JP2010097812A - Method for manufacturing solid battery - Google Patents

Method for manufacturing solid battery Download PDF

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JP2010097812A
JP2010097812A JP2008267504A JP2008267504A JP2010097812A JP 2010097812 A JP2010097812 A JP 2010097812A JP 2008267504 A JP2008267504 A JP 2008267504A JP 2008267504 A JP2008267504 A JP 2008267504A JP 2010097812 A JP2010097812 A JP 2010097812A
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glass
sulfide glass
positive electrode
negative electrode
layer
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JP5255979B2 (en
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Akitoshi Hayashi
Kenji Kimura
Masahiro Tatsumisago
健治 木村
晃敏 林
昌弘 辰巳砂
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Osaka Prefecture Univ
Toyota Motor Corp
トヨタ自動車株式会社
公立大学法人大阪府立大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation

Abstract

<P>PROBLEM TO BE SOLVED: To provide a battery having high quality by using sulfide glass having viscosity in a solid electrolyte. <P>SOLUTION: In a method for manufacturing a solid battery, a positive mix layer 100 includes sulfide glass 31 before baking, and a positive active material 110. The sulfide glass 31 and the positive active material 110 are press-molded and come in contact each other. A negative mix layer 200 includes the sulfide glass 31 before baking and a negative active material 210. The sulfide glass 31 and the negative active material 210 are press-molded and come in contact each other. A process decreasing electric resistance in a solid electrolyte layer 30 includes a process adjusting a heating condition according to the thickness by monitoring the thickness of a laminate in heating. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a solid battery, and more particularly to a method for manufacturing a solid battery using a solid electrolyte.

Conventional batteries include, for example, Japanese Unexamined Patent Application Publication No. 2004-265585 (Patent Document 1), Japanese Unexamined Patent Application Publication No. 2004-348972 (Patent Document 2), Japanese Unexamined Patent Application Publication No. 2004-348993 (Patent Document 3), and Japanese Unexamined Patent Application Publication No. 2003-208919. (Patent Document 4) and Japanese Patent No. 3198828 (Patent Document 5).
Japanese Patent Application Laid-Open No. 2004-265685 JP 2004-348972 A JP 2004-348773 A JP 2003-208919 A Japanese Patent No. 3198828

  Conventionally, lithium ion conductive glass ceramic has been obtained by using lithium sulfide as a starting material and forming sulfide glass by mechanical milling and firing it at a temperature higher than the glass transition temperature. An all solid state battery is manufactured using this lithium ion conductive glass ceramic. However, there is a problem that the quality of the battery is not stable.

  Accordingly, the present invention has been made to solve the above-described problems, and an object thereof is to provide a solid battery having a stable quality.

  The method for producing a solid battery according to the present invention includes a step of laminating an inorganic glass layer on a composite layer containing an active material of a positive electrode or a negative electrode, and a glass transition point of the inorganic glass or higher while pressing the laminate in the thickness direction. A step of forming a solid electrolyte layer by heating at a temperature and precipitating ceramics in the inorganic glass so that the electrical resistance in the inorganic glass layer is made smaller than before the ceramics are deposited. The step of forming the solid electrolyte layer includes a step of monitoring the thickness of the laminated body during heating and adjusting the heating conditions according to the thickness.

  Preferably, the step of forming the solid electrolyte layer includes a step of monitoring the electrical resistance of the laminate during heating and adjusting the heating conditions according to the electrical resistance.

  According to the present invention, a solid battery with stable quality can be provided.

  Embodiments of the present invention will be described below with reference to the drawings. In the following embodiments, the same or corresponding parts are denoted by the same reference numerals, and description thereof will not be repeated. In addition, the embodiments can be combined.

(Embodiment 1)
1 is a cross-sectional view of a battery according to Embodiment 1 of the present invention. Referring to FIG. 1, solid battery 1 includes positive electrode current collector 10, positive electrode mixture layer 100 in contact with positive electrode current collector 10, solid electrolyte layer 30 in contact with positive electrode mixture layer 100, and solid electrolyte. The negative electrode mixture layer 200 that contacts the layer 30 and the negative electrode current collector 20 that contacts the negative electrode mixture layer 200 are included. The positive electrode current collector 10 and the negative electrode current collector 20 are each made of a metal such as aluminum or copper. The positive electrode mixture layer 100 includes a positive electrode active material 110, a conductive aid 120 disposed adjacent to the positive electrode active material 110, and a sulfide glass 31 surrounding the positive electrode active material 110 and the conductive aid 120. .

The sulfide glass 31 mechanically seals a mixture of, for example, SiS 2 , phosphorus pentasulfide (P 2 S 5 ), and P 2 S 3 that are glass forming materials and lithium sulfide (Li 2 S) that is a glass modifier. Can be obtained. The lithium sulfide (Li 2 S) constituting the sulfide glass 31 may be manufactured by any manufacturing method, and may be used without particular limitation as long as it is industrially produced and sold. Can do.

Further, the particle size of lithium sulfide is not particularly limited.
Alternatively, the sulfide glass 31 may be manufactured by mechanically milling a mixture of lithium sulfide and phosphorus pentasulfide as a starting material, or a mixture of simple phosphorus and simple sulfur instead of phosphorus pentasulfide by mechanical milling. Good.

  As the positive electrode active material 110, for example, lithium cobalt oxide can be used. Moreover, as the conductive support material 120, for example, graphite can be used.

  The solid electrolyte layer 30 is composed of glass ceramics 32 as a solid electrolyte. This glass ceramic 32 is obtained by firing sulfide glass and has higher lithium ion conductivity than sulfide glass.

  The negative electrode mixture layer 200 includes a negative electrode active material 210 and a sulfide glass 31 that surrounds the negative electrode active material 210. Carbon can be used as the negative electrode active material 210.

  Although the conductive support material 120 is provided in the positive electrode mixture layer 100, the conductive support material 120 is not necessarily provided. In addition, although the conductive additive is not provided in the negative electrode mixture layer 200, the conductive additive may be provided in the negative electrode mixture layer 200.

  The sulfide glass 31 is in the form of particles, and an interface may appear between the particles of the adjacent sulfide glass 31. The positive electrode mixture layer 100 includes a sulfide glass 31 before firing and a positive electrode active material 110. The sulfide glass 31 and the positive electrode active material 110 are pressure-formed and are in contact with each other. The negative electrode mixture layer 200 includes a sulfide glass 31 before firing and a negative electrode active material 210. The sulfide glass 31 and the negative electrode active material 210 are pressure-formed and are in contact with each other. The solid battery 1 includes a positive electrode mixture layer 100, a negative electrode mixture layer 200, and a solid electrolyte layer 30 having glass ceramics 32 sandwiched between the positive electrode mixture layer 100 and the negative electrode mixture layer 200.

  Next, a method for manufacturing the battery shown in FIG. 1 will be described. FIG. 2 is a diagram illustrating raw materials for the positive electrode mixture layer and the negative electrode mixture layer. Referring to FIG. 2, first, positive electrode active material 110, conductive additive 120 and sulfide glass 31 are prepared as materials constituting the positive electrode mixture layer. In addition, a negative electrode active material 210 and a sulfide glass 31 are prepared as materials constituting the negative electrode mixture layer 200. The positive electrode active material 110, the conductive additive 120, the sulfide glass 31, and the negative electrode active material 210 are each powder, and for example, powder pulverized by milling can be used. Moreover, there is no restriction | limiting in particular about the particle size of each powder. The positive electrode mixture layer 100 can be obtained by sufficiently mixing the positive electrode active material 110, the conductive additive 120 and the sulfide glass 31 and then performing pressure molding in a mold. Moreover, the negative electrode active material layer 210 and the sulfide glass 31 are sufficiently mixed, and the negative electrode mixture layer 200 can be obtained by press-molding this in a mold.

  FIG. 3 is a diagram showing a first step of a method for producing a solid electrolyte layer. FIG. 4 is a diagram illustrating a second step of the method for manufacturing the solid electrolyte layer. Referring to FIG. 3, a sulfide glass 31 is first prepared. The sulfide glass 31 may have the same composition and particle size as the sulfide glass 31 constituting the positive electrode mixture layer 100 and the negative electrode mixture layer 200, or may have a different composition and particle size.

Referring to FIG. 4, glass ceramic 32 is deposited by firing sulfide glass at a temperature equal to or higher than the glass transition point of sulfide glass 31. Although the temperature and time of this heat treatment vary depending on the composition of the sulfide glass, for example, when lithium sulfide Li 2 S is used as the sulfide glass, it can be fired at a temperature of 150 ° C. to 500 ° C.

  FIG. 5 shows a method for manufacturing the solid state battery according to the first embodiment. Referring to FIG. 5, when manufacturing a solid battery, positive electrode composite material layer 100, sulfide glass 31 layer and negative electrode composite material layer 200 are laminated. In this laminated state, the molds 251 and 252 are pressurized in the directions indicated by the arrows 253 and 254. At the time of pressurization, heating is performed in a baking furnace 261. Stoppers 255 and 256 having a predetermined height H are provided between the molds 251 and 252 to prevent the distance between the molds 251 and 252 from becoming too small.

  A high ion conductive crystal is precipitated from the sulfide glass 31 by heating. At this time, heating is performed while applying pressure between the positive electrode current collector 10 and the negative electrode current collector 20 with the heated molds 251 and 252. Since the displacement of the mold is fixed at a predetermined value of the battery thickness, the lowering of the viscosity of the sulfide glass by heating and the precipitation of the high ion conductive crystal proceed simultaneously until the predetermined thickness is reached. The thickness is reduced, and a solid battery with high thickness accuracy can be obtained.

  FIG. 6 is a diagram illustrating the solid state battery after heating. After the heating, the molds 251 and 252 are in contact with the stoppers 255 and 256. By preventing the distance between the molds 251 and 252 from getting too close, the thickness of the battery is prevented from becoming too small. Glass ceramic 32 is deposited to form solid electrolyte layer 30.

  FIG. 7 is a graph showing the relationship among the heating time of the mold, the thickness of the laminated body, and the heating temperature of the mold in the manufacturing method according to this embodiment. In the figure, the left axis indicates the thickness and the right axis indicates the heating temperature. At the start of heating, the thickness of the laminate is larger than the target value. At this time, the temperature of the sulfide glass constituting the laminated body is raised by raising the heating temperature. When the temperature of the sulfide glass exceeds the glass transition point, the fluidity of the sulfide glass increases, and the sulfide glass particles are easily deformed. Along with this, the sulfide glass being pressed is deformed, and the thickness of the laminate is reduced. When the thickness of the laminate approaches a predetermined value, the heating temperature is lowered to lower the fluidity of the sulfide glass. Thereby, the thickness of the laminated body containing sulfide glass can be made into a predetermined value.

  8 and 9 are cross-sectional views of a solid state battery according to a comparative example. Referring to FIG. 8, if the thickness of one cell is smaller than a predetermined value, it is difficult to restrain it by restraining members 283 and 284. A plurality of cells are stacked between the opposing plate members 281 and 282 and fixed by the restraining members 283 and 284. However, when a predetermined gap A is generated between the plate member 281 and the cells, the restraining force is lost.

  FIG. 9 shows a cell that is too thick. As shown in FIG. 9, when the thickness of one cell becomes too large, a gap B is generated between the restraining member 284 and the plate material 281 and restraining becomes impossible.

  FIG. 10 shows a manufacturing method according to another aspect of this embodiment. Referring to FIG. 10, during heating in firing furnace 261, the electrical resistance between positive electrode current collector 10 and negative electrode current collector 20 is measured using resistance meter 273, and then heated after reaching a predetermined resistance value. You may manufacture a solid battery by the method of stopping.

  FIG. 11 is a graph showing the relationship between the electrical resistance in the thickness direction of the laminate, the heating temperature, and the heating time in the manufacturing method according to this embodiment. The electrical resistance between the positive electrode current collector 10 and the negative electrode current collector 20 before firing is higher than the target value. By continuing the heating, ceramics precipitate in the sulfide glass. Thereby, an electrical resistance falls. When the electric resistance begins to drop, the heating temperature is lowered. Thereby, it can be set as the electrical resistance of a target value.

  FIG. 12 is a graph showing the temperature and electrical resistance of sulfide glass. Referring to FIG. 12, the electrical resistance is substantially constant until the sulfide glass is heated and the temperature exceeds the glass transition point Tg (region A). When the heating is further continued, a high ion conductive crystal is precipitated and the electric resistance is lowered (region B). Further, when the heating is further continued to raise the temperature, a low ion conductive crystal is deposited (region C). If the heating is continued, the amount of low ion conductive crystals increases and the electrical resistance increases rapidly. Therefore, in this embodiment, the firing temperature of the sulfide glass is controlled so that the temperature is near the boundary between the region B and the region C.

  13 and 14 are diagrams showing a method of manufacturing a solid state battery according to still another aspect of this embodiment. Referring to FIG. 13, the laminate is heated with molds 251 and 252, and the electrical resistance between positive electrode current collector 10 and negative electrode current collector 20 is measured using resistance meter 273. That is, in this example, both the electrical resistance and the thickness of the laminate are controlled, and the heating temperature and the heating time are adjusted based on both data. As shown in FIG. 14, a battery cell having a predetermined thickness and a predetermined electric resistance can be obtained.

  The solid battery manufacturing method according to the present invention includes a step of laminating a sulfide glass 31 as an inorganic glass layer on a composite material layer containing a positive electrode or negative electrode active material, and an inorganic glass while pressing the laminate in the thickness direction. Forming a solid electrolyte layer 30 by heating at a temperature equal to or higher than the glass transition point of the glass and precipitating the glass ceramics 32 in the inorganic glass, thereby reducing the electrical resistance in the inorganic glass layer than before the ceramics are deposited. Prepare. The step of reducing the electrical resistance in the sulfide glass 31 includes the step of monitoring the thickness of the laminated body during heating and adjusting the heating conditions according to the thickness. The step of reducing the electrical resistance in the sulfide glass 31 includes a step of monitoring the electrical resistance of the laminate during heating and adjusting the heating conditions according to the electrical resistance.

An example is shown below about the manufacturing method of FIGS. 10, 13, and 14 which measures electrical resistance. The sulfide glass was obtained, for example, by treating a mixed powder of Li 2 S and P 2 S 5 having a molar ratio of 80:20 with a planetary ball mill for 20 hours (mechanical milling).

The positive electrode mixture was obtained by mixing LiCoO 2 , sulfide glass and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and sulfide glass at a weight ratio of 1: 1.

  By charging a positive electrode current collector (copper), a negative electrode mixture, glass ceramics, a positive electrode mixture and a negative electrode current collector (copper) in this order into a circular mold having a diameter of 10 mm that can be pressure-molded, and pressurizing at 10 MPa after the injection A pellet (laminated body) was obtained.

  The circular pellet obtained above is fired for several hours at a temperature (about 200 ° C.) above the glass transition point of the glass ceramic. During firing, the resistance of the circular pellet was monitored with an electric resistance meter (impedance meter), and the firing time was adjusted so that the value became 500Ω ± 5%, which was used as a solid battery. Thereby, the quantity of the high ion power transmission crystal which precipitates from glass ceramics was adjusted by adjustment of baking time.

The solid state battery obtained by the above procedure is charged at a current amount of 50 μA until the charge amount per gram of LiCoO 2 becomes 110 mAh, and then discharged twice until the same current value becomes 3.0 V. After repeating, when the resistance value was confirmed with an impedance meter, the resistance value became 1000Ω ± 10%, and the variation amount of about half of the conventional variation amount ± 20% was realized.

An example is shown below about the manufacturing method of FIGS. 5, 6, 13 and 14 which measures the thickness of a laminated body. The glass ceramic was obtained, for example, by treating a mixed powder of Li 2 S and P 2 S 5 having a molar ratio of 80:20 with a planetary ball mill for 20 hours (mechanical milling).

The positive electrode mixture was obtained by mixing LiCoO 2 , sulfide glass and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and sulfide glass at a weight ratio of 1: 1.

  By charging a positive electrode current collector (copper), a negative electrode mixture, glass ceramics, a positive electrode mixture and a negative electrode current collector (copper) in this order into a circular mold having a diameter of 10 mm that can be pressure-molded, and pressurizing at 10 MPa after the injection A pellet (laminated body) was obtained.

  The circular pellet obtained above was pressed and held (2 hours, 10 MPa) with a mold having a surface temperature equal to or higher than the glass transition point of the glass ceramics (2 hours, 10 MPa) to obtain a solid battery. The mold was provided with a stopper so that the thickness of the battery did not become a predetermined thickness or less.

The variation in thickness of the solid battery obtained by the above procedure was within 10%.
In the above description, the solid electrolyte in which superionic conductive crystals are precipitated by firing amorphous glass is combined with an amorphous state before firing and a crystalline state after firing. The type of the electrolyte is not limited as long as it has a property. For example, the portion corresponding to the amorphous portion of the present invention may be an amorphous solid electrolyte made of another material, and the portion corresponding to the crystalline portion is the same.

  In Embodiment 1, since the electrolyte in the positive electrode mixture layer 100 as the positive electrode active material layer and the negative electrode mixture layer 200 as the negative electrode active material layer is the sulfide glass 31 having viscosity, the positive electrode active material accompanying charge / discharge The expansion and contraction of 110 and the negative electrode active material 210 can be absorbed, and the ion conduction path can be prevented from being broken. This improves the life characteristics.

(Embodiment 2)
FIG. 15 is a cross-sectional view of a battery according to Embodiment 2 of the present invention. Referring to FIG. 15, in solid battery 1 according to the second embodiment, the embodiment is such that sulfide glass 31 and glass ceramics 32 are mixed in positive electrode mixture layer 100 and negative electrode mixture layer 200. Different from the battery according to 1. In the second embodiment, the shape of the battery is formed in the state of sulfide glass 31 and then fired. The conditions during the firing are adjusted to adjust the crystallinity, and a part remains in the glass state. That is, in positive electrode composite material layer 100 according to the second embodiment, sulfide glass 31 is fired at a temperature equal to or higher than the glass transition point of sulfide glass 31, and a portion of sulfide glass 31 is transferred to glass ceramics 32. Yes. A solid battery 1 as a battery includes a positive electrode mixture layer 100, a negative electrode mixture layer 200, and a solid electrolyte layer 30 including glass ceramics 32 sandwiched between the positive electrode mixture layer 100 and the negative electrode mixture layer 200.

  That is, by using the viscous sulfide glass 31 for the solid electrolyte constituting the positive electrode mixture layer 100 and the negative electrode mixture layer 200, the ion conduction network is destroyed due to the expansion and contraction of the active material accompanying charge / discharge. Can prevent and improve the life characteristics.

  Next, a method for manufacturing the battery shown in FIG. 15 will be described. 16 and 17 are diagrams for illustrating a method of manufacturing the battery according to the second embodiment shown in FIG. First, referring to FIG. 16, positive electrode active material 110, negative electrode active material 210, sulfide glass 31, and conductive additive 120 are prepared as raw material materials.

  Referring to FIG. 17, positive electrode mixture layer 100 is formed by mixing positive electrode active material 110, conductive additive 120, and sulfide glass 31 and performing pressure molding. Also, the negative electrode active material layer 210 and the sulfide glass 31 are mixed and pressed to form the negative electrode mixture layer 200. A sulfide glass 31 is filled between the positive electrode mixture layer 100 and the negative electrode mixture layer 200. By firing the positive electrode mixture layer 100, the solid electrolyte layer 30, and the negative electrode mixture layer 200 in this manner, a superionic conductive crystal is deposited on a part of the sulfide glass 31 to constitute the glass ceramic shown in FIG. At this time, a part of the sulfide glass 31 is left as it is by controlling the firing conditions.

  Thereby, since a part of electrolyte is comprised with the glass which has viscosity, the expansion / contraction of the active material accompanying charging / discharging is absorbed, and destruction of an ion conduction path | route can be prevented. Therefore, the life characteristics are improved.

Examples are shown below. The sulfide glass was obtained, for example, by treating a mixed powder of Li 2 S and P 2 S 5 having a molar ratio of 80:20 with a planetary ball mill for 20 hours (mechanical milling).

The positive electrode mixture was obtained by mixing LiCoO 2 , sulfide glass and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and sulfide glass at a weight ratio of 1: 1.

  A negative electrode mixture, sulfide glass, and a positive electrode mixture were placed in this order into a circular mold having a diameter of 10 mm that can be pressure-molded, and then circular pellets were obtained by pressurizing at 10 MPa.

  The circular pellet obtained above is fired for several hours near the glass transition point of sulfide glass (about 200 ° C.). At that time, the holding time is adjusted in accordance with the reaction progress rate of the sulfide glass at the corresponding temperature obtained in advance. Although depending on the ionic conductivity of the sulfide glass ion, the residual amount of the sulfide glass was set to 10% in this example.

As a comparative example, a solid battery was prepared by the following method.
A glass ceramic was obtained by firing the sulfide glass obtained by the same method as in this example for several hours at a temperature near the glass transition point (about 200 ° C.).

The positive electrode mixture was obtained by mixing LiCoO 2 , glass ceramics, and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and sulfide glass at a weight ratio of 1: 1.

  A negative electrode mixture, glass-ceramic sulfide glass, and positive electrode mixture were put in this order into a circular mold having a diameter of 10 mm that could be pressure-molded, and then circular pellets were obtained by pressurizing at 10 MPa.

Both of the solid batteries prepared as Examples and Comparative Examples were subjected to charge / discharge for 10 cycles at a current density of 64 μA / cm 2 after the batteries were prepared, and then subjected to a charge / discharge test for 100 cycles. In each battery, the decrease rate of the dischargeable capacity and the increase rate of the battery resistance after the implementation when the dischargeable capacity and the battery resistance before the 100-cycle charge / discharge test were taken as a reference were confirmed. As a result, in this example, the dischargeable capacity decrease rate was 14% and the battery resistance increase rate was 23%. In the comparative example, the dischargeable capacity decrease rate was 26% and the battery resistance increase rate was 48%. Was effective in improving the battery life characteristics.

(Embodiment 3)
FIG. 18 is a cross-sectional view of a battery according to Embodiment 3 of the present invention. Referring to FIG. 18, in the solid battery 1 according to the third embodiment, the embodiment is that the sulfide glass 31 and the glass ceramic 32 as the solid electrolyte are sintered before pressure molding. 2. Different from the solid battery 1 according to 2. That is, in the second embodiment, the glass ceramics 32 are formed by sintering after pressure molding, whereas in the third embodiment, the solid battery 1 is configured by pressure molding after firing. .

  FIG. 19 is a diagram for explaining a battery manufacturing method according to the third embodiment shown in FIG. Referring to FIG. 19, positive electrode active material 110, conductive additive 120, glass ceramic 32, sulfide glass 31, and negative electrode active material 210 are prepared as raw materials. The material of the positive electrode mixture layer 100 is the positive electrode active material 110, the conductive additive 120, the sulfide glass 31, and the glass ceramics 32 constitute the positive electrode mixture layer 100. The negative electrode active material 210, the sulfide glass 31 and the glass ceramic 32 constitute the negative electrode mixture layer 200. The glass ceramic 32 is obtained by firing the sulfide glass 31, and the glass ceramic 32 is deposited by firing at a temperature equal to or higher than the glass transition point of the sulfide glass 31. The glass ceramic 32 is a superionic conductor. The positive electrode active material layer 110, the conductive additive 120, the sulfide glass 31 and the glass ceramic 32 are mixed and then pressure-molded to form the positive electrode mixture layer 100. The negative electrode active material layer 210, the sulfide glass 31, and the glass ceramics 32 are mixed and pressure-molded to form the negative electrode mixture layer 200. The solid electrolyte layer 30 is formed by press-molding the sulfide glass 31 and the glass ceramic 32. By combining these, the solid battery shown in FIG. 8 is completed.

  The solid battery 1 according to the third embodiment configured as described above has the same effect as the solid battery 1 according to the second embodiment.

Examples are shown below. The sulfide glass was obtained, for example, by treating a mixed powder of Li 2 S and P 2 S 5 having a molar ratio of 80:20 with a planetary ball mill for 20 hours (mechanical milling). The glass ceramic was obtained by firing this sulfide glass for several hours at a temperature near the glass transition point (about 200 ° C.).

  A mixture of sulfide glass and glass ceramic (hereinafter referred to as a mixture) was obtained by mixing the sulfide glass and glass ceramic in a weight ratio of 3 to 7.

The positive electrode mixture was obtained by mixing a mixture of LiCoO 2 , sulfide glass and ceramics and a conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing a graphite, sulfide glass, and ceramic mixture in a weight ratio of 1: 1.

  A negative electrode mixture, sulfide glass, and a positive electrode mixture were placed in this order into a circular mold having a diameter of 10 mm that can be pressure-molded, and then circular pellets were obtained by pressurizing at 10 MPa.

As a comparative example, a solid battery was prepared by the following method.
A glass ceramic was obtained by firing the sulfide glass obtained by the same method as in this example at a temperature near the glass transition point (200 ° C.) for several hours.

The positive electrode mixture was obtained by mixing LiCoO 2 , glass ceramics, and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and glass ceramics at a weight ratio of 1: 1.

  A negative electrode mixture, glass ceramics, and positive electrode mixture were charged in this order into a circular mold having a diameter of 10 mm that could be pressure-molded, and then circular pellets were obtained by pressurizing at 10 MPa.

Both of the solid batteries prepared as Examples and Comparative Examples were subjected to charge / discharge for 10 cycles at a current density of 64 μA / cm 2 after the batteries were prepared, and then subjected to a charge / discharge test for 100 cycles. In each battery, the decrease rate of the dischargeable capacity and the increase rate of the battery resistance after the implementation when the dischargeable capacity and the battery resistance before the 100-cycle charge / discharge test were taken as a reference were confirmed. As a result, in this example, the dischargeable capacity decrease rate was 14% and the battery resistance increase rate was 23%. In the comparative example, the dischargeable capacity decrease rate was 26% and the battery resistance increase rate was 48%. Was effective in improving the battery life characteristics.

  In the above description, the solid electrolyte in which superionic conductive crystals are precipitated by firing amorphous glass is combined with an amorphous state before firing and a crystalline state after firing. The type of the electrolyte is not limited as long as it is a solid electrolyte. For example, the portion corresponding to the amorphous portion of the present invention may be an amorphous solid electrolyte made of another material, and the portion corresponding to the crystalline portion is the same.

  Furthermore, in this example, a mixture of sulfide glass and glass ceramics was used as the solid electrolyte, but the holding time was determined according to the reaction progress rate of the sulfide glass at the firing temperature obtained in advance when firing the sulfide glass. It is also possible to obtain a mixture by leaving a part of the sulfide glass unreacted by adjusting.

(Embodiment 4)
FIG. 20 is a cross-sectional view of a battery according to Embodiment 4 of the present invention. Referring to FIG. 20, solid battery 1 according to the fourth embodiment of the present invention is different from the battery according to the first embodiment in that glass ceramics 32 is deposited at both ends 2 and 3. Different. That is, the glass ceramics 32 are deposited at both ends 2 and 3 as the periphery of the battery by firing only around the solid battery 1 at a temperature equal to or higher than the glass transition point. Due to the mixed state of the positive electrode mixture layer 100 and the negative electrode mixture layer 200 and, in some cases, the sulfide glass as the solid electrolyte constituting the solid electrolyte layer 30, the viscous sulfide glass expands the active material accompanying charge / discharge. Repeat contraction. This can prevent the ion conduction network from being destroyed and improve the life characteristics. Furthermore, the life characteristics can be further improved by firing only the periphery of the battery configured as described above and completely converting the periphery of the battery into glass ceramics. That is, when the sulfide glass 31 is present in the solid electrolyte, only the periphery of the solid battery 1 is baked (heated) so that only the periphery of the battery is made into glass ceramics. Since this glass ceramic 32 has no fluidity, it is possible to prevent the outflow of the sulfide glass 31 caused by the increase in internal pressure of the solid battery 1 due to charge / discharge.

  FIG. 21 is a diagram for explaining a battery manufacturing method according to the fourth embodiment shown in FIG. First, the solid battery 1 is produced by the same method as in the first embodiment. Thereafter, the heater 4 is brought into contact with both end portions 2 and 3 of the solid battery 1. And the both ends 2 and 3 of the solid battery 1 are heated to the temperature more than a glass transition point using the heater 4. FIG. Thereby, the glass ceramics 32 are deposited on the outer peripheral portion shown in FIG. In this embodiment, the example in which the outer peripheral portion of the battery according to the first embodiment is made into glass ceramics has been shown. However, the outer peripheral portion of the solid battery 1 according to another embodiment may be made into glass ceramics.

  The battery according to the fourth embodiment configured as described above has the same effect as the battery according to the first embodiment.

Examples are shown below. The sulfide glass was obtained, for example, by treating a mixed powder of Li 2 S and P 2 S 5 having a molar ratio of 80:20 with a planetary ball mill for 20 hours (mechanical milling). The glass ceramic was obtained by firing this sulfide glass for several hours at a temperature near the glass transition point (about 200 ° C.).

The positive electrode mixture was obtained by mixing LiCoO 2 , sulfide glass and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and sulfide glass at a weight ratio of 1: 1.

  A negative electrode mixture, glass ceramics, and positive electrode mixture were charged in this order into a pressure-moldable circular mold having a diameter of 10 mm, and a pellet-shaped solid battery was obtained by pressurizing at 10 MPa.

  Only the periphery of the solid battery was installed in a circular shape with a diameter of 10 mm, which can be adjusted in temperature, and the periphery of the battery was heated so as to be slightly higher (about 220 degrees) than the temperature near the glass transition point. The heating time is adjusted according to the region to be glass-ceramics based on the thermal conductivity into the battery obtained in advance and the reaction progress rate of the sulfide glass at the firing temperature. In this example, the heating time was set to several minutes, and the region of about 1 to 2 mm from the periphery toward the center was made into glass ceramics.

As a comparative example, a solid battery was prepared by the following method.
A glass ceramic was obtained by firing the sulfide glass obtained by the same method as in this example at a temperature near the glass transition point (200 ° C.) for several hours.

The positive electrode mixture was obtained by mixing LiCoO 2 , sulfide glass and conductive additive (graphite) in a weight ratio of 40: 60: 4. The negative electrode mixture was obtained by mixing graphite and sulfide glass at a weight ratio of 1: 1.

  A negative electrode mixture, glass ceramics, and positive electrode mixture were charged in this order into a pressure-moldable circular mold having a diameter of 10 mm, and a pellet-shaped solid battery was obtained by pressurizing at 10 MPa.

Both of the solid batteries prepared as Examples and Comparative Examples were subjected to charge / discharge for 10 cycles at a current density of 64 μA / cm 2 after the batteries were prepared, and then subjected to a charge / discharge test for 100 cycles. In each battery, the decrease rate of the dischargeable capacity and the increase rate of the battery resistance after the implementation when the dischargeable capacity and the battery resistance before the 100-cycle charge / discharge test were taken as a reference were confirmed. As a result, in this example, the dischargeable capacity decrease rate was 10% and the battery resistance increase rate was 19%. In the comparative example, the dischargeable capacity decrease rate was 14% and the battery resistance increase rate was 23%. Was effective in improving the battery life characteristics.

(Embodiment 5)
FIG. 22 is a sectional view of a battery according to the fifth embodiment of the present invention. Referring to FIG. 22, in solid battery 1 according to the fifth embodiment, sulfide glass layer 40 is provided between solid electrolyte layer 30 and positive electrode mixture layer 100, and solid electrolyte layer 30 and negative electrode mixture are provided. It differs from solid battery 1 according to the first embodiment in that sulfide glass layer 40 is also provided between layers 200. Note that sulfide glass layer 40 may be provided in the battery according to the first embodiment.

  The solid electrolyte layer 30 is made of glass ceramics in this embodiment, but sulfide glass 31 may be mixed in part of the glass ceramics 32.

  Although the solid electrolyte in the positive electrode mixture layer 100 is the glass ceramics 32, a part of the glass ceramics 32 may be the sulfide glass 31. Although the solid electrolyte in the negative electrode mixture layer 200 is the glass ceramics 32, a part of the glass ceramics 32 may be the sulfide glass 31.

  That is, the sulfide glass layer 40 of FIG. 22 can be applied to any battery of all the embodiments. Moreover, although the sulfide glass layer 40 is provided on both sides of the solid electrolyte layer 30, the sulfide glass layer 40 may be provided on only one of them.

  Next, a method for manufacturing the battery shown in FIG. 22 will be described. 23 and 24 are diagrams for illustrating a method of manufacturing the battery according to the fifth embodiment shown in FIG. First, referring to FIG. 23, a positive electrode active material 110, a conductive additive 120, a glass ceramic 32, and a negative electrode active material 210 are prepared. The positive electrode active material 110, the conductive additive 120, and the glass ceramics 32 constitute the positive electrode mixture layer 100, and the negative electrode active material 210 and the glass ceramics 32 constitute the negative electrode mixture layer 200.

Moreover, the sulfide glass 31 for sulfide glass layers is prepared.
Referring to FIG. 24, positive electrode active material layer 110, conductive additive 120, and glass ceramics 32 are mixed and subjected to pressure molding to form positive electrode mixture layer 100. Further, the sulfide glass layer 40 is formed by pressure forming the sulfide glass 31. The glass ceramic 32 is formed by press molding the glass ceramic 32. The negative electrode mixture layer 200 is formed by press-molding the negative electrode active material 210 and the glass ceramic 32.

  Each of the negative electrode mixture layer 200, the sulfide glass layer 40, the solid electrolyte layer 30, and the positive electrode mixture layer 100 is formed by pressure to form the battery shown in FIG.

  In the battery configured as described above, by providing the sulfide glass layer 40 between the positive electrode mixture layer 100 and the solid electrolyte layer 30, the contact area between the positive electrode mixture layer 100 and the solid electrolyte layer 30 increases. Contact resistance is improved. Further, by providing the sulfide glass layer 40 between the negative electrode mixture layer 200 and the solid electrolyte layer 30, the contact area between the negative electrode mixture layer 200 and the solid electrolyte layer 30 is increased, and the contact resistance is improved. This improves the output of the battery. Thereby, even if the manufacturing method which comprises the positive electrode composite material layer 100, the negative electrode composite material layer 200, and the solid electrolyte layer 30 separately and comprises a battery is employ | adopted, increase in battery resistance can be prevented.

Examples are shown below. The sulfide glass was obtained, for example, by treating a mixed powder of Li 2 S and P 2 S 5 having a molar ratio of 80:20 with a planetary ball mill for 20 hours (mechanical milling). The glass ceramic was obtained by firing this sulfide glass for several hours at a temperature near the glass transition point (about 200 ° C.).

For the positive electrode mixture, LiCoO 2 , glass ceramics, and conductive additive (graphite) are mixed at a weight ratio of 40: 60: 4, put into a circular mold having a diameter of 10 mm that can be pressure-molded, and then pressurized at 10 MPa. To obtain a round pellet. Further, the negative electrode mixture was obtained as a circular pellet by mixing graphite and glass ceramics in a weight ratio of 1: 1, putting into a circular mold having a diameter of 10 mm that can be pressure-molded, and pressurizing at 10 MPa after the charging.

  The glass-ceramic layer was also put into a circular mold having a diameter of 10 mm that can be pressure-molded, and was pressed as a circular pellet by pressurizing at 10 MPa.

  A negative electrode mixture layer is placed in a circular mold having a diameter of 10 mm, which can be pressure-molded, and 1/10 the amount of sulfide glass of the solid electrolyte is dispersed thereon, and a glass ceramic layer is placed thereon. On top of that, 1/10 of the amount of the above-mentioned solid electrolyte sulfide glass was sprayed, a positive electrode mixture layer was placed thereon, and then pressurized at 10 MPa to obtain a pellet-shaped solid battery.

  As a comparative example, a solid battery produced in the same manner as above except that the sulfide glass was not sprayed was obtained.

Both of the solid batteries prepared as Examples and Comparative Examples were charged and discharged for 10 cycles at a current density of 64 μA / cm 2 after the batteries were prepared, and then the internal resistances of the batteries were compared. Based on the comparative example, it was confirmed that there was an 18% resistance reduction in the example.

  In the above description, the solid electrolyte in which superionic conductive crystals are precipitated by firing amorphous glass is combined with an amorphous state before firing and a crystalline state after firing. The type of the electrolyte is not limited as long as it is a solid electrolyte. For example, the portion corresponding to the amorphous portion of the present invention may be an amorphous solid electrolyte made of another material, and the portion corresponding to the crystalline portion is the same.

(Embodiment 6)
FIG. 25 is a sectional view of a battery according to the sixth embodiment of the present invention. Referring to FIG. 25, the battery according to the sixth embodiment is different from the battery according to the first embodiment in that a plurality of cells are stacked and connected in series. One cell has an electromotive force of 3.6V. Note that this electromotive force can be changed in various ways depending on the materials constituting the positive electrode active material 110 and the negative electrode active material 210.

  Further, the number of stacked layers can be determined by the value of the voltage required for the battery and the electromotive force of one cell. In FIG. 25, one cell is from the negative electrode current collector 20 to the positive electrode current collector 10, and the positive electrode mixture layer 100, the solid electrolyte layer 30, and the negative electrode mixture layer 200 are provided in one cell. A plurality of cells are connected in series by contacting the negative electrode current collector 20 and the positive electrode current collector 10 of adjacent cells.

  The positive electrode mixture layer 100 includes a positive electrode active material 110, a conductive additive 120, and glass ceramics 32. The solid electrolyte layer 30 has a glass ceramic 32. The negative electrode mixture layer 200 includes a negative electrode active material 210 and a glass ceramic 32.

  Next, a method for manufacturing the battery shown in FIG. 25 will be described. FIG. 26 to FIG. 28 are diagrams for explaining a method of manufacturing the positive electrode mixture layer. Referring to FIG. 26, first, sulfide glass 31, positive electrode active material 110, and conductive additive 120 are prepared as raw materials for the positive electrode mixture layer. These are mixed to form a mixture.

  Referring to FIG. 27, a composite of positive electrode active material 110 and sulfide glass 31 is formed by pressurizing the mixture. In the composite, the sulfide glass 31, the positive electrode active material 110, and the conductive additive 120 are in close contact.

  Referring to FIG. 28, glass composite 32 is deposited by firing the composite produced in the above-described process at a temperature equal to or higher than the glass transition point of sulfide glass 31. Glass ceramics are superionic conductive layers.

  FIG. 29 to FIG. 31 are diagrams for explaining a method of manufacturing a solid electrolyte layer. Referring to FIG. 29, first, a sulfide glass 31 constituting a solid electrolyte layer is prepared.

  Referring to FIG. 30, sulfide glass 31 is pressurized. Since the sulfide glass 31 has viscosity, it flows and becomes dense by pressurization.

  Referring to FIG. 31, glass ceramics 32 is deposited by firing a densified sulfide glass at a temperature equal to or higher than its glass transition point.

  32 to 34 are views for explaining a method of manufacturing the negative electrode mixture layer. Referring to FIG. 32, negative electrode active material 210 and sulfide glass 31 constituting negative electrode mixture layer 200 are mixed to produce a mixture.

  Referring to FIG. 33, the mixture is pressurized. Since the sulfide glass 31 has viscosity, it flows and becomes dense by pressurization. As a result, a composite of the negative electrode active material 210 and the sulfide glass 31 is formed.

  Referring to FIG. 34, the composite is fired. At this time, the glass ceramics 32 are precipitated by firing at a temperature equal to or higher than the glass transition point of the sulfide glass 31.

  One cell of the solid battery 1 shown in FIG. 15 can be manufactured by laminating the positive electrode mixture layer 100, the solid electrolyte layer 30, and the negative electrode mixture layer 200 manufactured as described above and applying pressure. A plurality of such cells are manufactured, and the positive electrode current collector 10 and the negative electrode current collector 20 are connected to each other, whereby the solid battery 1 shown in FIG. 15 can be manufactured.

  The battery according to the sixth embodiment configured as described above has the same effect as the battery according to the first embodiment.

(Embodiment 7)
35 to 37 are diagrams for explaining another method of manufacturing the battery shown in FIG. Referring to FIG. 35, first, positive electrode active material 110, negative electrode active material 210, conductive additive 120, and sulfide glass 31 before firing are prepared as raw materials.

  Referring to FIG. 36, positive electrode active material 110, sulfide glass 31, negative electrode active material 210, and conductive additive 120 are mixed and pressure-molded to form positive electrode mixture layer 100, solid as shown in FIG. The electrolyte layer 30 and the negative electrode mixture layer 200 are formed. In the positive electrode mixture layer 100, the positive electrode active material 110, the conductive additive 120, and the sulfide glass 31 exist. A sulfide glass 31 exists in the solid electrolyte layer 30. A negative electrode active material 210 and a sulfide glass 31 exist in the negative electrode mixture layer 200.

  Referring to FIG. 37, the mixture produced by the above method is fired. At this time, the glass ceramics 32 are deposited by firing at a temperature equal to or higher than the glass transition point of the sulfide glass 31. Thereby, the solid battery 1 can be comprised.

  The composite material layer according to the present invention includes sulfide glass before firing and an active material of a positive electrode or a negative electrode, and the sulfide glass and the active material are pressure-molded and are in contact with each other.

  In the composite material layer configured as described above, the sulfide glass has viscosity and is excellent in pressure moldability. Therefore, the sulfide glass is in close contact with the surrounding active material and has excellent pressure moldability. Further, the conductivity is improved by the close contact.

  Preferably, the sulfide glass is fired at a temperature equal to or higher than the glass transition point of the sulfide glass, and a part of the sulfide glass is transferred to the glass ceramic. In this case, the destruction of the ion conduction network due to the expansion and contraction of the active material during charging and discharging can be suppressed by the viscosity of the sulfide glass.

  A solid battery according to the present invention includes a positive electrode mixture layer, a negative electrode mixture layer, and a solid electrolyte layer containing sulfide glass sandwiched and fired between the positive electrode and the negative electrode mixture layer. Includes a sulfide glass before firing and a positive electrode active material, and the sulfide glass and the positive electrode active material are pressure-formed and are in contact with each other, and the sulfide glass of the positive electrode active material is a glass of sulfide glass. Fired at a temperature equal to or higher than the transition point, a portion of the sulfide glass has transitioned to glass ceramics, and the negative electrode mixture layer includes sulfide glass and a negative electrode active material. Are pressed into contact with each other, and the sulfide glass of the negative electrode mixture layer is fired at a temperature equal to or higher than the glass transition point of the sulfide glass, and a part of the sulfide glass is transferred to the glass ceramic. In the solid battery configured as described above, the sulfide glass has viscosity and is excellent in pressure moldability. Therefore, it adheres closely to the surrounding active material and has excellent pressure moldability. Further, the conductivity is improved by the close contact.

  Preferably, the sulfide glass of the solid electrolyte is baked at a temperature equal to or higher than the glass transition point of the sulfide glass, and the sulfide glass is transferred to the glass ceramic.

  A solid state battery according to the present invention includes a positive electrode mixture layer, a negative electrode mixture layer, and a solid electrolyte layer containing sulfide glass sandwiched and fired between the positive electrode and the negative electrode mixture layer. Contains sulfide glass and a positive electrode active material, and the sulfide glass and the positive electrode active material are pressure-molded and in contact with each other, and the sulfide glass is fired at a temperature equal to or higher than the glass transition point of the sulfide glass. The sulfide glass has transitioned to glass ceramics, and the negative electrode mixture layer includes sulfide glass and a negative electrode active material, and the sulfide glass and the negative electrode active material are pressure-molded and in contact with each other. The sulfide glass is fired at a temperature equal to or higher than the glass transition point of the sulfide glass, and the sulfide glass is transferred to glass ceramics.

  A solid battery according to the present invention includes a positive electrode mixture layer, a negative electrode mixture layer, and glass ceramics sandwiched between the positive electrode and the negative electrode mixture layer. The positive electrode mixture layer includes sulfide glass and a positive electrode active material, and the sulfide glass and the positive electrode active material are pressure-formed and are in contact with each other. The negative electrode mixture layer includes sulfide glass and a negative electrode active material, and the sulfide glass and the negative electrode active material are pressure-molded and are in contact with each other.

  In the solid state battery configured as described above, the breakage of the ion conduction network due to the expansion and contraction of the active material during charging and discharging can be suppressed by the viscosity of the sulfide glass.

  A composite layer according to another aspect of the present invention includes a mixture of sulfide glass and glass ceramics, and an active material of a positive electrode or a negative electrode, and the mixture and the active material are pressure-molded and brought into contact with each other. Yes.

  In the composite material layer configured as described above, the sulfide glass has viscosity and is excellent in pressure moldability. Therefore, the sulfide glass is in close contact with the surrounding active material and has excellent pressure moldability. Further, the conductivity is improved by the close contact.

  A solid state battery according to still another aspect of the present invention includes a positive electrode mixture layer, a negative electrode mixture layer, and a solid electrolyte layer including sulfide glass and glass ceramic sandwiched between the positive electrode and the negative electrode mixture layer. Prepare. The positive electrode mixture layer includes a mixture of sulfide glass and glass ceramics and a positive electrode active material, and the mixture and the positive electrode active material are pressure-formed and are in contact with each other. The negative electrode mixture layer includes a mixture of sulfide glass and glass ceramics and a negative electrode active material, and the mixture and the negative electrode active material are pressure-molded and are in contact with each other.

  In the solid state battery configured as described above, the breakage of the ion conduction network due to the expansion and contraction of the active material during charging and discharging can be suppressed by the viscosity of the sulfide glass.

  Preferably, the sulfide glass around the solid state battery is completely transferred to glass ceramics. In this case, it is possible to prevent the sulfide glass from flowing out due to expansion and contraction during charging, and to ensure conductivity.

  The method for producing a composite layer according to the present invention includes a step of producing a mixture of sulfide glass and a positive electrode or a negative electrode active material, and a step of forming the mixture layer of a positive electrode or a negative electrode by pressure-molding the mixture. Prepare.

Preferably, the step of manufacturing the mixture includes a step of manufacturing a mixture including a conductive additive.
Preferably, the method includes a step of firing the composite layer at a temperature equal to or higher than the glass transition point of the sulfide glass to leave a part of the sulfide glass and depositing glass ceramics on the remaining sulfide glass.

  Preferably, the method includes the step of precipitating glass ceramics on the sulfide glass by firing the composite material layer at a temperature equal to or higher than the glass transition point of the sulfide glass.

  The solid battery manufacturing method according to the present invention includes a step of sandwiching a sulfide glass between a positive electrode mixture layer and a negative electrode mixture layer, and a positive electrode mixture layer, a sulfide glass, and a negative electrode mixture layer. And a step of precipitating glass ceramics on the sulfide glass by firing at a temperature not lower than the transition point. The positive electrode mixture layer and the negative electrode mixture layer are produced by any one of the methods described above.

  Although the embodiment of the present invention has been described above, the embodiment shown here can be variously modified. First, the manufacturing method shown in FIGS. 5 to 14 can be applied to each embodiment, and a solid state battery is manufactured by adjusting the heating temperature while measuring the thickness and / or electric resistance of the laminate. Can be created.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is sectional drawing of the battery according to Embodiment 1 of this invention. It is a figure which shows the raw material of a positive mix layer and a negative mix layer. It is a figure which shows the 1st process of the manufacturing method of a solid electrolyte layer. It is a figure which shows the 2nd process of the manufacturing method of a solid electrolyte layer. 3 is a diagram showing a method for manufacturing the solid state battery according to Embodiment 1. FIG. It is a figure which shows the solid battery after completion | finish of a heating. It is a graph which shows the relationship between the heating time of the metal mold | die in the manufacturing method according to this embodiment, the thickness of a laminated body, and the heating temperature of a metal mold | die. It is sectional drawing of the solid battery according to a comparative example. It is sectional drawing of the solid battery according to a comparative example. It is a figure which shows the manufacturing method according to another situation of this embodiment. It is a graph which shows the relationship between the electrical resistance of the thickness direction of a laminated body, the heating temperature, and the heating time in the manufacturing method according to this Embodiment. It is a graph which shows the temperature and electrical resistance of sulfide glass. It is a figure which shows the manufacturing method of the solid battery according to another situation of this embodiment. It is a figure which shows the manufacturing method of the solid battery according to another situation of this embodiment. It is sectional drawing of the battery according to Embodiment 2 of this invention. Fig. 16 is a diagram for illustrating a method for manufacturing the battery according to the second embodiment shown in Fig. 15. Fig. 16 is a diagram for illustrating a method for manufacturing the battery according to the second embodiment shown in Fig. 15. It is sectional drawing of the battery according to Embodiment 3 of this invention. It is a figure for demonstrating the manufacturing method of the battery according to Embodiment 3 shown in FIG. It is sectional drawing of the battery according to Embodiment 4 of this invention. It is a figure for demonstrating the manufacturing method of the battery according to Embodiment 4 shown in FIG. It is sectional drawing of the battery according to Embodiment 5 of this invention. FIG. 23 is a diagram for illustrating a method for manufacturing the battery according to Embodiment 5 shown in FIG. 22. FIG. 23 is a diagram for illustrating a method for manufacturing the battery according to Embodiment 5 shown in FIG. 22. It is sectional drawing of the battery according to Embodiment 6 of this invention. It is a figure for demonstrating the manufacturing method of a positive mix layer. It is a figure for demonstrating the manufacturing method of a positive mix layer. It is a figure for demonstrating the manufacturing method of a positive mix layer. It is a figure for demonstrating the manufacturing method of a solid electrolyte layer. It is a figure for demonstrating the manufacturing method of a solid electrolyte layer. It is a figure for demonstrating the manufacturing method of a solid electrolyte layer. It is a figure for demonstrating the manufacturing method of a negative mix layer. It is a figure for demonstrating the manufacturing method of a negative mix layer. It is a figure for demonstrating the manufacturing method of a negative mix layer. FIG. 26 is a diagram for explaining another method for manufacturing the battery shown in FIG. 25. FIG. 26 is a diagram for explaining another method for manufacturing the battery shown in FIG. 25. FIG. 26 is a diagram for explaining another method for manufacturing the battery shown in FIG. 25.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Solid battery, 10 Positive electrode collector, 20 Negative electrode collector, 30 Solid electrolyte layer, 31 Sulfide glass, 32 Glass ceramics, 100 Positive electrode material layer, 110 Positive electrode active material, 120 Conductive auxiliary material, 200 Negative electrode material Layer, 210 Negative electrode active material.

Claims (2)

  1. A step of laminating an inorganic glass layer on a composite layer containing a positive electrode or negative electrode active material;
    The laminated body is heated to a temperature equal to or higher than the transition point of the inorganic glass while pressing the laminate in the thickness direction, thereby precipitating ceramics in the inorganic glass layer, thereby reducing the electrical resistance of the inorganic glass compared to before the ceramics are deposited, and a solid electrolyte. Forming a layer,
    The step of reducing the electrical resistance in the solid electrolyte layer includes a step of monitoring the thickness of the laminate during heating and adjusting the heating conditions according to the thickness.
  2.   The method of forming a solid electrolyte layer according to claim 1, wherein the step of forming the solid electrolyte layer includes a step of monitoring an electrical resistance of the laminate during heating and adjusting a heating condition according to the electrical resistance.
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JP2013214421A (en) * 2012-04-02 2013-10-17 National Institute Of Advanced Industrial & Technology Carbon-solid electrolyte complex and manufacturing method of the same

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