 焼結密度が90%以上の酸化物焼結体よりなる固体電解質であって、
前記固体電解質は、断面が凹凸を繰り返す形状をもつことを特徴とする固体電解質。 - 請求項1~12のいずれか1項に記載の固体電解質と、前記固体電解質を挟んで相対する位置に配置された正極及び負極とを有することを特徴とする二次電池。
- 請求項1~12のいずれか1項に記載の固体電解質からなるセパレータと、前記セパレータを挟んで相対する位置に配置された正極及び負極と、前記セパレータを挟んで前記正極を配置した正極側及び前記負極を配置した負極側の少なくとも一方に充填された電解液とを有することを特徴とする二次電池。
- 前記負極は、リチウム金属からなる請求項13又は14に記載の二次電池。
- 前記正極及び前記負極の少なくとも一方は、電極活物質を有し、前記電極活物質は、前記固体電解質の前記多孔質部に形成された孔内に入り込んでいる請求項13~15のいずれか1項に記載の二次電池。
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CN104272518B (zh) | 2016-10-19 |
JP2013232284A (ja) | 2013-11-14 |
JP5447578B2 (ja) | 2014-03-19 |
CN104272518A (zh) | 2015-01-07 |
DE112013002219T5 (de) | 2015-01-15 |
US20150111110A1 (en) | 2015-04-23 |
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