JP2012248468A - Electrode body for all-solid battery, all-solid battery and methods for producing electrode body and all-solid battery - Google Patents

Electrode body for all-solid battery, all-solid battery and methods for producing electrode body and all-solid battery Download PDF

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JP2012248468A
JP2012248468A JP2011120496A JP2011120496A JP2012248468A JP 2012248468 A JP2012248468 A JP 2012248468A JP 2011120496 A JP2011120496 A JP 2011120496A JP 2011120496 A JP2011120496 A JP 2011120496A JP 2012248468 A JP2012248468 A JP 2012248468A
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JP5494572B2 (en
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Kokichi Doi
孝吉 土井
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Toyota Motor Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

PROBLEM TO BE SOLVED: To provide an electrode body for all-solid battery which can secure lithium ion conductivity with a simple process and without limiting kinds of a solid electrolyte while reducing the proportion of an electrolyte more than in a conventional method and which can obtain high capacity density; an all-solid battery; and methods for producing the electrode body and the all-solid battery.SOLUTION: In an electrode body 60 for an all-solid battery comprising an electrode laminate including one or more of solid electrolyte layer 61 and one or more of active material layer 64, a separator layer is arranged in a direction intersecting the lamination direction of the electrode laminate so as to come into contact with the end of the electrode laminate.

Description

本発明は、全固体電池用の電極体及び全固体電池並びにそれらの製造方法に関する。   The present invention relates to an electrode body for an all solid state battery, an all solid state battery, and a method for producing them.

近年、二次電池は、パソコン、ビデオカメラ、及び携帯電話等の電源として、あるいは自動車や電力貯蔵用の電源として、なくてはならない重要な構成要素となってきている。   In recent years, a secondary battery has become an indispensable component as a power source for personal computers, video cameras, mobile phones, and the like, or as a power source for automobiles and power storage.

二次電池の中でも特にリチウムイオン二次電池は、他の二次電池よりも容量密度が高く、高電圧での動作が可能という特徴を有している。そのため、小型軽量化を図りやすい二次電池として情報関連機器や通信機器に使用されており、近年、低公害車としての電気自動車やハイブリッド自動車用の高出力且つ高容量のリチウムイオン二次電池の開発が進められている。   Among secondary batteries, a lithium ion secondary battery has a feature that it has a higher capacity density than other secondary batteries and can operate at a high voltage. Therefore, it is used in information-related equipment and communication equipment as secondary batteries that are easy to reduce in size and weight. In recent years, high-output and high-capacity lithium-ion secondary batteries for electric vehicles and hybrid vehicles as low-pollution vehicles have been used. Development is underway.

リチウムイオン二次電池またはリチウム二次電池には、正極層及び負極層と、これらの間に配置されるリチウム塩を含む電解質とが備えられ、電解質は、非水系の液体又は固体によって構成される。電解質に非水系の液体電解質が用いられる場合には、電解液が正極層の内部へと浸透するため、正極層を構成する正極活物質と電解質との界面が形成されやすく、性能を向上させやすい。ところが、広く用いられている電解液は可燃性であるため、短絡時の温度上昇を抑える安全装置の取り付けや短絡防止等の安全性を確保するためのシステムを搭載する必要がある。これに対し、液体電解質を固体電解質に変えて、電池を全固体化した全固体電池は、電池内に可燃性の有機溶媒を用いないので、安全装置の簡素化が図れ、製造コストや生産性に優れると考えられており、開発が進められている。   A lithium ion secondary battery or a lithium secondary battery includes a positive electrode layer and a negative electrode layer, and an electrolyte containing a lithium salt disposed between the positive electrode layer and the negative electrode layer, and the electrolyte is constituted by a non-aqueous liquid or solid. . When a non-aqueous liquid electrolyte is used for the electrolyte, the electrolyte solution penetrates into the positive electrode layer, so that an interface between the positive electrode active material constituting the positive electrode layer and the electrolyte is easily formed, and performance is easily improved. . However, since widely used electrolytes are flammable, it is necessary to install a system for ensuring safety such as attachment of a safety device that suppresses temperature rise at the time of short circuit and prevention of short circuit. In contrast, an all-solid battery in which the liquid electrolyte is changed to a solid electrolyte to make the battery all solid does not use a flammable organic solvent in the battery, so the safety device can be simplified, and manufacturing costs and productivity can be reduced. It is considered excellent and is being developed.

固体電解質層が正極層と負極層との間に配設される全固体電池では、活物質及び電解質が固体であるため、電解質が活物質の内部へ浸透しにくく、活物質と電解質との界面が低減しやすい。それゆえ、全固体電池では、活物質の粉末と固体電解質の粉末とを混合した混合粉末を含有する合材を電極として用いることにより、界面の面積を増大させている。   In an all-solid battery in which the solid electrolyte layer is disposed between the positive electrode layer and the negative electrode layer, the active material and the electrolyte are solid, so that the electrolyte hardly penetrates into the active material, and the interface between the active material and the electrolyte Is easy to reduce. Therefore, in the all-solid battery, the area of the interface is increased by using, as an electrode, a composite material containing a mixed powder obtained by mixing an active material powder and a solid electrolyte powder.

全固体電池における正極合材及び負極合材は一般に、活物質、固体電解質等の粒子を混合してスラリーとし、所定の膜厚に塗工及び乾燥することによって得られ得る。   In general, the positive electrode mixture and the negative electrode mixture in an all-solid battery can be obtained by mixing particles such as an active material and a solid electrolyte into a slurry, and coating and drying to a predetermined film thickness.

ただし、全固体電池は、液系リチウム電池に比べてリチウム伝導度が低いために、電解質割合を多くしてリチウムイオン伝導性を確保する必要があった。上記のような工程では、活物質、固体電解質等の各粒子は正極合材及び負極合材中でランダムに配列することになるため、パーコレーションリミットにより、合材層の厚さ方向について連続的なリチウムイオン伝導パスを形成するには多量の電解質を投入する必要があった。このように、リチウムイオン伝導度を確保するために多くの電解質を混合する必要があり、その分、活物質の体積割合を少なくせざるをえず、出力密度を確保しつつ、容量密度を確保することが困難であった。   However, since the all-solid-state battery has a lower lithium conductivity than the liquid lithium battery, it is necessary to ensure the lithium ion conductivity by increasing the electrolyte ratio. In the process as described above, since the particles such as the active material and the solid electrolyte are randomly arranged in the positive electrode mixture and the negative electrode mixture, the percolation limit causes continuous particles in the thickness direction of the mixture layer. In order to form a lithium ion conduction path, it was necessary to add a large amount of electrolyte. In this way, it is necessary to mix many electrolytes in order to ensure lithium ion conductivity, and accordingly, the volume ratio of the active material must be reduced, and the capacity density is ensured while ensuring the output density. It was difficult to do.

このような課題に対して、従来、リチウムイオン伝導度を確保するために、熱分解によって除去可能な多孔体構造を有する鋳型に電解質を含浸させ、焼成することによって、骨格構造を有した電解質構造を形成すること（特許文献１）が提案され、また、フォトレジストにより形成した、リチウムと合金化する金属の多孔質体からなる島状電極を用いること（特許文献２）が提案されている。   Conventionally, in order to ensure lithium ion conductivity, an electrolyte structure having a skeleton structure is obtained by impregnating an electrolyte in a mold having a porous structure that can be removed by thermal decomposition and firing. (Patent Document 1) is proposed, and the use of an island-shaped electrode made of a porous metal made of a metal alloyed with lithium formed by a photoresist is proposed (Patent Document 2).

特開２００６−２６０８８７号明細書Japanese Patent Application Laid-Open No. 2006-260887 特開２０１０−１４６７３２号明細書JP 2010-146732 A

しかしながら、特許文献１に記載される焼成プロセスは、硫化物系固体電解質に対しては適用することができない。また、特許文献１及び特許文献２に記載されるプロセスは、複雑なプロセスが必要となり、製造プロセスとして大型化及び量産化に適用しにくいといった問題がある。   However, the firing process described in Patent Document 1 cannot be applied to sulfide-based solid electrolytes. Further, the processes described in Patent Document 1 and Patent Document 2 require a complicated process, and there is a problem that it is difficult to apply the process to enlargement and mass production.

そこで、固体電解質の種類が制限されず且つ簡便なプロセスによって、従来よりも電解質の割合を減らしつつリチウムイオン伝導度を確保でき、高い容量密度を得ることができる全固体電池用の電極体及び全固体電池並びにそれらの製造方法が望まれている。   Therefore, the type of solid electrolyte is not limited, and a simple process can secure lithium ion conductivity while reducing the proportion of the electrolyte as compared with the conventional one, and an electrode body for an all-solid battery that can obtain a high capacity density and all Solid batteries and methods for their production are desired.

本発明は、規則的に配置した電解質層と活物質層とを含む電極体、及びその電極体を含む全固体電池、並びにそれらの製造方法を対象とする。   The present invention is directed to an electrode body including regularly arranged electrolyte layers and active material layers, an all-solid battery including the electrode body, and a method for manufacturing the same.

本発明は、１以上の固体電解質層及び１以上の活物質層を含む電極積層体からなる全固体電池用電極体であって、電極積層体の端部に接するように、電極積層体の積層方向と交差する方向にセパレータ層が配置される、全固体電池用電極体である。   The present invention is an electrode body for an all-solid battery comprising an electrode laminate including one or more solid electrolyte layers and one or more active material layers, wherein the electrode laminate is laminated so as to be in contact with an end of the electrode laminate. It is an electrode body for all-solid-state batteries in which a separator layer is arranged in a direction crossing the direction.

本発明はまた、１以上の第１の固体電解質層及び１以上の第１の活物質層を含む第１の電極積層体、１以上の第２の固体電解質層及び１以上の第２の活物質層を含む第２の電極積層体、並びに第１及び第２の電極積層体の間に、第１及び第２の電極積層体の端部に接するように、第１及び第２の電極積層体の積層方向と交差する方向に配置されたセパレータ層を含む、全固体電池である。   The present invention also provides a first electrode stack including one or more first solid electrolyte layers and one or more first active material layers, one or more second solid electrolyte layers, and one or more second active materials. The second electrode stack including the material layer, and the first and second electrode stacks between the first and second electrode stacks so as to be in contact with the end portions of the first and second electrode stacks It is an all-solid-state battery including a separator layer arranged in a direction crossing the stacking direction of the body.

本発明はまた、１以上の固体電解質層及び１以上の活物質層を含む電極積層体ブロックを形成する工程；並びに
電極積層体ブロックを、積層面に垂直方向に切断して、複数個の電極体を形成する工程；
を含む、全固体電池用電極体の製造方法であって、電極体の端部に接するように、電極体の積層方向と交差する方向にセパレータ層が配置される、全固体電池用電極体の製造方法である。 The present invention also includes a step of forming an electrode laminate block including one or more solid electrolyte layers and one or more active material layers; and a plurality of electrodes by cutting the electrode laminate block in a direction perpendicular to the laminate surface. Forming a body;
A method for producing an electrode body for an all-solid battery, comprising: a separator layer disposed in a direction intersecting with the stacking direction of the electrode bodies so as to be in contact with an end of the electrode body; It is a manufacturing method.

本発明はまた、１以上の第１の固体電解質層及び１以上の第１の活物質層を含む第１の電極積層体ブロックを形成する工程；
１以上の第２の固体電解質層及び１以上の第２の活物質層を含む第２の電極積層体ブロックを形成する工程；
第１の電極積層体ブロック及び第２の電極積層体ブロックを、それぞれの積層面に垂直方向に切断して、複数個の第１の電極体及び第２の電極体を形成する工程；並びに
一組の第１の電極体及び第２の電極体の間に、第１の電極体及び第２の電極体の端部に接するように、第１の電極体及び第２の電極体の積層方向と交差する方向にセパレータ層を配置して、セパレータ層の面に垂直方向にプレスする工程、
を含む、第１の電極体、セパレータ層、及び第２の電極体を含む全固体電池の製造方法である。 The present invention also includes a step of forming a first electrode laminate block including one or more first solid electrolyte layers and one or more first active material layers;
Forming a second electrode laminate block including one or more second solid electrolyte layers and one or more second active material layers;
Cutting the first electrode laminate block and the second electrode laminate block in the direction perpendicular to the respective laminate surfaces to form a plurality of first electrode bodies and second electrode bodies; and The stacking direction of the first electrode body and the second electrode body so as to be in contact with the ends of the first electrode body and the second electrode body between the first electrode body and the second electrode body of the set Placing the separator layer in a direction intersecting with and pressing in a direction perpendicular to the surface of the separator layer,
Is a manufacturing method of an all-solid-state battery including a first electrode body, a separator layer, and a second electrode body.

本発明によれば、固体電解質の種類が制限されず且つ簡便な製造方法で、高い容量密度を得ることができる全固体電池用の電極体及びその電極体を含む全固体電池を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the kind of solid electrolyte is not restrict | limited, The all-solid-state battery containing the electrode body for all-solid-state batteries which can obtain a high capacity | capacitance density with a simple manufacturing method, and the electrode body is provided. it can.

本発明の一実施態様における、基材上への固体電解質膜、導電助剤膜、及び活物質膜の形成方法の模式図である。It is a schematic diagram of the formation method of the solid electrolyte membrane on the base material, a conductive support film | membrane, and an active material film | membrane in one embodiment of this invention. 本発明の一実施態様における、固体電解質膜及び活物質膜を含む電極積層体の模式図である。It is a schematic diagram of the electrode laminated body containing the solid electrolyte membrane and the active material film in one embodiment of the present invention. 本発明の一実施態様における、固体電解質層、導電助剤層、及び活物質層を含む電極積層体ブロックの模式図である。It is a schematic diagram of the electrode laminated body block containing the solid electrolyte layer, the conductive support agent layer, and the active material layer in one embodiment of this invention. 本発明の一実施態様における、固体電解質層及び活物質層を含む電極積層体ブロックの模式図である。It is a schematic diagram of the electrode laminated body block containing the solid electrolyte layer and active material layer in one embodiment of this invention. 本発明の一実施態様における、電極積層体から切り出した固体電解質層、導電助剤層、及び活物質層を含む電極体の模式図である。It is a schematic diagram of the electrode body containing the solid electrolyte layer cut out from the electrode laminated body in one embodiment of this invention, a conductive support agent layer, and an active material layer. 本発明の一実施態様における、電極積層体から切り出した固体電解質層及び活物質層を含む電極体の模式図である。It is a schematic diagram of the electrode body containing the solid electrolyte layer and active material layer which were cut out from the electrode laminated body in one embodiment of this invention. 本発明の一実施態様における、固体電解質層、導電助剤層、及び活物質層を含む第１の電極積層体、固体電解質層及び活物質層を含む第２の電極積層体、並びに第１の電極積層体及び第２の電極積層体の間に形成されたセパレータ層を含む、全固体電池の断面模式図である。In one embodiment of the present invention, a first electrode laminate including a solid electrolyte layer, a conductive aid layer, and an active material layer, a second electrode laminate including a solid electrolyte layer and an active material layer, and a first It is a cross-sectional schematic diagram of an all-solid-state battery including a separator layer formed between the electrode laminate and the second electrode laminate. 本発明の一実施態様における、固体電解質層、導電助剤層、及び活物質層を含む第１の電極積層体、固体電解質層及び活物質層を含む第２の電極積層体、第１の電極積層体及び第２の電極積層体の間に形成されたセパレータ層、並びに第１の集電体及び第２の集電体を含む、全固体電池の断面模式図である。In one embodiment of the present invention, a first electrode laminate including a solid electrolyte layer, a conductive aid layer, and an active material layer, a second electrode laminate including a solid electrolyte layer and an active material layer, and a first electrode It is a cross-sectional schematic diagram of an all-solid-state battery including a separator layer formed between a laminate and a second electrode laminate, and a first current collector and a second current collector.

本発明は、全固体電池に用いられる電極体であって、固体電解質層及び活物質層がそれぞれ１以上の層数を有して積層された構造を有する電極積層体からなる電極体である。電極体は、全固体電池に用いられるときに、電極積層体の端部に接するように、電極積層体の積層方向と交差する方向にセパレータ層が配置される。   The present invention is an electrode body used for an all-solid battery, and is an electrode body composed of an electrode stack having a structure in which a solid electrolyte layer and an active material layer each have a number of layers of 1 or more. When the electrode body is used in an all-solid battery, a separator layer is disposed in a direction intersecting the stacking direction of the electrode stack so as to be in contact with the end of the electrode stack.

本発明の電極体によれば、固体電解質層及び活物質層が積層構造を有することによって、電極体内部に直線的な配向性を有した電解質層を形成することができるため、電極体に含まれる電解質の量を少なくしても、優れたリチウムイオン伝導性を有することができる。したがって、本発明の電極体においては、電解質量を従来の全固体電池の電極に含まれる量よりも減らすことができ、その分、活物質量を増やすことができるので、本発明の電極体を含む全固体電池と従来の全固体電池を比較すると、同じ体積の電池を作ったときは、本発明の電池の方が高容量を得ることができ、あるいは同じ性能の電池にしたときは、本発明の電池の方が小型に作ることが可能となる。   According to the electrode body of the present invention, since the solid electrolyte layer and the active material layer have a laminated structure, an electrolyte layer having linear orientation can be formed inside the electrode body. Even if the amount of electrolyte to be reduced is reduced, excellent lithium ion conductivity can be obtained. Therefore, in the electrode body of the present invention, the electrolytic mass can be reduced from the amount contained in the electrode of the conventional all-solid battery, and the amount of the active material can be increased accordingly. Comparing the all-solid battery and the conventional all-solid battery, when the battery of the same volume is made, the battery of the present invention can obtain a higher capacity, or when the battery of the same performance is made, The battery of the invention can be made smaller.

本発明において、１以上の固体電解質層及び１以上の活物質層は積層構造を有し、好ましくは交互に積層される。   In the present invention, one or more solid electrolyte layers and one or more active material layers have a laminated structure, and are preferably laminated alternately.

電解質層と活物質層とが交互に積層されることにより、活物質と電解質との界面を増加することができ、より効率的なリチウムイオンの伝導パスを形成することができる。   By alternately stacking the electrolyte layer and the active material layer, the interface between the active material and the electrolyte can be increased, and a more efficient lithium ion conduction path can be formed.

本発明において、固体電解質層に含まれる固体電解質材料としては、全固体電池の固体電解質として利用可能な材料を用いることができる。例えば、例えば、Ｌｉ2Ｓ−ＳｉＳ2、ＬｉＩ−Ｌｉ2Ｓ−ＳｉＳ2、ＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｓ5、ＬｉＩ−Ｌｉ2Ｓ−Ｂ2Ｓ3、Ｌｉ3ＰＯ4−Ｌｉ2Ｓ−Ｓｉ2Ｓ、Ｌｉ3ＰＯ4−Ｌｉ2Ｓ−ＳｉＳ2、ＬｉＰＯ4−Ｌｉ2Ｓ−ＳｉＳ、ＬｉＩ−Ｌｉ2Ｓ−Ｐ2Ｏ5、ＬｉＩ−Ｌｉ3ＰＯ4−Ｐ2Ｓ5、若しくはＬｉ2Ｓ−Ｐ2Ｓ5等の硫化物系固体電解質、Ｌｉ2Ｏ−Ｂ2Ｏ3−Ｐ2Ｏ5、Ｌｉ2Ｏ−ＳｉＯ2、Ｌｉ2Ｏ−Ｂ2Ｏ3、若しくはＬｉ2Ｏ−Ｂ2Ｏ3−ＺｎＯ等の酸化物系非晶質固体電解質、Ｌｉ1.3Ａｌ0.3Ｔｉ0.7（ＰＯ4）3、Ｌｉ1+x+yＡxＴｉ2-xＳｉyＰ3-yＯ12（Ａは、ＡｌまたはＧａ、０≦ｘ≦０．４、０＜ｙ≦０．６）、［（Ｂ1/2Ｌｉ1/2）1-zＣz］ＴｉＯ3（Ｂは、Ｌａ、Ｐｒ、Ｎｄ、またはＳｍ、ＣはＳｒまたはＢａ、０≦ｚ≦０．５）、Ｌｉ5Ｌａ3Ｔａ2Ｏ12、Ｌｉ7Ｌａ3Ｚｒ2Ｏ12、Ｌｉ6ＢａＬａ2Ｔａ2Ｏ12、若しくはＬｉ3.6Ｓｉ0.6Ｐ0.4Ｏ4等の結晶質酸化物、Ｌｉ3ＰＯ(4-3/2w)Ｎw（ｗ＜１）等の結晶質酸窒化物、またはＬｉＩ、ＬｉＩ−Ａｌ2Ｏ3、Ｌｉ3Ｎ、若しくはＬｉ3Ｎ−ＬｉＩ−ＬｉＯＨ等を用いることができる。硫化物系固体電解質が、優れたリチウムイオン伝導性を有する点で好ましく用いられる。また、本発明の固体電解質として、リチウム塩を含むポリエチレンオキシド、ポリプロピレンオキシド、ポリフッ化ビニリデン、またはポリアクリロニトリル等の半固体のポリマー電解質も使用することができる。 In the present invention, as the solid electrolyte material contained in the solid electrolyte layer, a material that can be used as a solid electrolyte of an all-solid battery can be used. For example, for example, Li 2 S-SiS 2, LiI-Li 2 S-SiS 2, LiI-Li 2 S-P 2 S 5, LiI-Li 2 S-B 2 S 3, Li 3 PO 4 -Li 2 S -Si 2 S, Li 3 PO 4 -Li 2 S-SiS 2, LiPO 4 -Li 2 S-SiS, LiI-Li 2 S-P 2 O 5, LiI-Li 3 PO 4 -P 2 S 5, or Sulfide-based solid electrolytes such as Li 2 S—P 2 S 5 , Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—SiO 2 , Li 2 O—B 2 O 3 , or Li 2 O Oxide-based amorphous solid electrolyte such as -B 2 O 3 -ZnO, Li 1.3 Al 0.3 Ti 0.7 (PO 4 ) 3 , Li 1 + x + y A x Ti 2-x Si y P 3-y O 12 (A is Al or Ga, 0 ≦ x ≦ 0.4, 0 <y ≦ 0.6), [(B 1/2 Li 1/2 ) 1−z C z ] TiO 3 (B is La, Pr, Nd, or Sm, Is Sr or Ba, 0 ≦ z ≦ 0.5) , Li 5 La 3 Ta 2 O 12, Li 7 La 3 Zr 2 O 12, Li 6 BaLa 2 Ta 2 O 12 or Li 3.6 Si 0.6 P 0.4 O 4 , Crystalline oxide such as Li 3 PO (4-3 / 2w) N w (w <1), or LiI, LiI—Al 2 O 3 , Li 3 N, or Li 3 N -LiI-LiOH or the like can be used. A sulfide-based solid electrolyte is preferably used in that it has excellent lithium ion conductivity. Further, as the solid electrolyte of the present invention, a semi-solid polymer electrolyte such as polyethylene oxide, polypropylene oxide, polyvinylidene fluoride, or polyacrylonitrile containing a lithium salt can also be used.

本発明において、活物質層に含まれる活物質材料としては、全固体電池の電極活物質として利用可能な材料を用いることができる。活物質材料として、例えば、コバルト酸リチウム（ＬｉＣｏＯ2）、ニッケル酸リチウム（ＬｉＮｉＯ2）、マンガン酸リチウム（ＬｉＭｎ2Ｏ4）、ＬｉＣｏ1/3Ｎｉ1/3Ｍｎ1/3Ｏ2、Ｌｉ1+xＭｎ2-x-yＭyＯ4（Ｍは、Ａｌ、Ｍｇ、Ｃｏ、Ｆｅ、Ｎｉ、及びＺｎから選ばれる１種以上の金属元素）で表される組成の異種元素置換Ｌｉ−Ｍｎスピネル、チタン酸リチウム（ＬｉxＴｉＯy）、リン酸金属リチウム（ＬｉＭＰＯ4、ＭはＦｅ、Ｍｎ、Ｃｏ、またはＮｉ）、酸化バナジウム（Ｖ2Ｏ5）及び酸化モリブデン（ＭｏＯ3）等の遷移金属酸化物、硫化チタン（ＴｉＳ2）、グラファイト及びハードカーボン等の炭素材料、リチウムコバルト窒化物（ＬｉＣｏＮ）、リチウムシリコン酸化物（ＬｉxＳｉyＯz）、リチウム金属（Ｌｉ）、リチウム合金（ＬｉＭ、Ｍは、Ｓｎ、Ｓｉ、Ａｌ、Ｇｅ、Ｓｂ、またはＰ）、リチウム貯蔵性金属間化合物（ＭｇxＭまたはＮｙＳｂ、ＭはＳｎ、Ｇｅ、またはＳｂ、ＮはＩｎ、Ｃｕ、またはＭｎ）等、並びにこれらの誘導体が挙げられる。 In the present invention, as the active material contained in the active material layer, a material that can be used as an electrode active material of an all-solid battery can be used. Examples of the active material include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , Li 1 + x Mn 2-xy M y O 4 (M is, Al, Mg, Co, Fe, Ni, and one or more metal elements selected from Zn) different element substituted Li-Mn spinel composition represented by, Transition metal oxidation such as lithium titanate (Li x TiO y ), lithium metal phosphate (LiMPO 4 , M is Fe, Mn, Co, or Ni), vanadium oxide (V 2 O 5 ), and molybdenum oxide (MoO 3 ) things, titanium sulfide (TiS 2), carbon materials such as graphite and hard carbon, lithium-cobalt nitride (LiCoN), lithium silicon oxide (Li x Si y O z) , lithium metal (L ), Lithium alloy (LiM, M is, Sn, Si, Al, Ge, Sb, or P), lithium storage intermetallic compound (Mg x M or NySb, M is Sn, Ge or Sb, N is an In,,, Cu, or Mn) and the like, and derivatives thereof.

電極積層体は、固体電解質層及び活物質層の層間の少なくとも１つに導電助剤層を含むことができる。活物質の電子導電性が不足する場合に所望により電極積層体に導電助剤層を加えることができ、電極体の電子導電性を向上することができる。さらに好ましくは、電極積層体は、固体電解質層／導電助剤層／活物質層の３層の繰り返しを含むか、または固体電解質層／導電助剤層／活物質層の３層の繰り返しからなることができ、さらに電子導電性を向上することができる。   The electrode laminate can include a conductive additive layer in at least one of the solid electrolyte layer and the active material layer. When the electronic conductivity of the active material is insufficient, a conductive auxiliary agent layer can be added to the electrode laminate as desired, and the electronic conductivity of the electrode body can be improved. More preferably, the electrode laminate includes a repetition of three layers of solid electrolyte layer / conductive auxiliary agent layer / active material layer, or consists of repetition of three layers of solid electrolyte layer / conductive auxiliary agent layer / active material layer. In addition, the electronic conductivity can be improved.

本発明においては、導電助剤層も連続性を有するため、例えばカーボンを導電助剤として用いる場合、電極積層体の全体量に対して約１ｗｔ％以下等の少量のカーボンで電子導電性を確保することができ、またカーボンの種類が限定されない。導電助剤層に含まれる導電助剤の材料としては、特に制限されるものではなく、黒鉛、カーボンブラック、アセチレンブラック等の全固体電池に従来使用される材料を用いることができる。   In the present invention, since the conductive auxiliary agent layer also has continuity, for example, when carbon is used as the conductive auxiliary agent, electronic conductivity is ensured by a small amount of carbon such as about 1 wt% or less with respect to the total amount of the electrode laminate. The type of carbon is not limited. The material of the conductive assistant contained in the conductive assistant layer is not particularly limited, and materials conventionally used for all solid state batteries such as graphite, carbon black, and acetylene black can be used.

固体電解質層及び活物質層は、それぞれバインダーを含んでもよい。バインダーの材料としては、ポリテトラフルオロエチレン、ポリトリフルオロエチレン、ポリエチレン、ニトリルゴム、ポリブタジエンゴム、ブチルゴム、水素添加ブチレンゴム、ポリスチレン、スチレンブタジエンゴム、スチレンブタジエンラテックス、多硫化ゴム、ニトロセルロース、アクリロニトリルブタジエンゴム、ポリフッ化ビニル、ポリフッ化ビニリデン、フッ素ゴム等が望ましいが、特に制限されない。電極積層体に含まれ得るバインダー量は、従来の全固体電池に用いられる量またはそれよりも少なくすることができ、例えば電極積層体全体に対して約０．１〜５ｗｔ％である。   Each of the solid electrolyte layer and the active material layer may include a binder. As binder materials, polytetrafluoroethylene, polytrifluoroethylene, polyethylene, nitrile rubber, polybutadiene rubber, butyl rubber, hydrogenated butylene rubber, polystyrene, styrene butadiene rubber, styrene butadiene latex, polysulfide rubber, nitrocellulose, acrylonitrile butadiene rubber Polyvinyl fluoride, polyvinylidene fluoride, fluororubber and the like are desirable, but not particularly limited. The amount of binder that can be included in the electrode stack can be less than or the amount used in conventional all solid state batteries, for example, about 0.1-5 wt% with respect to the entire electrode stack.

本発明において、電極積層体に含まれる固体電解質の割合は、活物質にリチウムを十分に供給できる割合であればよい。従来の全固体電池が、電極中の電解質割合が、電極全体に対して少なくとも４０〜６０ｖｏｌ％程度が必要であったのに対し、本発明における電極積層体に含まれる電解質割合は、８〜１０Ｃのような高いＣレートで充放電させる場合においても４０ｖｏｌ％よりも少なくすることができ、好ましくは１０〜３０ｖｏｌ％、さらに好ましくは１５〜２５ｖｏｌ％にすることができる。   In this invention, the ratio of the solid electrolyte contained in an electrode laminated body should just be a ratio which can fully supply lithium to an active material. In the conventional all-solid-state battery, the electrolyte ratio in the electrode needs to be at least about 40 to 60 vol% with respect to the entire electrode, whereas the electrolyte ratio included in the electrode laminate in the present invention is 8 to 10 C. Even in the case of charging and discharging at a high C rate as described above, it can be made less than 40 vol%, preferably 10 to 30 vol%, more preferably 15 to 25 vol%.

本発明の電極体によれば、固体電解質層及び活物質層が積層構造を有することによって、効率的に電解質を介して活物質にリチウムを送り込み活物質からリチウムを取り出すことができ、従来よりも少ない電解質比率でも電池として機能することができる。固体電解質層及び活物質層が所定の厚みを有して交互に規則的に並んだ積層構造を有する場合は、より効率的に、電解質を介して活物質にリチウムを送り込み且つ活物質からリチウムを取り出すことができ、好ましい。   According to the electrode body of the present invention, since the solid electrolyte layer and the active material layer have a laminated structure, lithium can be efficiently fed into the active material through the electrolyte, and lithium can be taken out from the active material. Even a small electrolyte ratio can function as a battery. When the solid electrolyte layer and the active material layer have a laminated structure with a predetermined thickness and alternately arranged regularly, lithium is more efficiently fed into the active material through the electrolyte, and lithium is extracted from the active material. It can be taken out and is preferable.

本発明において、活物質層の一層あたりの厚みは、活物質として動作可能な範囲の厚みであればよく、例えば０．３〜８０μｍ厚、好ましくは１０〜４０μｍ厚にすることができる。   In the present invention, the thickness per layer of the active material layer may be a thickness that can be operated as an active material, and may be, for example, 0.3 to 80 μm, preferably 10 to 40 μm.

本発明において、固体電解質層の一層あたりの厚みは、活物質層の厚みに応じて、活物質層に十分なリチウムを供給できる厚みにすればよく、活物質層の厚みに対して約０．１〜０．７の比率の厚みを有することが好ましい。例えば４０μｍ厚の活物質層に対しては１０μｍ程度の電解質厚みを組み合わせると効果的である。   In the present invention, the thickness per layer of the solid electrolyte layer may be set to a thickness that can supply sufficient lithium to the active material layer according to the thickness of the active material layer, and is about 0. 0 to the thickness of the active material layer. It preferably has a thickness of 1 to 0.7. For example, for an active material layer having a thickness of 40 μm, it is effective to combine an electrolyte thickness of about 10 μm.

本発明の電極体において導電助剤層を用いる場合、導電助剤層の厚みについては、電極積層体が直線的な配向性構造を有することにより電子導電パスを容易に確保することができるため、活物質層及び固体電解質層の厚みに対して導電助剤層の厚みを薄くすることができる。   In the case of using a conductive additive layer in the electrode body of the present invention, the thickness of the conductive auxiliary layer can easily ensure an electronic conductive path by having a linear orientation structure of the electrode laminate, The thickness of the conductive auxiliary agent layer can be reduced with respect to the thickness of the active material layer and the solid electrolyte layer.

導電助剤層は、導電助剤として用いるカーボン等の粒子の一次粒子径程度の厚みにすることができ、例えば０．０５〜５μｍ、さらには０．０５〜１μｍの厚みにすることができる。活物質の電子伝導度に応じて導電助剤層の有無の選択及び厚みを変更することができ、例えば、活物質にコバルト酸リチウムを用いる場合は導電助剤層が無くてもよく、あるいは０．５μｍ厚以下で薄く設けてもよく、また電子伝導度の低い材料を活物質に用いる場合は２〜３μｍ程度の導電助剤層を設けてもよい。   The conductive auxiliary agent layer can have a thickness of about the primary particle diameter of particles such as carbon used as the conductive auxiliary agent, for example, 0.05 to 5 μm, and further 0.05 to 1 μm. Depending on the electronic conductivity of the active material, the selection and thickness of the conductive auxiliary layer can be changed. For example, when lithium cobaltate is used as the active material, the conductive auxiliary layer may be omitted or 0 The conductive auxiliary agent layer may be provided with a thickness of about 2 to 3 μm when a material having a low electron conductivity is used for the active material.

このように、本発明の電極体においては、電解質及び導電助剤の量を従来の固体電解質の電極体に含まれる量よりも少なくすることができるため、その分、電極体の単位体積当たりの活物質量を増やすことができる。   As described above, in the electrode body of the present invention, the amount of the electrolyte and the conductive additive can be made smaller than the amount contained in the electrode body of the conventional solid electrolyte, and accordingly, per unit volume of the electrode body. The amount of active material can be increased.

本発明の電極体は、必要とする電池の特性、大きさ等に応じて、例えば数ｍｍ角〜Ａ１〜サイズ等の任意の面積及び２０〜４００μｍ厚等の任意の厚みを有することができる。また、本発明の電極体によれば、上述のように電極体に含まれる活物質の割合を多くすることができるため、従来の全固体電池よりも小型または薄型の電池を作成することが可能である。   The electrode body of the present invention can have an arbitrary area such as several mm square to A1 size and an arbitrary thickness such as 20 to 400 μm, depending on the required characteristics and size of the battery. In addition, according to the electrode body of the present invention, since the proportion of the active material contained in the electrode body can be increased as described above, it is possible to create a battery that is smaller or thinner than the conventional all-solid battery. It is.

本発明はまた、１以上の第１の固体電解質層及び１以上の第１の活物質層を含む第１の電極積層体、１以上の第２の固体電解質層及び１以上の第２の活物質層を含む第２の電極積層体、並びに第１及び第２の電極積層体の間に、第１及び第２の電極積層体の端部に接するように、第１及び第２の電極積層体の積層方向と交差する方向に配置されたセパレータ層を含む、全固体電池を対象とする。   The present invention also provides a first electrode stack including one or more first solid electrolyte layers and one or more first active material layers, one or more second solid electrolyte layers, and one or more second active materials. The second electrode stack including the material layer, and the first and second electrode stacks between the first and second electrode stacks so as to be in contact with the end portions of the first and second electrode stacks An all-solid-state battery including a separator layer arranged in a direction intersecting with the stacking direction of the body is an object.

本発明の全固体電池において、第１の電極積層体及び第２の電極積層体はそれぞれ正極及び負極として機能し、それぞれ第１の活物質層及び第２の活物質層を含む。第１の活物質層及び第２の活物質層に含まれる活物質材料は、いずれかが正極活物質として機能する正極活物質であり、他方が負極活物質として機能する負極活物質であり、充放電電位が異なる電位を示す材料である。本発明において、正極活物質及び負極活物質には明確な区別はなく、上述の活物質材料から２種類の充放電電位を比較して、充放電電位が貴な電位を示すものを正極に、卑な電位を示すものを負極に用いて、任意の電圧の電池を構成することができる。   In the all solid state battery of the present invention, the first electrode laminate and the second electrode laminate function as a positive electrode and a negative electrode, respectively, and include a first active material layer and a second active material layer, respectively. One of the active material materials included in the first active material layer and the second active material layer is a positive electrode active material that functions as a positive electrode active material, and the other is a negative electrode active material that functions as a negative electrode active material, It is a material which shows the electric potential from which charging / discharging electric potential differs. In the present invention, there is no clear distinction between the positive electrode active material and the negative electrode active material, comparing two kinds of charge / discharge potentials from the above active material, A battery having an arbitrary voltage can be formed using a negative potential as a negative electrode.

また、第１の電極積層体及び第２の電極積層体はそれぞれ、第１の固体電解質層及び第２の固体電解質層を含む。第１の固体電解質層及び第２の固体電解質層に含まれる固体電解質材料は同じ固体電解質材料であることが好ましい。   The first electrode laminate and the second electrode laminate each include a first solid electrolyte layer and a second solid electrolyte layer. The solid electrolyte materials contained in the first solid electrolyte layer and the second solid electrolyte layer are preferably the same solid electrolyte material.

セパレータ層に含まれる材料は固体電解質であり、第１及び第２の固体電解質層に含まれる固体電解質材料と同じ材料を用いることができる。   The material contained in the separator layer is a solid electrolyte, and the same material as the solid electrolyte material contained in the first and second solid electrolyte layers can be used.

セパレータ層は、正極活物質層と負極活物質層との接触を防止し、固体電解質として機能することができる厚みを有することができ、例えば３〜５０μｍ厚であることができる。   The separator layer can have a thickness that prevents contact between the positive electrode active material layer and the negative electrode active material layer and can function as a solid electrolyte, and can be, for example, 3 to 50 μm thick.

第１の電極積層体、セパレータ層、及び第２の電極積層体を含む全固体電池の両端面に接して、第１及び第２の電極積層体の積層方向と交差する方向に、第１の集電体及び第２の集電体を配置することができる。   The first electrode stack, the separator layer, and the first electrode stack are in contact with both end faces of the all-solid-state battery including the second electrode stack and intersect the stacking direction of the first and second electrode stacks. A current collector and a second current collector can be disposed.

第１の集電体及び第２の集電体は、いずれかが正極集電体として機能し、他方が負極集電体として機能するものであり、第１の集電体及び第２の集電体の材料は、正極集電体及び負極集電体としての機能を有するものであれば限定されない。正極集電体の材料としては、導電性を有するものであれば特に限定されるものではなく、例えばＳＵＳ、アルミニウム、ニッケル、鉄、チタン、およびカーボン等を挙げることができ、ＳＵＳ及びアルミニウムが好ましい。さらに、正極集電体の形状としては、例えば、箔状、板状、メッシュ状等を挙げることができ、中でも箔状が好ましい。負極集電体の材料としては、導電性を有するものであれば特に限定されるものではないが、例えばＳＵＳ、銅、ニッケル、およびカーボン等を挙げることができ、ＳＵＳ及び銅が好ましい。さらに、負極集電体の形状としては、例えば、箔状、板状、メッシュ状等を挙げることができ、中でも箔状が好ましい。   One of the first current collector and the second current collector functions as a positive electrode current collector, and the other functions as a negative electrode current collector. The first current collector and the second current collector The material of the electric body is not limited as long as it has a function as a positive electrode current collector and a negative electrode current collector. The material of the positive electrode current collector is not particularly limited as long as it has conductivity, and examples thereof include SUS, aluminum, nickel, iron, titanium, and carbon, and SUS and aluminum are preferable. . Furthermore, examples of the shape of the positive electrode current collector include a foil shape, a plate shape, and a mesh shape. Among these, a foil shape is preferable. The material for the negative electrode current collector is not particularly limited as long as it has conductivity, and examples thereof include SUS, copper, nickel, and carbon, and SUS and copper are preferable. Furthermore, examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh shape. Among these, a foil shape is preferable.

第１の集電体及び第２の集電体の厚みは、特に限定されるものではなく、例えば１０〜５００μｍ程度の厚みの金属箔を用いることができる。   The thicknesses of the first current collector and the second current collector are not particularly limited, and for example, a metal foil having a thickness of about 10 to 500 μm can be used.

本発明はまた、電解質層及び活物質層を積層した電極積層体ブロック形成し、電極積層体ブロックを所定の幅で切り出すことによる、積層構造を有する全固体リチウム電池用電極体、及びその電極体を含む全固体電池の製造方法を提供する。   The present invention also provides an electrode body block for an all-solid-state lithium battery having a laminated structure by forming an electrode laminate block in which an electrolyte layer and an active material layer are laminated, and cutting out the electrode laminate block with a predetermined width, and the electrode body The manufacturing method of the all-solid-state battery containing is provided.

本発明の全固体電池用電極体の製造方法は、
１以上の固体電解質層及び１以上の活物質層を含む電極積層体ブロックを形成する工程；並びに
電極積層体ブロックを、積層面に垂直方向に切断して、複数個の電極体を形成する工程；
を含む方法である。この方法により製造された電極体が全固体電池に用いられるときに、電極体の端部に接するように、電極体の積層方向と交差する方向にセパレータ層が配置される。 The method for producing an electrode body for an all solid state battery of the present invention comprises
A step of forming an electrode laminate block including one or more solid electrolyte layers and one or more active material layers; and a step of cutting the electrode laminate block in a direction perpendicular to the lamination surface to form a plurality of electrode bodies ;
It is a method including. When the electrode body manufactured by this method is used for an all-solid-state battery, the separator layer is arranged in a direction intersecting with the stacking direction of the electrode bodies so as to be in contact with the end of the electrode body.

電極積層体ブロックは、同じ基材上または異なる基材上に固体電解質膜及び活物質膜を形成し、固体電解質膜及び活物質膜を積層することにより、形成され得る。   The electrode laminate block can be formed by forming a solid electrolyte membrane and an active material membrane on the same substrate or different substrates, and laminating the solid electrolyte membrane and the active material membrane.

基材は、固体電解質膜または活物質膜をその上に形成することができるものであれば特に制限されるものではなく、フィルム状の柔軟性を有する基材や硬質基材等を用いることができ、例えばテフロン（登録商標）、ポリエチレンテレフタレート（ＰＥＴ）フィルム等の基材を用いることができる。   The substrate is not particularly limited as long as a solid electrolyte membrane or an active material film can be formed thereon, and a substrate having a film-like flexibility or a rigid substrate may be used. For example, a substrate such as Teflon (registered trademark) or polyethylene terephthalate (PET) film can be used.

固体電解質膜及び活物質膜の基材上への形成は、スラリー塗工プロセス、ブラスト法、エアロゾルデポジション法、コールドスプレー法、スパッタリング法、気相成長法、または溶射法等を用いて行うことができ、スラリー塗工プロセスが簡便なプロセスで固体電解質膜及び活物質膜を得ることができ、好ましく用いられる。   The solid electrolyte membrane and the active material membrane are formed on the substrate by using a slurry coating process, a blast method, an aerosol deposition method, a cold spray method, a sputtering method, a vapor phase growth method, or a thermal spray method. It is possible to obtain a solid electrolyte membrane and an active material membrane by a process with a simple slurry coating process, which is preferably used.

スラリー塗工プロセスとしては、ダム式スラリーコーター、ドクターブレード法、グラビヤ転写法、リバースロールコータ等が挙げられる。   Examples of the slurry coating process include a dam type slurry coater, a doctor blade method, a gravure transfer method, and a reverse roll coater.

スラリー塗工プロセスによって固体電解質膜及び活物質膜を基材上へ形成する場合、固体電解質スラリー及び活物質スラリーの調製に用いる溶媒は、固体電解質及び活物質の性能に悪影響を与えないものであれば特に限定されないが、例えば炭化水素系有機溶媒のヘプタン、トルエン、ヘキサン等が挙げられ、好ましくは脱水処理して水分含有量を低くした炭化水素系有機溶媒が用いられる。   When the solid electrolyte membrane and the active material membrane are formed on the substrate by the slurry coating process, the solvent used for preparing the solid electrolyte slurry and the active material slurry should not adversely affect the performance of the solid electrolyte and the active material. Although not particularly limited, for example, hydrocarbon organic solvents such as heptane, toluene, hexane and the like can be mentioned. Preferably, a hydrocarbon organic solvent whose water content is reduced by dehydration treatment is used.

固体電解質膜及び活物質膜は、次に挙げる方法によって積層され得る。一実施態様において、固体電解質及び活物質のそれぞれのスラリーを調製し、調製した電解質スラリーを基材上に塗工及び乾燥して電解質膜を形成し、調製した活物質スラリーを電解質膜の上に塗工及び乾燥して活物質膜を形成して、電解質膜及び活物質膜の積層体を形成することができ、このようにして別個の基材上に電解質膜及び活物質膜の積層体を複数組形成し、各積層体を基材から剥離して、所望の層数まで各積層体を積層及びプレスして、電極積層体ブロックを形成することができる。   The solid electrolyte membrane and the active material membrane can be laminated by the following method. In one embodiment, each slurry of a solid electrolyte and an active material is prepared, and the prepared electrolyte slurry is coated and dried on a substrate to form an electrolyte membrane, and the prepared active material slurry is applied to the electrolyte membrane. The active material film can be formed by coating and drying to form a laminate of the electrolyte membrane and the active material film. In this way, the laminate of the electrolyte membrane and the active material film can be formed on separate substrates. A plurality of sets are formed, each laminate is peeled from the substrate, and each laminate is laminated and pressed to a desired number of layers to form an electrode laminate block.

別法では、固体電解質及び活物質のそれぞれのスラリーを調製し、基材上に調製した電解質スラリーを塗工及び乾燥して電解質膜を形成し、その電解質膜の上に調製した活物質スラリーを塗工及び乾燥して活物質膜を形成して、電解質膜及び活物質膜の積層体Ａを形成し、別個の基材上に活物質スラリーを塗工及び乾燥して活物質膜を形成し、その活物質膜の上に電解質スラリーを塗工及び乾燥して電解質膜を形成して、活物質膜及び電解質膜の積層体Ｂを複数組形成した後、基材上の積層体Ａをベースとして、積層体Ｂを、積層体Ａに転写して、転写した側から基材を剥離し、順次、所望の層数まで積層体Ｂの転写及び基材の剥離を繰り返して電極積層体ブロックを形成してもよい。ベースとした基材は任意の工程で剥離され得、例えば電極積層体ブロックの形成後、またはその後の電極積層体ブロックの切断後の工程等で剥離され得る。この場合、得られた電極積層体ブロックの密度に応じてプレスの有無を選択してもよい。   In another method, each slurry of a solid electrolyte and an active material is prepared, and the electrolyte slurry prepared on a substrate is applied and dried to form an electrolyte membrane, and the prepared active material slurry is formed on the electrolyte membrane. The active material film is formed by coating and drying to form a laminate A of the electrolyte film and the active material film, and the active material slurry is applied and dried on a separate substrate to form the active material film. The electrolyte slurry is applied and dried on the active material film to form an electrolyte film, and a plurality of stacked bodies B of the active material film and the electrolyte film are formed, and then the stacked body A on the base is used as a base. As described above, the laminate B is transferred to the laminate A, the substrate is peeled off from the transferred side, and the transfer of the laminate B and the peeling of the substrate are sequentially repeated up to the desired number of layers to form the electrode laminate block. It may be formed. The base material used as a base can be peeled off in any step, for example, after the formation of the electrode laminate block, or after the cutting of the electrode laminate block. In this case, the presence or absence of pressing may be selected according to the density of the obtained electrode laminate block.

別法では、固体電解質及び活物質のそれぞれのスラリーを調製し、一つの基材上に、調製した電解質スラリーを塗工及び乾燥して電解質膜を形成し、調製した活物質スラリーを電解質膜の上に塗工及び乾燥して活物質膜を形成し、さらに所望の層数まで、電解質スラリー及び活物質スラリーの塗工及び乾燥を繰り返して、電極積層体ブロックを形成することができる。この場合、得られた電極積層体ブロックの密度に応じてプレスの有無を選択してもよい。   In another method, each slurry of a solid electrolyte and an active material is prepared, and the prepared electrolyte slurry is applied and dried on one substrate to form an electrolyte membrane, and the prepared active material slurry is applied to the electrolyte membrane. The active material film is formed by coating and drying on the electrode, and the electrode slurry block can be formed by repeating coating and drying of the electrolyte slurry and the active material slurry up to a desired number of layers. In this case, the presence or absence of pressing may be selected according to the density of the obtained electrode laminate block.

別法では、固体電解質及び活物質のそれぞれのスラリーを調製し、別個の基材上に、調製した固体電解質スラリー及び活物質スラリーを塗工及び乾燥して、固体電解質膜及び活物質膜をそれぞれの基材上に形成し、各基材から剥離した固体電解質膜と活物質膜とを所望の層数まで積層及びプレスして、電極積層体ブロックを形成することができる。   In another method, each slurry of the solid electrolyte and the active material is prepared, and the prepared solid electrolyte slurry and the active material slurry are coated and dried on separate substrates, respectively. The electrode laminate block can be formed by laminating and pressing the solid electrolyte film and the active material film formed on each of the substrates and peeled from each substrate to a desired number of layers.

別法では、固体電解質及び活物質のそれぞれのスラリーを調製し、別個の基材上に、調製した固体電解質のスラリー及び活物質のスラリーを塗工及び乾燥して、固体電解質膜及び活物質膜をそれぞれの基材上に形成し、固体電解質膜上に活物質膜を転写、あるいは活物質膜上に固体電解質膜を転写し、これを繰り返すことによって所望の層数まで転写して電極積層体ブロックを形成することができる。この場合、得られた電極積層体ブロックの密度に応じてプレスの有無を選択してもよい。   In another method, each slurry of the solid electrolyte and the active material is prepared, and the prepared solid electrolyte slurry and the active material slurry are coated and dried on separate substrates, so that the solid electrolyte membrane and the active material membrane are coated. Is formed on each base material, and the active material film is transferred onto the solid electrolyte film, or the solid electrolyte film is transferred onto the active material film, and this is repeated until the desired number of layers is transferred to the electrode laminate. Blocks can be formed. In this case, the presence or absence of pressing may be selected according to the density of the obtained electrode laminate block.

上述の方法におけるプレス及び転写は、電極積層体ブロックが切断され得る密度に圧密化することができる圧力で行うことができ、例えば１〜５０ＭＰａで行うことができる。圧力を加える時間及び温度は特に限定されるものではなく、所望の密度が得られるように設定することができる。   The pressing and transfer in the above-described method can be performed at a pressure that can be consolidated to a density at which the electrode laminate block can be cut, and can be performed at, for example, 1 to 50 MPa. The time and temperature at which the pressure is applied are not particularly limited, and can be set so as to obtain a desired density.

上述の方法におけるプレス及び転写の方法は、特に限定されるものではなく、市販の加圧成型装置を用いて行うことができ、一軸プレス、静水圧プレス、またはホットプレス等の方法が挙げられ、例えば、所定サイズの金型に固体電解質膜及び活物質膜の積層体を入れて一軸プレスを行うことにより、加圧成型することができる。   The method of pressing and transferring in the above method is not particularly limited, and can be performed using a commercially available pressure molding apparatus, and examples thereof include a uniaxial press, a hydrostatic press, or a hot press. For example, pressure molding can be performed by putting a laminate of a solid electrolyte membrane and an active material membrane in a predetermined size mold and performing uniaxial pressing.

上述のいずれの方法においても、電解質膜及び活物質膜の積層は任意の順番で行われ得る。例えば、電解質膜及び活物質膜を交互に積層してもよく、あるいは電解質膜または活物質膜が２層以上連続して積層してもよい。所望の厚みに塗工及び乾燥して形成した電解質膜及び活物質膜を、交互に積層することがコスト面及び電池特性面で有利であり好ましい。   In any of the above-described methods, the lamination of the electrolyte membrane and the active material film can be performed in an arbitrary order. For example, electrolyte films and active material films may be alternately stacked, or two or more electrolyte films or active material films may be stacked in succession. It is preferable in terms of cost and battery characteristics that the electrolyte membrane and the active material membrane formed by coating and drying to a desired thickness are alternately laminated.

本発明において、電解質膜及び活物質膜を積層した電極積層体ブロックは、下記に説明するように、複数個の電極体に切断され、セパレータ面に対して電極体の積層面が垂直方向に配置された全固体電池用の電極として使用される。したがって、電極積層体ブロックの積層厚みが、全固体電池に用いる電極の一辺の長さに対応し得るため、電極積層体ブロックの積層厚みが厚いほど全固体電池の電極面積を大きくすることができる。   In the present invention, the electrode laminate block in which the electrolyte membrane and the active material membrane are laminated is cut into a plurality of electrode bodies, and the laminate surface of the electrode bodies is arranged in the vertical direction with respect to the separator surface as described below. Used as an electrode for the all-solid-state battery. Therefore, since the lamination thickness of the electrode laminate block can correspond to the length of one side of the electrode used in the all-solid battery, the electrode area of the all-solid battery can be increased as the laminate thickness of the electrode laminate block is increased. .

よって、電極積層体ブロックは、所望の電池特性を有する全固体電池に用いる電極体として必要となる面積に応じて、任意の厚みに積層することができ、例えば約１０ｍｍ〜約１０００ｍｍ、あるいは約２０ｍｍ〜約１００ｍｍの積層厚みにすることができる。   Therefore, the electrode laminate block can be laminated to any thickness depending on the area required as an electrode body used for an all-solid battery having desired battery characteristics, for example, about 10 mm to about 1000 mm, or about 20 mm. Lamination thicknesses of up to about 100 mm can be achieved.

同様に、電解質層及び活物質層の積層数についても、所望の電池特性に応じて所望の積層数にすることができ、各層の合計で２層以上、例えば各層の合計で１００層〜１０００００層に積層することができる。   Similarly, the number of layers of the electrolyte layer and the active material layer can be set to a desired number of layers according to desired battery characteristics. The total number of each layer is two or more, for example, the total number of each layer is 100 to 100,000 layers. Can be laminated.

所望により、電極の電子導電性を向上するために、固体電解質層及び活物質層の層間に導電助剤層を形成することができる。電極積層体ブロック中への導電助剤層の形成は、上述の電解質層及び活物質層を含む電極積層体ブロックの形成と同様の方法を用いて行うことができる。導電助剤膜の形成は、例えばスプレー塗工プロセスを用いて行うことができ、あるいは上述の電解質膜及び活物質膜と同様のスラリー塗工プロセス、ブラスト法、エアロゾルデポジション法、コールドスプレー法、スパッタリング法、気相成長法、または溶射法等を用いて行うことができる。上述のように、本発明においては、活物質層及び固体電解質層の厚みに対して導電助剤層の厚みを薄く形成しても十分な電子導電性を得ることができるため、スプレー塗工プロセスが好ましく用いられる。   If desired, a conductive assistant layer can be formed between the solid electrolyte layer and the active material layer in order to improve the electronic conductivity of the electrode. Formation of the conductive auxiliary agent layer in the electrode laminate block can be performed using the same method as the formation of the electrode laminate block including the electrolyte layer and the active material layer described above. The formation of the conductive assistant film can be performed using, for example, a spray coating process, or a slurry coating process similar to the above-described electrolyte film and active material film, a blast method, an aerosol deposition method, a cold spray method, A sputtering method, a vapor phase growth method, a thermal spraying method, or the like can be used. As described above, in the present invention, sufficient electroconductivity can be obtained even if the thickness of the conductive auxiliary agent layer is reduced relative to the thickness of the active material layer and the solid electrolyte layer. Is preferably used.

スプレー塗工プロセスやスラリー塗工プロセス等のスラリーを用いて塗工を行うプロセスによって導電助剤膜を形成する場合、導電助剤スラリーの調製に用いる溶媒は、導電助剤の性能に悪影響を与えないものであれば特に限定されないが、例えば炭化水素系有機溶媒のヘプタン、トルエン、ヘキサン等が挙げられ、好ましくは脱水処理して水分含有量を低くした炭化水素系有機溶媒が用いられる。   When the conductive additive film is formed by a process of applying slurry using a slurry such as spray coating process or slurry coating process, the solvent used for preparing the conductive additive slurry has an adverse effect on the performance of the conductive additive. For example, hydrocarbon organic solvents such as heptane, toluene, and hexane may be used, and hydrocarbon organic solvents having a low water content by dehydration are preferably used.

電極積層体ブロックは、図３の切断箇所３６または図４の切断箇所４６のように、積層面に垂直方向に、例えば５０〜１００μｍ程度の幅で切断され、所定の大きさを有する複数の電極体が得られ得る。本発明において、上記切断幅は、電池にしたときの電極の厚み方向（セパレーター面に垂直方向）の厚みとなるため、電池の所望の特性及び大きさに応じて、切断幅を変更することができる。また、所望により、前記切断に加えて、積層面に垂直方向であって前記切断方向に対して垂直方向にも切断して、得られる電極体の大きさを調整してもよく、あるいは得られる電極体の取り個数を増やしてもよい。   The electrode laminate block is cut at a width of, for example, about 50 to 100 μm in a direction perpendicular to the laminated surface, and has a predetermined size, such as the cut portion 36 of FIG. 3 or the cut portion 46 of FIG. The body can be obtained. In the present invention, the cutting width is the thickness of the electrode in the battery thickness direction (perpendicular to the separator surface), so the cutting width can be changed according to the desired characteristics and size of the battery. it can. Further, if desired, in addition to the cutting, the size of the obtained electrode body may be adjusted or obtained by cutting also in the direction perpendicular to the lamination surface and perpendicular to the cutting direction. The number of electrode bodies may be increased.

切断方法は、特に限定されるものではなく、市販の切断装置を用いて行うことができ、ダイヤモンド外周刃切断、ダイサー、ギロチン、またはレーザー等の方法が挙げられ、切断面の品質、電極積層体の厚み、コスト等を考慮して切断方法を選択することができる。   The cutting method is not particularly limited, and can be performed using a commercially available cutting device, and examples thereof include diamond peripheral blade cutting, dicer, guillotine, or laser, and the quality of the cut surface, electrode laminate The cutting method can be selected in consideration of the thickness, cost and the like.

本発明はまた、１以上の第１の固体電解質層及び１以上の第１の活物質層を含む第１の電極積層体ブロックを形成する工程；
１以上の第２の固体電解質層及び１以上の第２の活物質層を含む第２の電極積層体ブロックを形成する工程；
第１の電極積層体ブロック及び第２の電極積層体ブロックを、それぞれの積層面に垂直方向に切断して、複数個の第１の電極体及び第２の電極体を形成する工程；並びに
一組の第１の電極体及び第２の電極体の間に、第１の電極体及び第２の電極体の端部に接するように、第１の電極体及び第２の電極体の積層方向と交差する方向にセパレータ層を配置して、セパレータ層の面に垂直方向にプレスする工程、
を含む、第１の電極体、セパレータ層、及び第２の電極体を含む全固体電池の製造方法である。 The present invention also includes a step of forming a first electrode laminate block including one or more first solid electrolyte layers and one or more first active material layers;
Forming a second electrode laminate block including one or more second solid electrolyte layers and one or more second active material layers;
Cutting the first electrode laminate block and the second electrode laminate block in the direction perpendicular to the respective laminate surfaces to form a plurality of first electrode bodies and second electrode bodies; and The stacking direction of the first electrode body and the second electrode body so as to be in contact with the ends of the first electrode body and the second electrode body between the first electrode body and the second electrode body of the set Placing the separator layer in a direction intersecting with and pressing in a direction perpendicular to the surface of the separator layer,
Is a manufacturing method of an all-solid-state battery including a first electrode body, a separator layer, and a second electrode body.

第１の電極積層体ブロック及び第２の電極積層体ブロックは、それぞれ切り出されて全固体電池の正極及び負極として用いられるものである。第１の電極積層体ブロックは第１の固体電解質層及び第１の活物質層を含み、第２の電極積層体ブロックは第２の固体電解質層及び第２の活物質層を含み、それぞれ、上述の同様の方法で電極積層体ブロックが作成され得る。第１の活物質層及び第２の活物質層に含まれる活物質材料は、いずれかが正極活物質として機能する正極活物質であり、他方が負極活物質として機能する負極活物質であり、充放電電位が異なる電位を示す材料である。本発明において、正極活物質及び負極活物質には明確な区別はなく、上述の活物質材料から２種類の充放電電位を比較して、充放電電位が貴な電位を示すものを正極に、卑な電位を示すものを負極に用いて、任意の電圧の電池を構成することができる。   A 1st electrode laminated body block and a 2nd electrode laminated body block are cut out, respectively, and are used as a positive electrode and a negative electrode of an all-solid-state battery. The first electrode laminate block includes a first solid electrolyte layer and a first active material layer, and the second electrode laminate block includes a second solid electrolyte layer and a second active material layer, respectively. An electrode laminate block can be created in the same manner as described above. One of the active material materials included in the first active material layer and the second active material layer is a positive electrode active material that functions as a positive electrode active material, and the other is a negative electrode active material that functions as a negative electrode active material, It is a material which shows the electric potential from which charging / discharging electric potential differs. In the present invention, there is no clear distinction between the positive electrode active material and the negative electrode active material, comparing two kinds of charge / discharge potentials from the above active material, A battery having an arbitrary voltage can be formed using a negative potential as a negative electrode.

また、第１の電極積層体及び第２の電極積層体はそれぞれ、第１の固体電解質層及び第２の固体電解質層を含む。第１の固体電解質層及び第２の固体電解質層に含まれる固体電解質材料は同じ固体電解質材料であることが好ましい。   The first electrode laminate and the second electrode laminate each include a first solid electrolyte layer and a second solid electrolyte layer. The solid electrolyte materials contained in the first solid electrolyte layer and the second solid electrolyte layer are preferably the same solid electrolyte material.

第１の電極積層体ブロック及び第２の電極積層体ブロックのうち、少なくとも一方の電極積層体ブロックが導電助剤層を含むことができる。   Of the first electrode laminate block and the second electrode laminate block, at least one electrode laminate block may include a conductive additive layer.

第１の電極体及び第２の電極体は、セパレータを挟んで、第１の電極体及び第２の電極体の積層方向がセパレータ面と交差する方向で向かい合って配置されるが、第１の電極体及び第２の電極体に含まれる固体電解質、活物質、及び所望による導電助剤層のそれぞれの厚みは、第１の電極体及び第２の電極体において同じでもよく、あるいは異なってもよい。また、例えば、第１の電極体に固体電解質、導電助剤層、及び活物質が含まれ、第２の電極体に固体電解質及び活物質が含まれる場合、第１の電極体における固体電解質、導電助剤層、及び活物質を１組としたときの厚みと、第２の電極体における固体電解質及び活物質を１組としたときの厚みは、同じでもよく、あるいは異なってもよい。これらの厚みは電極体中のリチウム伝導性を考慮して決定することができる。   The first electrode body and the second electrode body are arranged facing each other in a direction in which the stacking direction of the first electrode body and the second electrode body intersects the separator surface with the separator interposed therebetween. The thicknesses of the solid electrolyte, the active material, and the optional conductive additive layer included in the electrode body and the second electrode body may be the same or different in the first electrode body and the second electrode body. Good. Further, for example, when the first electrode body includes a solid electrolyte, a conductive additive layer, and an active material, and the second electrode body includes a solid electrolyte and an active material, the solid electrolyte in the first electrode body, The thickness when the conductive auxiliary agent layer and the active material are set as one set and the thickness when the solid electrolyte and the active material in the second electrode body are set as one set may be the same or different. These thicknesses can be determined in consideration of lithium conductivity in the electrode body.

本発明の電極体に含まれるセパレータは、電極体中に含まれる電解質膜の形成方法と同様にして基材上にセパレータ膜を形成して、セパレータ膜を基材から剥離することによって作成してもよい。また、セパレータは、単層構造または複層構造であることができる。   The separator included in the electrode body of the present invention is prepared by forming a separator film on a substrate in the same manner as the method for forming an electrolyte film included in the electrode body and peeling the separator film from the substrate. Also good. The separator may have a single layer structure or a multilayer structure.

第１の電極体、セパレータ、及び第２の電極体を含む積層体を、第１の電極体及び第２の電極体の積層面に平行方向に（セパレータ面に垂直方向に）所定圧力でプレスして、第１の電極体、セパレータ、及び第２の電極体を含む本発明の全固体電池を得ることができる。   The laminated body including the first electrode body, the separator, and the second electrode body is pressed at a predetermined pressure in a direction parallel to the laminated surface of the first electrode body and the second electrode body (in a direction perpendicular to the separator surface). And the all-solid-state battery of this invention containing a 1st electrode body, a separator, and a 2nd electrode body can be obtained.

電極体及びセパレータをプレスする方法は、特に限定されるものではなく、市販の加圧成型装置を用いて行うことができ、一軸プレス、静水圧プレス、またはホットプレス等の方法が挙げられ、例えば、所定サイズの金型に、第１の電極体、セパレータ、及び第２の電極体を入れて一軸プレスを行うことにより加圧成型することができる。   The method for pressing the electrode body and the separator is not particularly limited, and can be performed using a commercially available pressure molding apparatus, and examples thereof include a uniaxial press, an isostatic press, and a hot press. The first electrode body, the separator, and the second electrode body are placed in a predetermined size mold, and press molding can be performed by uniaxial pressing.

電極体及びセパレータをプレスする圧力は、第１の電極体、セパレータ、及び第２の電極体を密着させ、且つ第１の電極体、セパレータ、及び第２の電極体に含まれる空隙を少なくして密度を高め、電池としての性能を高めるためことができる所望の圧力で行うことができ、例えば５０〜１０００ＭＰａで行うことができる。圧力を加える時間及び温度は特に限定されるものではなく、所望の密度が得られるように設定することができる。   The pressure for pressing the electrode body and the separator allows the first electrode body, the separator, and the second electrode body to be in close contact with each other, and the voids included in the first electrode body, the separator, and the second electrode body are reduced. For example, it can be performed at a desired pressure that can increase the density and enhance the performance as a battery, for example, 50 to 1000 MPa. The time and temperature at which the pressure is applied are not particularly limited, and can be set so as to obtain a desired density.

得られた全固体電池において、セパレータに対して反対側の、第１の電極体及び第２の電極体の端部に接するように、第１の電極体及び第２の電極体の積層方向と交差する方向に、第１の集電体及び第２の集電体をそれぞれ配置することができる。集電体の配置前に、カーボンスプレーを第１の電極体及び第２の電極体の端部にコーティングして集電体との接触性を向上してもよく、及び／または集電体の配置後に集電体面に垂直方向にプレス成型してもよい。   In the obtained all-solid-state battery, the stacking direction of the first electrode body and the second electrode body is in contact with the ends of the first electrode body and the second electrode body on the side opposite to the separator. The first current collector and the second current collector can be respectively disposed in the intersecting direction. Before placing the current collector, the carbon spray may be coated on the ends of the first electrode body and the second electrode body to improve the contact with the current collector, and / or You may press-mold in the direction perpendicular | vertical to the electrical power collector surface after arrangement | positioning.

別の態様において、第１の集電体、第１の電極体、セパレータ、第２の電極体、及び第２の集電体を、同時にプレス成型してもよい。   In another aspect, the first current collector, the first electrode body, the separator, the second electrode body, and the second current collector may be simultaneously press-molded.

（実施例１）
電解質スラリーの調製
平均粒径４μｍのＬｉ2Ｓ／Ｐ2Ｓ5硫化物系固体電解質を質量比２倍の脱水ヘプタン中に入れ、遊星ボールミルによるメカニカルミリングを２０時間行い、次いで、バインダーとして電解質比で０．５ｗｔ％の水素添加ブチレンゴムを加え、ビーズミルによる破砕を行い、平均粒径０．５μｍの電解質を含むスラリーを得た。 Example 1
Preparation of electrolyte slurry Li 2 S / P 2 S 5 sulfide-based solid electrolyte with an average particle size of 4 μm is placed in dehydrated heptane with a mass ratio of 2 times, mechanical milling with a planetary ball mill is performed for 20 hours, and then the electrolyte ratio is used as a binder. Then, 0.5 wt% hydrogenated butylene rubber was added and crushed by a bead mill to obtain a slurry containing an electrolyte having an average particle size of 0.5 μm.

正極活物質スラリーの調製
正極活物質として、平均粒径４μｍのＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2三元系活物質粒子を用い、０．５ｗｔ％の水素添加ブチレンゴムを加えて、固形分が６０ｗｔ％になるように脱水ヘプタンを加えてスラリーを得た。
導電助剤スラリーの調製
一次粒径５０ｎｍのアセチレンブラックに、固形分濃度が１ｗｔ％になるように脱水ヘプタンを加え、ビーズミルにより調合して、導電助剤スラリーとしてのカーボンインクを得た。 Preparation of positive electrode active material slurry As positive electrode active material, LiNi 1/3 Co 1/3 Mn 1/3 O 2 ternary active material particles with an average particle size of 4 μm were used, and 0.5 wt% hydrogenated butylene rubber was added. Then, dehydrated heptane was added so that the solid content was 60 wt% to obtain a slurry.
Preparation of Conductive Aid Slurry Dehydrated heptane was added to acetylene black having a primary particle size of 50 nm so that the solid content concentration was 1 wt%, and the mixture was prepared by a bead mill to obtain a carbon ink as a conductive auxiliary slurry.

負極活物質スラリーの調製
負極活物質として平均粒径２０μｍのグラファイトを粉砕して平均粒径４μｍのグラファイトを得て、これに０．５ｗｔ％の水素添加ブチレンゴムを加えて、固形分が６０ｗｔ％になるように脱水ヘプタンを加えてスラリーを得た。 Preparation of Negative Electrode Active Material Slurry Graphite with an average particle size of 20 μm was pulverized as a negative electrode active material to obtain graphite with an average particle size of 4 μm, and 0.5 wt% of hydrogenated butylene rubber was added thereto to obtain a solid content of 60 wt%. A slurry was obtained by adding dehydrated heptane.

第１の電極積層体ブロック及び第１の電極体の形成   Formation of first electrode laminate block and first electrode body

電解質膜の形成
図１に示すように、調製した電解質スラリーを、テフロン（登録商標）基材１５上に、ダム式スラリーコーターを用いて塗工及び乾燥を行い、４μｍ厚の電解質膜１１を形成した。 Formation of Electrolyte Membrane As shown in FIG. 1, the prepared electrolyte slurry is coated and dried on a Teflon (registered trademark) substrate 15 using a dam type slurry coater to form an electrolyte membrane 11 having a thickness of 4 μm. did.

導電助剤膜の形成
図１に示すように、形成した電解質膜１１上に、調製したカーボンインクを、スプレー噴霧を用いて塗工及び乾燥を行い、０．３μｍ厚の導電助剤膜１２を形成した。 Formation of Conductive Auxiliary Film As shown in FIG. 1, the prepared carbon ink is applied and dried using spray spraying on the formed electrolyte film 11 to form a conductive auxiliary film 12 having a thickness of 0.3 μm. Formed.

活物質膜の形成
図１に示すように、形成した導電助剤膜１２上に、調製した活物質スラリーを、ダム式スラリーコーターを用いて塗工及び乾燥を行い、１６μｍ厚の活物質膜１３を形成した。 Formation of Active Material Film As shown in FIG. 1, the prepared active material slurry is applied and dried using a dam type slurry coater on the conductive auxiliary agent film 12, and an active material film 13 having a thickness of 16 μm is formed. Formed.

上述のようにして、基材１５上に、電解質膜１１、導電助剤膜１２、及び活物質膜１３の３層の積層体を形成後、１００℃で３０分間、乾燥を行った。次いで、乾燥した電極積層体を７０ｍｍ四方の大きさに切り出し、基材を剥離して、５８００組の前記３層の積層体を積層して積層体を得た。   As described above, a three-layer laminate of the electrolyte membrane 11, the conductive additive film 12, and the active material film 13 was formed on the substrate 15, and then dried at 100 ° C. for 30 minutes. Next, the dried electrode laminate was cut into a size of 70 mm square, the substrate was peeled, and 5800 sets of the three-layer laminate were laminated to obtain a laminate.

得られた積層体を積層面に垂直方向に５ＭＰａの圧力でプレス成型し、図３に示すような、５０ｍｍ厚の第１の電極積層体ブロック３０を得た。   The obtained laminated body was press-molded at a pressure of 5 MPa in a direction perpendicular to the laminated surface to obtain a first electrode laminated body block 30 having a thickness of 50 mm as shown in FIG.

第１の電極積層体ブロック３０を、ダイヤモンド外周刃切断加工により、第１の電極積層体ブロック３０の積層面に垂直方向に長さ５０ｍｍになるように切断し、次いで６５μｍ幅になるように複数の電極体を切り出し、図５に示すような、長さ５０ｍｍ、幅５０ｍｍ、厚み６５μｍの複数個の第１の電極体５０を得た。   The first electrode laminate block 30 is cut to a length of 50 mm in a direction perpendicular to the lamination surface of the first electrode laminate block 30 by a diamond outer peripheral cutting process, and then a plurality of pieces are formed to have a width of 65 μm. A plurality of first electrode bodies 50 having a length of 50 mm, a width of 50 mm, and a thickness of 65 μm as shown in FIG. 5 were obtained.

第２の電極積層体ブロック及び第２の電極体の形成   Formation of second electrode laminate block and second electrode body

電解質膜の形成
図２に示すように、上で調製した電解質スラリーを、テフロン（登録商標）基材２５上に、ダム式スラリーコーターを用いて塗工及び乾燥を行い、４μｍ厚の電解質膜２１を形成した。 Formation of Electrolyte Membrane As shown in FIG. 2, the electrolyte slurry prepared above is coated and dried on a Teflon (registered trademark) substrate 25 using a dam type slurry coater, and a 4 μm thick electrolyte membrane 21 is formed. Formed.

負極活物質膜の形成
図２に示すように、形成した電解質膜２１上に、調製した負極活物質スラリーを、ダム式スラリーコーターを用いて塗工及び乾燥を行い、１６．３μｍ厚の活物質膜２４を形成した。 Formation of Negative Electrode Active Material Film As shown in FIG. 2, the prepared negative electrode active material slurry is applied and dried using a dam type slurry coater on the electrolyte membrane 21 to obtain a 16.3 μm thick active material. A film 24 was formed.

上述のようにして、基材２５上に、電解質膜２１及び活物質膜２４の２層の積層体を形成後、１００℃で３０分間、乾燥を行った。次いで、乾燥した電極積層体を７０ｍｍ四方の大きさに切り出し、基材を剥離して、５８００組の前記２層の積層体を積層して積層体を得た。   As described above, a two-layer laminate of the electrolyte membrane 21 and the active material film 24 was formed on the substrate 25, and then dried at 100 ° C. for 30 minutes. Next, the dried electrode laminate was cut into a size of 70 mm square, the substrate was peeled off, and 5800 sets of the two-layer laminate were laminated to obtain a laminate.

得られた積層体を積層面に垂直方向に５ＭＰａの圧力でプレス成型し、図４に示すような、５０ｍｍ厚の第２の電極積層体ブロック４０を得た。   The obtained laminate was press-molded at a pressure of 5 MPa in a direction perpendicular to the laminate surface to obtain a second electrode laminate block 40 having a thickness of 50 mm as shown in FIG.

第２の電極積層体ブロック４０を、ダイヤモンド外周刃切断加工により、第２の電極積層体ブロック４０の積層面に垂直方向に長さ５０ｍｍになるように切断し、次いで９４μｍ幅になるように複数の電極体を切り出し、図６に示すような、長さ５０ｍｍ、幅５０ｍｍ、厚み９４μｍの複数個の第２の電極体６０を得た。   The second electrode laminate block 40 is cut so as to have a length of 50 mm in a direction perpendicular to the lamination surface of the second electrode laminate block 40 by cutting with a diamond outer peripheral blade, and then a plurality of pieces are formed so as to have a width of 94 μm. A plurality of second electrode bodies 60 having a length of 50 mm, a width of 50 mm, and a thickness of 94 μm as shown in FIG. 6 were obtained.

セパレータ膜の形成
電解質膜の形成と同様にして、Ｌｉ2Ｓ／Ｐ2Ｓ5硫化物系固体電解質を含む電解質スラリーを調製して、ダム式スラリーコーターにより４０μｍ厚になるようにテフロン（登録商標）基材上に塗工及び乾燥を行い、セパレータ膜を形成した。 Formation of separator film In the same manner as the formation of the electrolyte film, an electrolyte slurry containing a Li 2 S / P 2 S 5 sulfide-based solid electrolyte was prepared, and Teflon (registered trademark) was formed so as to have a thickness of 40 μm by a dam type slurry coater. ) Coating and drying were performed on the substrate to form a separator film.

全固体電池の形成
セパレータ膜を基材から剥離して、第１の電極体５０及び第２の電極体６０の間に、第１の電極体５０及び第２の電極体６０の端部に接するように、第１の電極体５０及び第２の電極体６０の積層方向と交差する方向にセパレータ膜を配置して、電極体５０の積層面に平行方向に（セパレータ膜の面に垂直方向に）、４２１．４ＭＰａの圧力でプレス成型し、図７に示すような、第１の電極体７０ａ、セパレータ７７、及び第２の電極体７０ｂを含み、長さ５０ｍｍ及び幅５０ｍｍの電極面積、並びに厚み１５３μｍを有する全固体電池７０を形成した。 Formation of all-solid-state battery The separator film is peeled off from the base material and is in contact with the end portions of the first electrode body 50 and the second electrode body 60 between the first electrode body 50 and the second electrode body 60. As described above, the separator film is arranged in a direction crossing the stacking direction of the first electrode body 50 and the second electrode body 60, and is parallel to the stacking surface of the electrode body 50 (in the direction perpendicular to the surface of the separator film). ), Press-molded at a pressure of 421.4 MPa, and includes a first electrode body 70a, a separator 77, and a second electrode body 70b as shown in FIG. 7, an electrode area having a length of 50 mm and a width of 50 mm, and An all-solid battery 70 having a thickness of 153 μm was formed.

セパレータ７７とは反対側の第１の電極体７０ａ及び第２の電極体７０ｂの端部に接するように、第１の電極体７０ａ及び第２の電極体７０ｂの積層方向と交差する方向に、第１の集電体８８として２５μｍ厚のＳＵＳ箔、及び第２の集電体８９として１５μｍ厚の銅箔をそれぞれ配置して、セパレータ層の面に垂直方向に、４２１．４ＭＰａの圧力でプレス成型し、長さ５０ｍｍ及び幅５０ｍｍの電極面積、並びに厚み１９０μｍを有する全固体電池８０を得た。   In a direction intersecting with the stacking direction of the first electrode body 70a and the second electrode body 70b so as to be in contact with the end portions of the first electrode body 70a and the second electrode body 70b opposite to the separator 77, A SUS foil having a thickness of 25 μm is disposed as the first current collector 88 and a copper foil having a thickness of 15 μm is disposed as the second current collector 89, and is pressed in a direction perpendicular to the surface of the separator layer at a pressure of 421.4 MPa. The all-solid-state battery 80 which shape | molded and has an electrode area of length 50mm and width 50mm, and thickness 190micrometer was obtained.

（比較例１）
正極合材の形成
平均粒径４μｍのＬｉ2Ｓ／Ｐ2Ｓ5硫化物系固体電解質を質量比２倍の脱水ヘプタン中に入れ、遊星ボールミルによるメカニカルミリングを２０時間行い、次いで、バインダーとして電解質比で０．５ｗｔ％の水素添加ブチレンゴムを加え、ビーズミルによる破砕を行い、平均粒径０．５μｍの電解質スラリーを得た。 (Comparative Example 1)
Formation of positive electrode mixture Li 2 S / P 2 S 5 sulfide-based solid electrolyte having an average particle size of 4 μm is placed in dehydrated heptane having a mass ratio of 2 times, mechanical milling by a planetary ball mill is performed for 20 hours, and then an electrolyte as a binder Hydrogenated butylene rubber at a ratio of 0.5 wt% was added and crushed by a bead mill to obtain an electrolyte slurry having an average particle size of 0.5 μm.

調製した電解質スラリーに、正極活物質材料：電解質材料の体積比が８０：２０となるように、平均粒径４μｍのＬｉＮｉ1/3Ｃｏ1/3Ｍｎ1/3Ｏ2正極活物質、及び正極活物質に対して０．５ｗｔ％の水素添加ブチレンゴムを加えて、固形分が６０ｗｔ％になるように脱水ヘプタンを加えてスラリーとした。 LiNi 1/3 Co 1/3 Mn 1/3 O 2 positive electrode active material having an average particle diameter of 4 μm and a positive electrode so that the volume ratio of positive electrode active material: electrolyte material is 80:20 to the prepared electrolyte slurry 0.5 wt% hydrogenated butylene rubber was added to the active material, and dehydrated heptane was added to give a slurry so that the solid content was 60 wt%.

調製した正極材料を含むスラリーを、２５μｍ厚のＳＵＳ箔上に、ダム式スラリーコーターで塗工及び乾燥を行い、１３０μｍ厚の正極合材膜を形成した。   The slurry containing the prepared positive electrode material was coated and dried on a SUS foil having a thickness of 25 μm with a dam type slurry coater to form a positive electrode mixture film having a thickness of 130 μm.

負極合材の形成
上記と同様に調製した電解質スラリーに、負極活物質材料：電解質材料の体積比が８０：２０となるように、平均粒径２０μｍのグラファイト負極活物質、及び負極活物質に対して０．５ｗｔ％の水素添加ブチレンゴムを加えて、固形分が６０ｗｔ％になるように脱水ヘプタンを加えてスラリーとした。 Formation of Negative Electrode Mixture To a negative electrode active material having an average particle diameter of 20 μm and a negative electrode active material so that a volume ratio of negative electrode active material: electrolyte material is 80:20 0.5 wt% of hydrogenated butylene rubber was added, and dehydrated heptane was added so that the solid content was 60 wt% to obtain a slurry.

調製した負極材料を含むスラリーを、１５μｍ厚の銅箔上に、ダム式スラリーコーターで塗工及び乾燥を行い、１８８μｍ厚の負極合材膜を形成した。   The slurry containing the prepared negative electrode material was coated and dried on a 15 μm thick copper foil with a dam type slurry coater to form a negative electrode mixture film having a thickness of 188 μm.

セパレータの形成
上記と同様に、電解質スラリーを調製して、形成した負極合材膜上に、ダム式スラリーコーターで塗工及び乾燥を行い、４０μｍ厚のセパレータ膜を形成した。 Formation of Separator In the same manner as described above, an electrolyte slurry was prepared, and applied and dried with a dam type slurry coater on the formed negative electrode composite film to form a separator film having a thickness of 40 μm.

正極合材膜と、セパレータ膜をその上に形成した負極合材膜とを、正極合材膜／セパレータ膜／負極合材膜となるように積層し、積層面に垂直方向に５ＭＰａの圧力でプレス成型を行い複合成型体を得た。   A positive electrode composite film and a negative electrode composite film on which a separator film is formed are laminated so as to be a positive electrode composite film / separator film / negative electrode composite film, and at a pressure of 5 MPa in a direction perpendicular to the lamination surface Press molding was performed to obtain a composite molded body.

複合成型体を、ダイヤモンド外周刃切断加工により、複合成型体の積層面に垂直方向に切断加工して、長さ５０ｍｍ、幅５０ｍｍ、厚み２５５μｍの複数個の成型体片を得た。   The composite molded body was cut in a direction perpendicular to the laminated surface of the composite molded body by a diamond outer peripheral blade cutting process to obtain a plurality of molded body pieces having a length of 50 mm, a width of 50 mm, and a thickness of 255 μm.

次いで、得られた成型体片を積層面に垂直方向に４２１．４ＭＰａの圧力でプレス成型し、正極合材層、セパレータ、及び負極合材層からなる、長さ５０ｍｍ及び幅５０ｍｍの電極面積、並びに厚み２１９μｍを有する全固体電池を得た。   Subsequently, the obtained molded body piece was press-molded at a pressure of 421.4 MPa in a direction perpendicular to the lamination surface, and an electrode area having a length of 50 mm and a width of 50 mm consisting of a positive electrode mixture layer, a separator, and a negative electrode mixture layer, In addition, an all-solid battery having a thickness of 219 μm was obtained.

電池性能評価
実施例１及び比較例１において作成した全固体電池について、充放電評価を行った。充放電の電圧範囲を２．５〜４．５５Ｖとし、０．１Ｃ及び２Ｃでの容量密度を測定した。表１に充放電評価結果を示す。 Battery performance evaluation The all-solid-state battery created in Example 1 and Comparative Example 1 was subjected to charge / discharge evaluation. The charge / discharge voltage range was 2.5 to 4.55 V, and the capacity density at 0.1 C and 2 C was measured. Table 1 shows the charge / discharge evaluation results.

Figure 2012248468
Figure 2012248468

実施例１で作成した全固体電池については、電解質割合が２０ｖｏｌ％と少ないにもかかわらず、０．１Ｃ及び２Ｃにおいて１８８ｍＡｈ／ｇの比容量が得られた。比較例１で作成した電解質割合が２０ｖｏｌ％全固体電池は、０．１Ｃにおいて８０ｍＡｈ／ｇ、及び２Ｃにおいて２０ｍＡｈ／ｇの比容量が得られた。   For the all solid state battery prepared in Example 1, a specific capacity of 188 mAh / g was obtained at 0.1 C and 2 C, although the electrolyte ratio was as low as 20 vol%. An all-solid battery having an electrolyte ratio of 20 vol% prepared in Comparative Example 1 has a specific capacity of 80 mAh / g at 0.1 C and 20 mAh / g at 2 C.

このように、実施例１で作成した全固体電池は、同じ電解質割合を有する比較例１で作成した全固体電池に比べて、高い比容量を有していた。   Thus, the all solid state battery produced in Example 1 had a higher specific capacity than the all solid state battery produced in Comparative Example 1 having the same electrolyte ratio.

これらの結果から、本発明の全固体電池用電極体及び全固体電池並びそれらの製造方法によれば、固体電解質の種類が制限されず且つ簡便なプロセスによって、従来よりも電解質の割合を少なくして活物質の割合を高く設計することが可能となり、高い容量密度を有する全固体電池を得ることが可能となることが分かった。   From these results, according to the all-solid-state battery electrode body and all-solid-state battery of the present invention and the manufacturing method thereof, the type of the solid electrolyte is not limited, and the ratio of the electrolyte is reduced as compared with the conventional process by a simple process. Thus, it has been found that it is possible to design a high proportion of the active material, and it is possible to obtain an all solid state battery having a high capacity density.

１１ 電解質膜
１２ 導電助剤膜
１３ 正極活物質膜
１５ 基材
１ａ 塗工ヘッド
１ｂ スプレーヘッド
２１ 電解質膜
２４ 負極活物質膜
２５ 基材
２ａ 塗工ヘッド
３０ 第１の電極積層体ブロック
３１ 電解質層
３２ 導電助剤層
３３ 正極活物質層
３６ 切断箇所
４０ 第２の電極積層体ブロック
４１ 電解質層
４４ 負極活物質層
４６ 切断箇所
５０ 第１の電極体
５１ 電解質層
５２ 導電助剤層
５３ 正極活物質層
６０ 第２の電極体
６１ 電解質層
６４ 負極活物質層
７０ 全固体電池
７０ａ 第１の電極体
７０ｂ 第２の電極体
７１ 電解質層
７２ 導電助剤層
７３ 正極活物質層
７４ 負極活物質層
７７ セパレータ
８０ 集電体を有する全固体電池
８１ 電解質層
８２ 導電助剤層
８３ 正極活物質層
８４ 負極活物質層
８７ セパレータ
８８ 第１の集電体
８９ 第２の集電体 DESCRIPTION OF SYMBOLS 11 Electrolyte film 12 Conductive auxiliary agent film 13 Positive electrode active material film 15 Base material 1a Coating head 1b Spray head 21 Electrolyte film 24 Negative electrode active material film 25 Base material 2a Coating head 30 1st electrode laminated body block 31 Electrolyte layer 32 Conductive aid layer 33 Positive electrode active material layer 36 Cut portion 40 Second electrode laminate block 41 Electrolyte layer 44 Negative electrode active material layer 46 Cut portion 50 First electrode body 51 Electrolyte layer 52 Conductive aid layer 53 Positive electrode active material layer 60 second electrode body 61 electrolyte layer 64 negative electrode active material layer 70 all solid state battery 70a first electrode body 70b second electrode body 71 electrolyte layer 72 conductive auxiliary agent layer 73 positive electrode active material layer 74 negative electrode active material layer 77 separator 80 All-solid-state battery having current collector 81 Electrolyte layer 82 Conductive auxiliary agent layer 83 Positive electrode active material layer 84 Negative electrode active material layer 87 Separator 88 The current collector 89 the second of the current collector of

Claims (8)

１以上の固体電解質層及び１以上の活物質層を含む電極積層体からなる全固体電池用電極体であって、前記電極積層体の端部に接するように、前記電極積層体の積層方向と交差する方向にセパレータ層が配置される、全固体電池用電極体。   An electrode body for an all-solid battery comprising an electrode laminate including one or more solid electrolyte layers and one or more active material layers, wherein the electrode laminate is laminated so as to be in contact with an end of the electrode laminate. An electrode body for an all-solid battery, in which separator layers are arranged in the intersecting direction. 前記１以上の固体電解質層及び前記１以上の活物質層が交互に積層された、請求項１に記載の全固体電池用電極体。   The electrode body for an all-solid-state battery according to claim 1, wherein the one or more solid electrolyte layers and the one or more active material layers are alternately laminated. 前記１以上の固体電解質層及び前記１以上の活物質層の層間の少なくとも１つに導電助剤層を含む、請求項１または２に記載の全固体電池用電極体。   The electrode body for an all-solid-state battery according to claim 1 or 2, comprising a conductive additive layer in at least one of the one or more solid electrolyte layers and the one or more active material layers. １以上の第１の固体電解質層及び１以上の第１の活物質層を含む第１の電極積層体、１以上の第２の固体電解質層及び１以上の第２の活物質層を含む第２の電極積層体、並びに前記第１及び第２の電極積層体の間に、前記第１及び第２の電極積層体の端部に接するように、前記第１及び第２の電極積層体の積層方向と交差する方向に配置されたセパレータ層を含む、全固体電池。   A first electrode stack including one or more first solid electrolyte layers and one or more first active material layers, a first electrode stack including one or more second solid electrolyte layers and one or more second active material layers. Two electrode stacks, and the first and second electrode stacks so as to be in contact with the end portions of the first and second electrode stacks between the first and second electrode stacks. An all-solid-state battery including a separator layer arranged in a direction crossing the stacking direction. １以上の固体電解質層及び１以上の活物質層を含む電極積層体ブロックを形成する工程；並びに
前記電極積層体ブロックを、積層面に垂直方向に切断して、複数個の電極体を形成する工程；
を含む、全固体電池用電極体の製造方法であって、前記電極体の端部に接するように、前記電極体の積層方向と交差する方向にセパレータ層が配置される、全固体電池用電極体の製造方法。 Forming an electrode laminate block including one or more solid electrolyte layers and one or more active material layers; and cutting the electrode laminate block in a direction perpendicular to the laminate surface to form a plurality of electrode bodies. Process;
An electrode for an all-solid battery, comprising: a separator layer disposed in a direction intersecting with the stacking direction of the electrode bodies so as to be in contact with an end of the electrode body Body manufacturing method. 前記電極積層体ブロックを形成する工程が、前記１以上の固体電解質層及び前記１以上の活物質層を交互に積層することを含む、請求項５に記載の全固体電池用電極体の製造方法。   The method for producing an electrode body for an all solid state battery according to claim 5, wherein the step of forming the electrode laminate block includes alternately laminating the one or more solid electrolyte layers and the one or more active material layers. . 前記電極積層体ブロックを形成する工程が、前記１以上の固体電解質層及び前記１以上の活物質層の層間の少なくとも１つに導電助剤層を形成することを含む、請求項５または６に記載の全固体電池用電極体の製造方法。   The step of forming the electrode laminate block includes forming a conductive assistant layer in at least one of the one or more solid electrolyte layers and the one or more active material layers. The manufacturing method of the electrode body for all-solid-state batteries of description. １以上の第１の固体電解質層及び１以上の第１の活物質層を含む第１の電極積層体ブロックを形成する工程；
１以上の第２の固体電解質層及び１以上の第２の活物質層を含む第２の電極積層体ブロックを形成する工程；
前記第１の電極積層体ブロック及び前記第２の電極積層体ブロックをそれぞれ、積層面に垂直方向に切断して、複数個の第１の電極体及び第２の電極体を形成する工程；並びに
一組の前記第１の電極体及び前記第２の電極体の間に、第１の電極体及び第２の電極体の端部に接するように、第１の電極体及び第２の電極体の積層方向と交差する方向にセパレータ層を配置して、前記セパレータ層の面に垂直方向にプレスする工程、
を含む、第１の電極体、セパレータ層、及び第２の電極体を含む全固体電池の製造方法。 Forming a first electrode laminate block including one or more first solid electrolyte layers and one or more first active material layers;
Forming a second electrode laminate block including one or more second solid electrolyte layers and one or more second active material layers;
Cutting the first electrode laminate block and the second electrode laminate block in a direction perpendicular to the lamination surface to form a plurality of first electrode bodies and second electrode bodies; and The first electrode body and the second electrode body are in contact with the end portions of the first electrode body and the second electrode body between the pair of the first electrode body and the second electrode body. Placing the separator layer in a direction crossing the laminating direction, and pressing in a direction perpendicular to the surface of the separator layer,
A method for manufacturing an all-solid battery including a first electrode body, a separator layer, and a second electrode body.
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JP7130911B2 (en) 2020-03-03 2022-09-06 三星エスディアイ株式会社 Positive electrode for all-solid secondary battery, and all-solid secondary battery including the same
US11909043B2 (en) 2020-03-03 2024-02-20 Samsung Sdi Co., Ltd. Positive electrode for all-solid secondary battery and all-solid secondary battery including the same

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