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JP7827490B2 - Method for manufacturing an electrochemical cell - Google Patents
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JP7827490B2 - Method for manufacturing an electrochemical cell - Google Patents

Method for manufacturing an electrochemical cell

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JP7827490B2
JP7827490B2 JP2022032672A JP2022032672A JP7827490B2 JP 7827490 B2 JP7827490 B2 JP 7827490B2 JP 2022032672 A JP2022032672 A JP 2022032672A JP 2022032672 A JP2022032672 A JP 2022032672A JP 7827490 B2 JP7827490 B2 JP 7827490B2
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solid electrolyte
positive electrode
negative electrode
layer
electrolyte layer
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JP2023128368A (en
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竜 鈴木
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Seiko Instruments Inc
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Seiko Instruments Inc
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Priority to PCT/JP2022/047130 priority patent/WO2023166824A1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562Solid materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0585Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

本発明は、電気化学セルの製造方法に関する。 The present invention relates to a method for manufacturing an electrochemical cell.

リチウムイオン二次電池の電解液や、電解液を高分子ポリマーに保持させたゲル電解質に代えて、無機材料からなる固体電解質を用いる全固体電池(電気化学セル)が知られている。
全固体電池においては、無機材料間の接触抵抗に起因して、固体電解質内部の内部抵抗が高くなる。
2. Description of the Related Art All-solid-state batteries (electrochemical cells) are known that use a solid electrolyte made of an inorganic material instead of the electrolyte solution of lithium-ion secondary batteries or a gel electrolyte in which an electrolyte solution is held in a polymer.
In all-solid-state batteries, the internal resistance of the solid electrolyte increases due to contact resistance between inorganic materials.

こうした問題に対して、例えば、特許文献1には、固体電解質を含む固体電解質層の表面に凹凸を形成して内部抵抗を低減した全固体電池が提案されている。 To address these issues, for example, Patent Document 1 proposes an all-solid-state battery in which internal resistance is reduced by forming irregularities on the surface of the solid electrolyte layer containing the solid electrolyte.

特開2008-243735号公報Japanese Patent Application Laid-Open No. 2008-243735

特許文献1の全固体電池(リチウムイオン二次電池)に用いられる電極体100は、図15に示すように、正極層120と、負極層130と、正極層120と負極層130との間に位置する固体電解質層110とを有する。固体電解質層110には、正極層120に向いて開口する正極凹部111が形成されている。これにより、断面視において、固体電解質層110の正極層120側には、正極凹部111と正極凸部112とが交互に形成されている。固体電解質層110には、負極層130に向いて開口する負極凹部115が形成されている。これにより、断面視において、固体電解質層110の負極層130側には、負極凹部115と負極凸部116とが交互に形成されている。 As shown in FIG. 15 , the electrode body 100 used in the all-solid-state battery (lithium ion secondary battery) of Patent Document 1 includes a positive electrode layer 120, a negative electrode layer 130, and a solid electrolyte layer 110 located between the positive electrode layer 120 and the negative electrode layer 130. The solid electrolyte layer 110 has positive electrode recesses 111 that open toward the positive electrode layer 120. As a result, in a cross-sectional view, positive electrode recesses 111 and positive electrode protrusions 112 are alternately formed on the positive electrode layer 120 side of the solid electrolyte layer 110. The solid electrolyte layer 110 has negative electrode recesses 115 that open toward the negative electrode layer 130. As a result, in a cross-sectional view, negative electrode recesses 115 and negative electrode protrusions 116 are alternately formed on the negative electrode layer 130 side of the solid electrolyte layer 110.

特許文献1の発明は、正極凹部111と負極凹部115との距離D8と、正極凸部112と負極凸部116との距離D9とが異なる。すなわち、正極層120と負極層130との距離が不均一となっている。このため、固体電解質層110の内部抵抗が低いところと高いところとができ、電流密度に差ができ、電池反応が不均一になる。その結果、全固体電池の電極利用率(電気容量)の低下や、特定部位の劣化が促進されることによる電池寿命の低下が起きる。 In the invention of Patent Document 1, the distance D8 between the positive electrode recess 111 and the negative electrode recess 115 is different from the distance D9 between the positive electrode protrusion 112 and the negative electrode protrusion 116. In other words, the distance between the positive electrode layer 120 and the negative electrode layer 130 is uneven. This creates areas of low and high internal resistance in the solid electrolyte layer 110, resulting in differences in current density and uneven battery reactions. This results in a decrease in the electrode utilization rate (electrical capacity) of the all-solid-state battery and a shortened battery life due to accelerated deterioration of specific areas.

そこで、本発明は、電気容量をより高められ、電池寿命をより高められる電気化学セルの製造方法を目的とする。 Therefore, an object of the present invention is to provide a method for manufacturing an electrochemical cell that can increase the electric capacity and the battery life.

上記課題を解決するために、本発明は以下の態様を有する。
本発明に係る電気化学セルの製造方法は、正極活物質を含む正極層と、負極活物質を含む負極層と、固体電解質を含む固体電解質層と、を有し、前記固体電解質層は、前記正極層と前記負極層との間に位置し、前記固体電解質層は、前記正極層側に開口し、前記正極層の一部が入り込む正極凹部を複数有し、前記固体電解質層は、前記負極層側に開口し、前記負極層の一部が入り込む負極凹部を複数有し、前記正極凹部と、前記負極凹部とが、前記固体電解質層の面方向にずれている、電気化学セルの製造方法であって、固体電解質層の一方の面に負極凹部を形成した後、前記固体電解質層の一方の面を覆うとともに前記負極凹部を埋める負極層を形成し、この後、前記固体電解質層の他方の面に前記負極凹部とずらした位置に正極凹部を形成し、この後、前記固体電解質層の他方の面を覆うとともに前記正極凹部を埋める正極層を形成することを特徴とする
In order to solve the above problems, the present invention has the following aspects.
A method for manufacturing an electrochemical cell according to the present invention includes a cathode layer including a cathode active material, an anode layer including an anode active material, and a solid electrolyte layer including a solid electrolyte , the solid electrolyte layer being located between the cathode layer and the anode layer, the solid electrolyte layer having a plurality of cathode recesses that open to the cathode layer side and into which a portion of the cathode layer fits, and the solid electrolyte layer having a plurality of anode recesses that open to the anode layer side and into which a portion of the anode layer fits, the cathode recesses and the anode recesses being offset in a surface direction of the solid electrolyte layer, the method comprising the steps of: forming anode recesses on one surface of the solid electrolyte layer; forming anode layer that covers one surface of the solid electrolyte layer and fills the anode recesses; then forming cathode recesses on the other surface of the solid electrolyte layer at a position offset from the anode recesses; and then forming cathode layer that covers the other surface of the solid electrolyte layer and fills the cathode recesses .

この構成によれば、固体電解質層の内部抵抗を均一にでき、電流密度の均一性を高められる。このため、電気容量をより高められ、電池寿命をより高められる。 This configuration makes it possible to uniform the internal resistance of the solid electrolyte layer and improve the uniformity of current density. This in turn increases the electrical capacity and extends the battery life.

また、前記固体電解質層は、前記正極凹部及び前記負極凹部を各々2個以上有し、平面視において、前記固体電解質層の面方向で、前記正極凹部と、前記負極凹部とが交互に位置していてもよい。
この構成によれば、電流密度の均一性をさらに高められる。
The solid electrolyte layer may have two or more positive electrode recesses and two or more negative electrode recesses, and the positive electrode recesses and the negative electrode recesses may be alternately positioned in a surface direction of the solid electrolyte layer in a plan view.
This configuration further improves the uniformity of the current density.

また、前記正極凹部の深さが、前記固体電解質層の厚さの1/2よりも深く、前記負極凹部の深さが、前記固体電解質層の厚さの1/2よりも深くてもよい。
この構成によれば、電気容量をさらに高められる。
The depth of the positive electrode recess may be greater than half the thickness of the solid electrolyte layer, and the depth of the negative electrode recess may be greater than half the thickness of the solid electrolyte layer.
This configuration further increases the electrical capacity.

また、前記固体電解質層の厚さと前記正極凹部の深さとの差と、前記固体電解質層の厚さと前記負極凹部の深さとの差と、前記固体電解質層の厚さ方向の断面視における前記正極凹部と前記負極凹部との距離と、が互いに等しくてもよい。
この構成によれば、電流密度の均一性をさらに高められる。
Furthermore, the difference between the thickness of the solid electrolyte layer and the depth of the positive electrode recess, the difference between the thickness of the solid electrolyte layer and the depth of the negative electrode recess, and the distance between the positive electrode recess and the negative electrode recess in a cross-sectional view in the thickness direction of the solid electrolyte layer may be equal to each other.
This configuration further improves the uniformity of the current density.

本発明の電気化学セルの製造方法によれば、電気容量をより高められ、電池寿命をより高められる。 According to the method for producing an electrochemical cell of the present invention, the electric capacity can be increased and the battery life can be extended.

本発明の一実施形態に係る電気化学セルの外観を示す斜視図である。1 is a perspective view showing the appearance of an electrochemical cell according to one embodiment of the present invention. 同電気化学セルに収容する電極体の一例を示す断面図である。FIG. 2 is a cross-sectional view showing an example of an electrode body housed in the electrochemical cell. 正極凹部と負極凹部との位置関係の一例を示す平面図である。FIG. 2 is a plan view showing an example of the positional relationship between a positive electrode recess and a negative electrode recess. 正極凹部と負極凹部との位置関係の一例を示す平面図である。FIG. 2 is a plan view showing an example of the positional relationship between a positive electrode recess and a negative electrode recess. 図2の電極体の製造方法を示す断面図である。3A to 3C are cross-sectional views showing a method for manufacturing the electrode body of FIG. 2. 図2の電極体の製造方法を示す断面図である。3A to 3C are cross-sectional views showing a method for manufacturing the electrode body of FIG. 2. 図2の電極体の製造方法を示す断面図である。3A to 3C are cross-sectional views showing a method for manufacturing the electrode body of FIG. 2. 図2の電極体の製造方法を示す断面図である。3A to 3C are cross-sectional views showing a method for manufacturing the electrode body of FIG. 2. 図2の電極体の製造方法を示す断面図である。3A to 3C are cross-sectional views showing a method for manufacturing the electrode body of FIG. 2. 図2の電極体の製造方法を示す断面図である。3A to 3C are cross-sectional views showing a method for manufacturing the electrode body of FIG. 2. 本発明の一実施形態に係る電気化学セルに収容する電極体の他の例を示す断面図である。FIG. 4 is a cross-sectional view showing another example of an electrode assembly housed in an electrochemical cell according to an embodiment of the present invention. 本発明の一実施形態に係る電気化学セルに収容する電極体の他の例を示す斜視図である。FIG. 10 is a perspective view showing another example of an electrode assembly housed in an electrochemical cell according to an embodiment of the present invention. 本発明の一実施形態に係る電気化学セルに収容する電極体の他の例を示す斜視図である。FIG. 10 is a perspective view showing another example of an electrode assembly housed in an electrochemical cell according to an embodiment of the present invention. 本発明の一実施形態に係る電気化学セルに収容する電極体の他の例を示す斜視図である。FIG. 10 is a perspective view showing another example of an electrode assembly housed in an electrochemical cell according to an embodiment of the present invention. 従来の全固体電池に用いられる電極体の一例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of an electrode body used in a conventional all-solid-state battery.

以下、本発明に係る電気化学セルの実施形態について図面を参照して説明する。以下の実施形態では、電気化学セルの一例として、コイン型の全固体電池(以下、単に「電池」ともいう。)を挙げ、この電池の構成について説明する。
なお、以下の説明に用いる図面では、各部材を認識可能な大きさとするため、各部材の縮尺を適宜変更し、表示している。
Hereinafter, embodiments of an electrochemical cell according to the present invention will be described with reference to the drawings. In the following embodiments, a coin-type all-solid-state battery (hereinafter simply referred to as a "battery") will be taken as an example of an electrochemical cell, and the configuration of this battery will be described.
In the drawings used in the following description, the scale of each component is appropriately changed to make it recognizable.

≪電気化学セル≫
図1に示すように、本実施形態の電池(電気化学セル)1は、平面視円形状のボタン型の電池である。この電池1は、容器状の外装体2と外装体2の内部に収容された電極体とを備えている。
Electrochemical Cell
1, the battery (electrochemical cell) 1 of this embodiment is a button-type battery that is circular in plan view. The battery 1 includes a container-shaped exterior body 2 and an electrode assembly housed inside the exterior body 2.

外装体2は、ラミネートフィルムにより形成されている。ラミネートフィルムは、金属箔と内側面に設けられ金属箔を被覆する融着層と、外側面に設けられ金属箔を被覆する保護層とを有する。
金属箔は、例えば、アルミニウムやステンレス鋼等の外気や水蒸気を遮断する金属により形成されている。
融着層は、例えば、ポリエチレンやポリプロピレン等のポリオレフィンや、2種類以上の樹脂を含むコポリマーから形成されている。
保護層は、例えば、上述のポリオレフィンや、ポリエチレンテレフタレート等のポリエステル、ナイロン等のポリアミドから形成されている。
The exterior body 2 is formed of a laminate film. The laminate film has a metal foil, a bonding layer provided on the inner surface to cover the metal foil, and a protective layer provided on the outer surface to cover the metal foil.
The metal foil is made of a metal that blocks outside air and water vapor, such as aluminum or stainless steel.
The fusion layer is formed from, for example, a polyolefin such as polyethylene or polypropylene, or a copolymer containing two or more types of resin.
The protective layer is formed from, for example, the above-mentioned polyolefin, polyester such as polyethylene terephthalate, or polyamide such as nylon.

電極体は、正極活物質を含む正極層と負極活物質を含む負極層と、正極層と負極層との間に位置する固体電解質層とを有する。固体電解質層は、固体電解質を含む。
本実施形態の電極体3Aは、図2に示すように、正極層20と、負極層30と、正極層20と負極層30との間に位置する固体電解質層10とを有する。
固体電解質層10は、正極層20側に開口する正極凹部11を有する。正極凹部11には、正極層20が入り込んでいる。
固体電解質層10は、負極層30側に開口する負極凹部15を有する。負極凹部15には、負極層30が入り込んでいる。
正極凹部11と負極凹部15とは、固体電解質層10の面方向(X方向)にずれて位置している。
The electrode assembly has a positive electrode layer containing a positive electrode active material, a negative electrode layer containing a negative electrode active material, and a solid electrolyte layer located between the positive electrode layer and the negative electrode layer. The solid electrolyte layer contains a solid electrolyte.
As shown in FIG. 2, the electrode body 3A of this embodiment has a positive electrode layer 20, a negative electrode layer 30, and a solid electrolyte layer 10 located between the positive electrode layer 20 and the negative electrode layer 30.
The solid electrolyte layer 10 has a positive electrode recess 11 that opens to the positive electrode layer 20 side. The positive electrode layer 20 fits into the positive electrode recess 11.
The solid electrolyte layer 10 has an anode recess 15 that opens to the anode layer 30 side. The anode recess 15 is filled with the anode layer 30.
The positive electrode recess 11 and the negative electrode recess 15 are positioned so as to be shifted in the plane direction (X direction) of the solid electrolyte layer 10 .

電極体3Aの厚さT3Aは、例えば、500~4000μmが好ましく、800~3500μmがより好ましく、1000~3000μmがさらに好ましい。厚さT3Aが上記下限値以上であると、電池1の電気容量をより高められる。厚さT3Aが上記上限値以下であると、電池1をよりコンパクトにできる。
厚さT3Aは、例えば、電極体3Aを厚さ方向(Z方向)に切断した断面を顕微鏡等で観察することにより求められる。
The thickness T3A of the electrode body 3A is, for example, preferably 500 to 4000 μm, more preferably 800 to 3500 μm, and even more preferably 1000 to 3000 μm. When the thickness T3A is equal to or greater than the above lower limit, the electrical capacity of the battery 1 can be increased. When the thickness T3A is equal to or less than the above upper limit, the battery 1 can be made more compact.
The thickness T3A can be determined, for example, by observing a cross section of the electrode body 3A cut in the thickness direction (Z direction) using a microscope or the like.

<固体電解質層>
固体電解質層10は、固体電解質を含む。
固体電解質としては、全固体電池に用いられる公知のものを利用できる。固体電解質としては、酸化物系固体電解質が挙げられる。
酸化物系固体電解質としては、例えば、Li1.5Al0.5Ge1.512(LAGP)、LiLaZr12(LLZ)、Li1.3Al0.3Ti1.7(PO(LATP)、Li10GeP12(LGPS)、Li3.5Ge0.50.5(LGVO)、LiTaPO(LTPO)、La0.57Li0.29TiO(LLTO)、Li6.2Ga0.3La2.95Rb0.05Zr12(LGLRZO)、Li10GeO12(LGPO)、Li6.25LaZrAl0.2512等が挙げられる。
これらの固体電解質は、1種を単独で用いてもよく、2種以上を併用してもよい。
<Solid electrolyte layer>
The solid electrolyte layer 10 includes a solid electrolyte.
As the solid electrolyte, a known solid electrolyte used in all-solid-state batteries can be used, and examples of the solid electrolyte include oxide-based solid electrolytes.
Examples of oxide-based solid electrolytes include Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 (LAGP), Li 7 La 3 Zr 2 O 12 (LLZ), Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP), and Li. 10 GeP 2 S 12 (LGPS), Li 3.5 Ge 0.5 V 0.5 O 4 (LGVO), LiTa 2 PO 8 (LTPO), La 0.57 Li 0.29 TiO 3 (LLTO), Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr 2 O 12 ( LGLRZO ), Li10GeO2P12 ( LGPO), Li6.25La3Zr2Al0.25O12 , and the like .
These solid electrolytes may be used alone or in combination of two or more.

固体電解質層10の厚さT10は、例えば、300~3800μmが好ましく、500~3300μmがより好ましく、800~2800μmがさらに好ましい。厚さT10が上記下限値以上であると、電池1の強度をより高められる。厚さT10が上記上限値以下であると、電池1の内部抵抗をより低減できる。
厚さT10は、厚さT3Aと同様の方法により求められる。
The thickness T10 of the solid electrolyte layer 10 is, for example, preferably 300 to 3800 μm, more preferably 500 to 3300 μm, and even more preferably 800 to 2800 μm. When the thickness T10 is equal to or greater than the above lower limit, the strength of the battery 1 can be further increased. When the thickness T10 is equal to or less than the above upper limit, the internal resistance of the battery 1 can be further reduced.
The thickness T10 is determined in the same manner as the thickness T3A.

正極凹部11の深さD11は、例えば、200~3700μmが好ましく、400~3200μmがより好ましく、700~2700μmがさらに好ましい。深さD11が上記下限値以上であると、電池1の内部抵抗をより低減できる。深さD11が上記上限値以下であると、固体電解質層10の強度をより高められる。
深さD11は、厚さT3Aと同様の方法により求められる。
The depth D11 of the positive electrode recess 11 is, for example, preferably 200 to 3700 μm, more preferably 400 to 3200 μm, and even more preferably 700 to 2700 μm. When the depth D11 is equal to or greater than the above lower limit, the internal resistance of the battery 1 can be further reduced. When the depth D11 is equal to or less than the above upper limit, the strength of the solid electrolyte layer 10 can be further increased.
The depth D11 is determined in the same manner as the thickness T3A.

正極凹部11の幅W11は、例えば、1~100μmが好ましく、2~80μmがより好ましく、3~60μmがさらに好ましい。幅W11が上記下限値以上であると、正極凹部11に正極層20が入り込みやすい。幅W11が上記上限値以下であると、固体電解質層10の強度をより高められる。
幅W11は、厚さT3Aと同様の方法により求められる。
The width W11 of the positive electrode recess 11 is, for example, preferably 1 to 100 μm, more preferably 2 to 80 μm, and even more preferably 3 to 60 μm. When the width W11 is equal to or greater than the above lower limit, the positive electrode layer 20 easily enters the positive electrode recess 11. When the width W11 is equal to or less than the above upper limit, the strength of the solid electrolyte layer 10 can be further increased.
The width W11 is determined in the same manner as the thickness T3A.

2つの正極凹部11の間には、正極凸部12が形成されている。
正極凸部12の高さH12は、正極凹部11の深さD11と同様である。
正極凸部12の幅W12は、例えば、1~300μmが好ましく、2~240μmがより好ましく、3~180μmがさらに好ましい。幅W12が上記下限値以上であると、固体電解質層10の強度をより高められる。幅W12が上記上限値以下であると、電池1の内部抵抗をより低減できる。
幅W12は、厚さT3Aと同様の方法により求められる。
A positive electrode protrusion 12 is formed between the two positive electrode recesses 11 .
The height H12 of the positive electrode convex portion 12 is the same as the depth D11 of the positive electrode concave portion 11.
The width W12 of the positive electrode protrusion 12 is, for example, preferably 1 to 300 μm, more preferably 2 to 240 μm, and even more preferably 3 to 180 μm. When the width W12 is equal to or greater than the above lower limit, the strength of the solid electrolyte layer 10 can be further increased. When the width W12 is equal to or less than the above upper limit, the internal resistance of the battery 1 can be further reduced.
The width W12 is determined in the same manner as the thickness T3A.

負極凹部15の深さD15は、例えば、200~3700μmが好ましく、400~3200μmがより好ましく、700~2700μmがさらに好ましい。深さD15が上記下限値以上であると、電池1の内部抵抗をより低減できる。深さD15が上記上限値以下であると、固体電解質層10の強度をより高められる。
深さD15は、厚さT3Aと同様の方法により求められる。
The depth D15 of the negative electrode recess 15 is, for example, preferably 200 to 3700 μm, more preferably 400 to 3200 μm, and even more preferably 700 to 2700 μm. When the depth D15 is equal to or greater than the above lower limit, the internal resistance of the battery 1 can be further reduced. When the depth D15 is equal to or less than the above upper limit, the strength of the solid electrolyte layer 10 can be further increased.
The depth D15 is determined in the same manner as the thickness T3A.

負極凹部15の幅W15は、例えば、1~100μmが好ましく、2~80μmがより好ましく、3~60μmがさらに好ましい。幅W15が上記下限値以上であると、負極凹部15に負極層30が入り込みやすい。幅W15が上記上限値以下であると、固体電解質層10の強度をより高められる。
幅W15は、厚さT3Aと同様の方法により求められる。
The width W15 of the negative electrode recess 15 is, for example, preferably 1 to 100 μm, more preferably 2 to 80 μm, and even more preferably 3 to 60 μm. When the width W15 is equal to or greater than the above lower limit, the negative electrode layer 30 easily enters the negative electrode recess 15. When the width W15 is equal to or less than the above upper limit, the strength of the solid electrolyte layer 10 can be further increased.
The width W15 is determined in the same manner as the thickness T3A.

2つの負極凹部15の間には、負極凸部16が形成されている。
負極凸部16の高さH16は、負極凹部15の深さD15と同様である。
負極凸部16の幅W16は、例えば、1~300μmが好ましく、2~240μmがより好ましく、3~180μmがさらに好ましい。幅W16が上記下限値以上であると、固体電解質層10の強度をより高められる。幅W16が上記上限値以下であると、電池1の内部抵抗をより低減できる。
幅W16は、厚さT3Aと同様の方法により求められる。
A negative electrode protrusion 16 is formed between the two negative electrode recesses 15 .
The height H16 of the negative electrode protrusion 16 is the same as the depth D15 of the negative electrode recess 15.
The width W16 of the negative electrode protrusion 16 is, for example, preferably 1 to 300 μm, more preferably 2 to 240 μm, and even more preferably 3 to 180 μm. When the width W16 is equal to or greater than the above lower limit, the strength of the solid electrolyte layer 10 can be further increased. When the width W16 is equal to or less than the above upper limit, the internal resistance of the battery 1 can be further reduced.
The width W16 is determined in the same manner as the thickness T3A.

固体電解質層10の厚さT10と正極凹部11の深さD11との差(正極凹部11の最深部から負極層30までの距離)をD1とする。
固体電解質層10の厚さT10と負極凹部15の深さD15との差(負極凹部15の最深部から正極層20までの距離)をD2とする。
固体電解質層10の厚さ方向(Z方向)の断面視における、正極凹部11と負極凹部15との固体電解質層10の面方向(X方向)の距離をD3とする。
このとき、距離D1と距離D2と距離D3とは、互いに等しいことが好ましい。距離D1と距離D2と距離D3とが互いに等しいことで、固体電解質層10の内部の電流密度の均一性をさらに高められる。
ここで、「等しい」とは、距離の比(D1/D2、D1/D3等)が±5%以内であることをいうものとする。
The difference between the thickness T10 of the solid electrolyte layer 10 and the depth D11 of the positive electrode recess 11 (the distance from the deepest part of the positive electrode recess 11 to the negative electrode layer 30) is defined as D1.
The difference between the thickness T10 of the solid electrolyte layer 10 and the depth D15 of the negative electrode recess 15 (the distance from the deepest part of the negative electrode recess 15 to the positive electrode layer 20) is defined as D2.
In a cross-sectional view of the solid electrolyte layer 10 in the thickness direction (Z direction), the distance between the positive electrode recess 11 and the negative electrode recess 15 in the surface direction (X direction) of the solid electrolyte layer 10 is defined as D3.
In this case, it is preferable that the distance D1, the distance D2, and the distance D3 are equal to one another. By making the distance D1, the distance D2, and the distance D3 equal to one another, the uniformity of the current density inside the solid electrolyte layer 10 can be further improved.
Here, "equal" means that the ratio of the distances (D1/D2, D1/D3, etc.) is within ±5%.

固体電解質層10は、正極凹部11及び負極凹部15を各々2個以上有する。固体電解質層10において、固体電解質層10の面方向で、正極凹部11と負極凹部15とは、交互に位置していることが好ましい。正極凹部11と負極凹部15とが交互に位置していることで、固体電解質層10の内部の電流密度の均一性をさらに高められる。
ここで、「固体電解質層10の面方向で、正極凹部11と負極凹部15とが交互に位置している」とは、図3に示すように、平面視で、X方向及びY方向の双方に正極凹部11と負極凹部15とが交互に位置している場合のほか、図4に示すように、平面視で、X方向にのみ正極凹部11と負極凹部15とが交互に位置している場合を含むものとする。
なお、正極凹部11と負極凹部15とが交互に位置しているのは、平面視で、任意の方向に位置していればよい。
The solid electrolyte layer 10 has two or more positive electrode recesses 11 and two or more negative electrode recesses 15. In the solid electrolyte layer 10, the positive electrode recesses 11 and the negative electrode recesses 15 are preferably positioned alternately in the surface direction of the solid electrolyte layer 10. By positioning the positive electrode recesses 11 and the negative electrode recesses 15 alternately, the uniformity of the current density inside the solid electrolyte layer 10 can be further improved.
Here, "positive electrode recesses 11 and negative electrode recesses 15 are alternately positioned in the surface direction of solid electrolyte layer 10" includes not only a case where positive electrode recesses 11 and negative electrode recesses 15 are alternately positioned in both the X direction and the Y direction in plan view as shown in FIG. 3 , but also a case where positive electrode recesses 11 and negative electrode recesses 15 are alternately positioned only in the X direction in plan view as shown in FIG. 4 .
The positive electrode recesses 11 and the negative electrode recesses 15 may be alternately positioned in any direction in a plan view.

正極凹部11の深さD11は、固体電解質層10の厚さT10の1/2よりも深いことが好ましい。深さD11が厚さT10の1/2よりも深いと、正極凹部11の最深部が負極凸部16の内部に位置する。このため、固体電解質層10の内部の電流密度をより高められ、電池1の電気特性をより高められる。
深さD11の上限値は特に限定されず、厚さT10よりも小さければよい。
The depth D11 of the positive electrode recess 11 is preferably greater than half the thickness T10 of the solid electrolyte layer 10. When the depth D11 is greater than half the thickness T10, the deepest part of the positive electrode recess 11 is located inside the negative electrode protrusion 16. This further increases the current density inside the solid electrolyte layer 10, thereby further improving the electrical characteristics of the battery 1.
The upper limit of the depth D11 is not particularly limited as long as it is smaller than the thickness T10.

負極凹部15の深さD15は、固体電解質層10の厚さT10の1/2よりも深いことが好ましい。深さD15が厚さT10の1/2よりも深いと、負極凹部15の最深部が正極凸部12の内部に位置する。このため、固体電解質層10の内部の電流密度をより高められ、電池1の電気特性をより高められる。
深さD15の上限値は特に限定されず、厚さT10よりも小さければよい。
The depth D15 of the negative electrode recess 15 is preferably greater than half the thickness T10 of the solid electrolyte layer 10. When the depth D15 is greater than half the thickness T10, the deepest part of the negative electrode recess 15 is located inside the positive electrode projection 12. This further increases the current density inside the solid electrolyte layer 10, thereby further improving the electrical characteristics of the battery 1.
The upper limit of the depth D15 is not particularly limited as long as it is smaller than the thickness T10.

<正極層>
正極層20は、正極活物質を含む。
正極活物質としては、全固体電池に用いられる公知のものを利用できる。正極活物質としては、例えば、一元系正極材、二元系正極材、三元系正極材等が挙げられる。
一元系正極材としては、例えば、LiMO(Mは、Co、Ni、Mn、Al、Fe等の金属元素を表す)が挙げられる。
二元系正極材としては、例えば、Li1-xCoMnO(xは、0<x<1を満たす数)、LiFePO(xは、0<x≦1を満たす数)、Li13(xは、0<x≦1を満たす数)、Li1-xMn(xは、0<x<1を満たす数)、Li1-xNi0.5Mn1.5(xは、0<x<1を満たす数)等が挙げられる。
三元系正極材としては、例えば、LiNi1/3Mn1/3Co1/3等が挙げられる。
これらの正極活物質は、1種を単独で用いてもよく、2種以上を併用してもよい。
<Positive electrode layer>
The positive electrode layer 20 contains a positive electrode active material.
The positive electrode active material may be any known material used in all-solid-state batteries, such as a single-component positive electrode material, a binary positive electrode material, or a ternary positive electrode material.
An example of a single-component positive electrode material is LiMO 2 (M represents a metal element such as Co, Ni, Mn, Al, or Fe).
Examples of binary positive electrode materials include Li 1-x CoMnO 4 (x is a number that satisfies 0<x<1), Li x FePO 4 (x is a number that satisfies 0<x≦1), Li x V 6 O 13 (x is a number that satisfies 0<x≦1), Li 1-x Mn 2 O 4 (x is a number that satisfies 0<x<1), and Li 1-x Ni 0.5 Mn 1.5 O 4 (x is a number that satisfies 0<x<1).
An example of a ternary positive electrode material is LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
These positive electrode active materials may be used alone or in combination of two or more.

正極層20の厚さT20は、例えば、10~500μmが好ましく、30~400μmがより好ましく、80~300μmがさらに好ましい。厚さT20が上記下限値以上であると、電池1の電気容量をより高められる。厚さT20が上記上限値以下であると、電池1の内部抵抗をより低減できる。
厚さT20は、厚さT3Aと同様の方法により求められる。
The thickness T20 of the positive electrode layer 20 is, for example, preferably 10 to 500 μm, more preferably 30 to 400 μm, and even more preferably 80 to 300 μm. When the thickness T20 is equal to or greater than the above lower limit, the electrical capacity of the battery 1 can be further increased. When the thickness T20 is equal to or less than the above upper limit, the internal resistance of the battery 1 can be further reduced.
The thickness T20 is determined in the same manner as the thickness T3A.

<負極層>
負極層30は、負極活物質を含む。負極活物質としては、全固体電池に用いられる公知のものを利用できる。
負極活物質としては、例えば、金属リチウム、金属リチウムとリチウム以外の金属との合金等が挙げられる。負極活物質としては、この他、カーボンやグラファイト等の炭素材料系、SiやSiO等のシリコン材料系、LiTi12(LTO)等のリチウム遷移金属複合酸化物等が挙げられる。
負極活物質は、1種を単独で用いてもよく、2種以上を併用してもよい。
<Negative electrode layer>
The negative electrode layer 30 includes a negative electrode active material. As the negative electrode active material, a known material used in all-solid-state batteries can be used.
Examples of the negative electrode active material include metallic lithium, alloys of metallic lithium and metals other than lithium, etc. Other examples of the negative electrode active material include carbon materials such as carbon and graphite, silicon materials such as Si and SiO, and lithium transition metal composite oxides such as Li 4 Ti 5 O 12 (LTO).
The negative electrode active material may be used alone or in combination of two or more kinds.

負極層30の厚さT30は、例えば、10~500μmが好ましく、30~400μmがより好ましく、80~300μmがさらに好ましい。厚さT30が上記下限値以上であると、電池1の電気容量をより高められる。厚さT30が上記上限値以下であると、電池1の内部抵抗をより低減できる。
厚さT30は、厚さT3Aと同様の方法により求められる。
The thickness T30 of the negative electrode layer 30 is, for example, preferably 10 to 500 μm, more preferably 30 to 400 μm, and even more preferably 80 to 300 μm. When the thickness T30 is equal to or greater than the above lower limit, the electrical capacity of the battery 1 can be further increased. When the thickness T30 is equal to or less than the above upper limit, the internal resistance of the battery 1 can be further reduced.
The thickness T30 is determined in the same manner as the thickness T3A.

≪電気化学セルの製造方法≫
本発明の電気化学セルの製造方法は、固体電解質層の正極層側に開口し、正極層が入り込む正極凹部と、固体電解質層の負極層側に開口し、負極層が入り込む負極凹部とを、固体電解質層の面方向にずらして位置させる工程、を有する。
以下に、本実施形態の電気化学セルの製造方法について、図面を参照して、詳細に説明する。
<Electrochemical cell manufacturing method>
The method for manufacturing an electrochemical cell of the present invention includes a step of positioning a positive electrode recess that opens on the positive electrode layer side of the solid electrolyte layer and into which the positive electrode layer is fitted, and a negative electrode recess that opens on the negative electrode layer side of the solid electrolyte layer and into which the negative electrode layer is fitted, so as to be offset in the plane direction of the solid electrolyte layer.
The method for manufacturing an electrochemical cell according to this embodiment will be described in detail below with reference to the drawings.

図5に示すように、固体電解質層10を用意する。
固体電解質層10を製造するには、固体電解質の粉末を圧粉成形し、電気炉等で焼成して固体電解質層10とする。
固体電解質の粉末としては、上述した固体電解質層10に含まれる固体電解質の粉末が挙げられる。
As shown in FIG. 5, a solid electrolyte layer 10 is prepared.
To manufacture the solid electrolyte layer 10, a powder of the solid electrolyte is compacted and then fired in an electric furnace or the like to form the solid electrolyte layer 10.
The solid electrolyte powder may be the solid electrolyte powder contained in the solid electrolyte layer 10 described above.

焼成の雰囲気は、酸素欠損を抑える為、酸素を含む雰囲気が好ましく、水分の影響が懸念される場合は、ドライ雰囲気を選択することがさらに好ましい。焼成の際、固体電解質シートのゆがみを抑える為、セラミック板(AlやMgO等からなる)やグラファイト板等で挟むことが好ましい。セラミック板との反応や、Liの揮発を抑える為に、固体電解質と同じ材料や、Liを含有する酸化物等をシート化したものをセラミック板との間に挿入してもよい。 The firing atmosphere is preferably an oxygen-containing atmosphere to suppress oxygen deficiency, and if the influence of moisture is a concern, it is more preferable to select a dry atmosphere. During firing, to suppress distortion of the solid electrolyte sheet, it is preferable to sandwich it between ceramic plates (made of Al 2 O 3 , MgO, etc.) or graphite plates. To suppress reaction with the ceramic plates and volatilization of Li, a sheet of the same material as the solid electrolyte or an oxide containing Li may be inserted between the ceramic plates.

次に、図6に示すように、固体電解質層10の一方の面に、負極層30が入り込む負極凹部15を形成する。負極凹部15を形成する方法は特に限定されず、例えば、レーザーを用いる方法、フォトリソグラフィを用いる方法、金型を用いる方法等が挙げられる。
金型を用いる方法の場合、上述した固体電解質の粉末を金型に充填し、圧粉成形し、焼成することで、負極凹部15を有する固体電解質層10が得られる。
なお、負極凹部15は、あらかじめ形成されたものであってもよい。
6, an anode recess 15 into which the anode layer 30 fits is formed on one surface of the solid electrolyte layer 10. The method for forming the anode recess 15 is not particularly limited, and examples thereof include a method using a laser, a method using photolithography, and a method using a mold.
In the method using a mold, the solid electrolyte powder described above is filled into a mold, compacted, and fired to obtain the solid electrolyte layer 10 having the negative electrode recess 15 .
The negative electrode recess 15 may be formed in advance.

負極凹部15を形成することで、負極凹部15が形成されていない部分が、負極凸部16として残る。 By forming the negative electrode recess 15, the portion where the negative electrode recess 15 is not formed remains as the negative electrode protrusion 16.

負極凹部15は、2個以上形成されることが好ましい。負極凹部15を2個以上形成することで、電池1の内部抵抗をより低減できる。負極凹部15を形成する数は、特に限定されないが、上述した各形成方法による負極凹部15の形成のしやすさや、固体電解質層10の強度を維持する観点を考慮して適宜設定することができる。 It is preferable to form two or more negative electrode recesses 15. Forming two or more negative electrode recesses 15 can further reduce the internal resistance of the battery 1. The number of negative electrode recesses 15 to be formed is not particularly limited, but can be set appropriately taking into consideration the ease of forming the negative electrode recesses 15 using each of the formation methods described above and the need to maintain the strength of the solid electrolyte layer 10.

負極凹部15の深さD15は、固体電解質層10の厚さT10の1/2よりも深く形成されることが好ましい。負極凹部15の深さD15を固体電解質層10の厚さT10の1/2よりも深く形成することで、固体電解質層10の内部の電流密度をより高められ、電池1の電気特性をより高められる。 The depth D15 of the negative electrode recess 15 is preferably greater than half the thickness T10 of the solid electrolyte layer 10. By making the depth D15 of the negative electrode recess 15 greater than half the thickness T10 of the solid electrolyte layer 10, the current density inside the solid electrolyte layer 10 can be increased, thereby further improving the electrical characteristics of the battery 1.

次に、図7に示すように、負極層30を形成する。負極層30を形成する方法は特に限定されず、例えば、負極活物質を含む負極スラリーを用意し、負極スラリーに固体電解質層10をディッピングする方法、固体電解質層10にスクリーン印刷等により負極スラリーを塗工する方法等が挙げられる。 Next, as shown in FIG. 7, the negative electrode layer 30 is formed. The method for forming the negative electrode layer 30 is not particularly limited, and examples include a method in which a negative electrode slurry containing a negative electrode active material is prepared and the solid electrolyte layer 10 is dipped into the negative electrode slurry, or a method in which the negative electrode slurry is applied to the solid electrolyte layer 10 by screen printing or the like.

負極層30を形成した後、図8に示すように、固体電解質層10の他方の面(負極凹部15が形成されていない方の面)に形成された負極層30を研磨し、除去する。 After the anode layer 30 is formed, as shown in FIG. 8, the anode layer 30 formed on the other surface of the solid electrolyte layer 10 (the surface on which the anode recess 15 is not formed) is polished and removed.

次に、図7に示すように、固体電解質層10の他方の面に、正極層20が入り込む正極凹部11を形成する。正極凹部11を形成する方法は特に限定されず、例えば、レーザーを用いる方法、フォトリソグラフィを用いる方法等が挙げられる。
なお、正極凹部11は、あらかじめ形成されたものであってもよい。
正極凹部11を形成することで、正極凹部11が形成されていない部分が、正極凸部12として残る。
7, a positive electrode recess 11 into which the positive electrode layer 20 is inserted is formed on the other surface of the solid electrolyte layer 10. The method for forming the positive electrode recess 11 is not particularly limited, and examples thereof include a method using a laser and a method using photolithography.
The positive electrode recess 11 may be formed in advance.
By forming the positive electrode recess 11 , the portion where the positive electrode recess 11 is not formed remains as the positive electrode protrusion 12 .

正極凹部11は、負極凹部15に対して、固体電解質層10の面方向にずらして位置させる。正極凹部11と負極凹部15とを固体電解質層10の面方向にずらして位置させることで、固体電解質層10の内部抵抗を均一にでき、電流密度の均一性を高められる。このため、電池1の電気容量をより高められ、電池1の電池寿命をより高められる。
正極凹部11の位置は、照射するレーザーの位置、フォトリソグラフィのマスクの形状、金型の形状等により調節できる。
The positive electrode recess 11 is positioned with a deviation from the negative electrode recess 15 in the plane direction of the solid electrolyte layer 10. By positioning the positive electrode recess 11 and the negative electrode recess 15 with a deviation from the plane direction of the solid electrolyte layer 10, the internal resistance of the solid electrolyte layer 10 can be made uniform, and the uniformity of the current density can be improved. This allows the electric capacity of the battery 1 to be further increased, and the battery life of the battery 1 to be further improved.
The position of the positive electrode recess 11 can be adjusted by the position of the irradiated laser, the shape of the photolithography mask, the shape of the mold, and the like.

正極凹部11は、2個以上形成されることが好ましい。正極凹部11を2個以上形成することで、電池1の内部抵抗をより低減できる。正極凹部11を形成する数は、特に限定されないが、上述した各形成方法による正極凹部11の形成のしやすさや、固体電解質層10の強度を維持する観点を考慮して適宜設定することができる。
電流密度の均一性をより高められることから、正極凹部11を形成する数は、負極凹部15を形成する数と同じであることが好ましい。
It is preferable to form two or more positive electrode recesses 11. Forming two or more positive electrode recesses 11 can further reduce the internal resistance of the battery 1. The number of positive electrode recesses 11 to be formed is not particularly limited, but can be appropriately set taking into consideration the ease of forming the positive electrode recesses 11 by each of the above-mentioned formation methods and the viewpoint of maintaining the strength of the solid electrolyte layer 10.
The number of positive electrode recesses 11 formed is preferably the same as the number of negative electrode recesses 15 formed, since this can further improve the uniformity of the current density.

正極凹部11は、平面視において、固体電解質層10の面方向で、負極凹部15と交互に位置することが好ましい。正極凹部11と負極凹部15とを、交互に位置させることで、電流密度の均一性をさらに高められる。 The positive electrode recesses 11 are preferably positioned alternately with the negative electrode recesses 15 in the plane direction of the solid electrolyte layer 10 in a plan view. By positioning the positive electrode recesses 11 and the negative electrode recesses 15 alternately, the uniformity of the current density can be further improved.

正極凹部11の深さD11は、固体電解質層10の厚さT10の1/2よりも深く形成されることが好ましい。正極凹部11の深さD11を固体電解質層10の厚さT10の1/2よりも深く形成することで、固体電解質層10の内部の電流密度をより高められ、電池1の電気特性をより高められる。 The depth D11 of the positive electrode recess 11 is preferably greater than half the thickness T10 of the solid electrolyte layer 10. By making the depth D11 of the positive electrode recess 11 greater than half the thickness T10 of the solid electrolyte layer 10, the current density inside the solid electrolyte layer 10 can be increased, thereby further improving the electrical characteristics of the battery 1.

固体電解質層10の厚さT10と正極凹部11の深さD11との差(正極凹部11の最深部から負極層30までの距離)をD1とする。
固体電解質層10の厚さT10と負極凹部15の深さD15との差(負極凹部15の最深部から正極層20までの距離)をD2とする。
固体電解質層10の厚さ方向(Z方向)の断面視における、正極凹部11と負極凹部15との固体電解質層10の面方向(X方向)の距離をD3とする。
このとき、距離D1と距離D2と距離D3とが、互いに等しくなるように、正極凹部11を位置させることが好ましい。距離D1と距離D2と距離D3とが互いに等しくなるように、正極凹部11を位置させることで、固体電解質層10の内部の電流密度の均一性をさらに高められる。
ここで、「等しい」とは、距離の比(D1/D2、D1/D3等)が±5%以内であることをいうものとする。
The difference between the thickness T10 of the solid electrolyte layer 10 and the depth D11 of the positive electrode recess 11 (the distance from the deepest part of the positive electrode recess 11 to the negative electrode layer 30) is defined as D1.
The difference between the thickness T10 of the solid electrolyte layer 10 and the depth D15 of the negative electrode recess 15 (the distance from the deepest part of the negative electrode recess 15 to the positive electrode layer 20) is defined as D2.
In a cross-sectional view of the solid electrolyte layer 10 in the thickness direction (Z direction), the distance between the positive electrode recess 11 and the negative electrode recess 15 in the surface direction (X direction) of the solid electrolyte layer 10 is defined as D3.
In this case, it is preferable to position the positive electrode recess 11 so that the distance D1, the distance D2, and the distance D3 are equal to one another. By positioning the positive electrode recess 11 so that the distance D1, the distance D2, and the distance D3 are equal to one another, the uniformity of the current density inside the solid electrolyte layer 10 can be further improved.
Here, "equal" means that the ratio of the distances (D1/D2, D1/D3, etc.) is within ±5%.

次に、図10に示すように、正極層20を形成する。正極層20を形成する方法は特に限定されず、例えば、正極活物質を含む正極スラリーを用意し、正極スラリーに負極層30が形成された固体電解質層10をディッピングする方法、負極層30が形成された固体電解質層10にスクリーン印刷等により正極スラリーを塗工する方法等が挙げられる。 Next, as shown in FIG. 10, the positive electrode layer 20 is formed. The method for forming the positive electrode layer 20 is not particularly limited, and examples include a method in which a positive electrode slurry containing a positive electrode active material is prepared and the solid electrolyte layer 10 on which the negative electrode layer 30 has been formed is dipped into the positive electrode slurry, or a method in which the positive electrode slurry is applied to the solid electrolyte layer 10 on which the negative electrode layer 30 has been formed by screen printing or the like.

正極層20を形成した後、固体電解質層10の他方の面(負極凹部15が形成されていない方の面)以外に形成された正極層20を研磨し、除去する。
以上の工程により、図2に示すような、電極体3Aが得られる。
After the positive electrode layer 20 is formed, the positive electrode layer 20 formed on the other surface of the solid electrolyte layer 10 (the surface on which the negative electrode recess 15 is not formed) is polished and removed.
Through the above steps, an electrode body 3A as shown in FIG. 2 is obtained.

以上の説明では、固体電解質層10に負極層30を形成してから、正極層20を形成したが、本発明の電気化学セルの製造方法は、上述した実施形態に限定されない。
例えば、固体電解質層10に正極層20を形成してから、負極層30を形成してもよい。
正極凹部11を形成する際、金型を用いて正極凹部11を形成してもよい。
この場合、負極凹部15と正極凹部11とが形成された金型を用い、この金型に固体電解質の粉末を充填し、圧粉成形し、焼成することで、負極凹部15と正極凹部11とを有する固体電解質層10が得られる。この固体電解質層10に負極層30と正極層20とを順次形成することで、電極体3Aが得られる。
なお、負極層30と正極層20とを形成する順序は特に限定されず、負極層30を形成してから正極層20を形成してもよく、正極層20を形成してから負極層30を形成してもよい。
In the above description, the negative electrode layer 30 is formed on the solid electrolyte layer 10, and then the positive electrode layer 20 is formed, but the method for manufacturing an electrochemical cell of the present invention is not limited to the above-described embodiment.
For example, the positive electrode layer 20 may be formed on the solid electrolyte layer 10 and then the negative electrode layer 30 may be formed.
When forming the positive electrode recess 11, the positive electrode recess 11 may be formed using a mold.
In this case, a mold in which the anode recesses 15 and the cathode recesses 11 are formed is used, and the mold is filled with solid electrolyte powder, followed by powder compaction and firing, thereby obtaining the solid electrolyte layer 10 having the anode recesses 15 and the cathode recesses 11. The anode layer 30 and the cathode layer 20 are sequentially formed on the solid electrolyte layer 10, thereby obtaining the electrode body 3A.
The order in which the negative electrode layer 30 and the positive electrode layer 20 are formed is not particularly limited, and the negative electrode layer 30 may be formed before the positive electrode layer 20, or the positive electrode layer 20 may be formed before the negative electrode layer 30.

本発明の電気化学セルは、正極凹部と負極凹部とが、固体電解質層の面方向にずれているため、固体電解質層の内部抵抗を均一にでき、電流密度の均一性を高められる。このため、電気容量をより高められ、電池寿命をより高められる。
本発明の電気化学セルの製造方法は、正極凹部と負極凹部とを、固体電解質層の面方向にずらして位置させるため、固体電解質層の内部抵抗を均一にでき、電流密度の均一性を高められる。このため、電気容量をより高められ、電池寿命をより高められる。
In the electrochemical cell of the present invention, the positive electrode recesses and the negative electrode recesses are offset in the plane direction of the solid electrolyte layer, which makes it possible to uniform the internal resistance of the solid electrolyte layer and improve the uniformity of the current density, thereby further increasing the electric capacity and the battery life.
In the method for producing an electrochemical cell of the present invention, the positive electrode recesses and the negative electrode recesses are positioned so as to be offset in the planar direction of the solid electrolyte layer, thereby making it possible to uniform the internal resistance of the solid electrolyte layer and improve the uniformity of the current density, thereby further increasing the electric capacity and the battery life.

以上、本発明の電気化学セル及び電気化学セルの製造方法について説明したが、本発明は上記の実施形態に限定されるものではなく、その趣旨を逸脱しない範囲で適宜変更可能である。
例えば、図11に示すように、電極体3Bは、電極体3Aに比べて、正極凹部13の深さD13が浅く、負極凹部17の深さD17が浅くてもよい。
正極凹部13の深さD13が、深さD11よりも浅いことで、固体電解質層10の厚さT10と正極凹部13の深さD13との差(正極凹部13の最深部から負極層30までの距離)D4を、距離D1よりも大きくできる。このため、特定部位の劣化を抑制でき、電池寿命をより高められる。
負極凹部17の深さD17が、深さD15よりも浅いことで、固体電解質層10の厚さT10と負極凹部17の深さD17との差(負極凹部17の最深部から正極層20までの距離)D5を、距離D2よりも大きくできる。このため、特定部位の劣化を抑制でき、電池寿命をより高められる。
図11において、距離D4と距離D5とは等しい。このため、固体電解質層10の内部の電流密度を均一にできる。
ここで、「等しい」とは、距離の比(D4/D5)が±5%以内であることをいうものとする。
The electrochemical cell and the method for manufacturing an electrochemical cell according to the present invention have been described above, but the present invention is not limited to the above-described embodiments and can be modified as appropriate within the scope of the invention.
For example, as shown in FIG. 11, the electrode body 3B may have a shallower depth D13 of the positive electrode recess 13 and a shallower depth D17 of the negative electrode recess 17 than the electrode body 3A.
Because the depth D13 of the positive electrode recess 13 is shallower than the depth D11, the difference D4 between the thickness T10 of the solid electrolyte layer 10 and the depth D13 of the positive electrode recess 13 (the distance from the deepest part of the positive electrode recess 13 to the negative electrode layer 30) can be made larger than the distance D1. This makes it possible to suppress deterioration of specific portions and further extend the battery life.
Because the depth D17 of the negative electrode recess 17 is shallower than the depth D15, the difference D5 between the thickness T10 of the solid electrolyte layer 10 and the depth D17 of the negative electrode recess 17 (the distance from the deepest part of the negative electrode recess 17 to the positive electrode layer 20) can be made larger than the distance D2. This makes it possible to suppress deterioration of a specific portion and further extend the battery life.
11, the distance D4 is equal to the distance D5, which allows the current density inside the solid electrolyte layer 10 to be uniform.
Here, "equal" means that the ratio of the distances (D4/D5) is within ±5%.

正極凹部13の幅W13は、正極凹部11の幅W11と同様である。正極凹部13の幅W13は、正極凹部11の幅W11と同じでもよく、異なっていてもよい。
正極凸部14の高さH14は、正極凹部13の深さD13と同様である。
正極凸部14の幅W14は、正極凸部12の幅W12と同様である。正極凸部14の幅W14は、正極凸部12の幅W12と同じでもよく、異なっていてもよい。
The width W13 of the positive electrode recess 13 is the same as the width W11 of the positive electrode recess 11. The width W13 of the positive electrode recess 13 may be the same as or different from the width W11 of the positive electrode recess 11.
The height H14 of the positive electrode convex portion 14 is the same as the depth D13 of the positive electrode concave portion 13.
The width W14 of the positive electrode convex portion 14 is the same as the width W12 of the positive electrode convex portion 12. The width W14 of the positive electrode convex portion 14 may be the same as or different from the width W12 of the positive electrode convex portion 12.

負極凹部17の幅W17は、負極凹部15の幅W15と同様である。負極凹部17の幅W17は、負極凹部15の幅W15と同じでもよく、異なっていてもよい。
負極凸部18の高さH18は、負極凹部17の深さD17と同様である。
負極凸部18の幅W18は、負極凸部16の幅W16と同様である。負極凸部18の幅W18は、負極凸部16の幅W16と同じでもよく、異なっていてもよい。
The width W17 of the negative electrode recess 17 is the same as the width W15 of the negative electrode recess 15. The width W17 of the negative electrode recess 17 may be the same as or different from the width W15 of the negative electrode recess 15.
The height H18 of the negative electrode convex portion 18 is the same as the depth D17 of the negative electrode concave portion 17.
The width W18 of the negative electrode protrusion 18 is the same as the width W16 of the negative electrode protrusion 16. The width W18 of the negative electrode protrusion 18 may be the same as or different from the width W16 of the negative electrode protrusion 16.

図12に示すように、電極体3Cは、直線状の正極凹部11と、直線状の負極凹部15とを有していてもよい。 As shown in FIG. 12, the electrode body 3C may have a linear positive electrode recess 11 and a linear negative electrode recess 15.

図13に示すように、電極体3Dは、円柱状の正極凹部と、円柱状の負極凹部とを有していてもよい。 As shown in FIG. 13, the electrode body 3D may have a cylindrical positive electrode recess and a cylindrical negative electrode recess.

図14に示すように、電極体3Eは、ビア加工された正極凹部と、ビア加工された負極凹部とを有していてもよい。 As shown in FIG. 14, an electrode body 3E may have a positive electrode recess with a via formed therein and a negative electrode recess with a via formed therein.

例えば、固体電解質層の形状は、平面視円形状ではなく、平面視多角形状であってもよい。
例えば、電極体は、1つではなく、2つ以上積層されていてもよい。
For example, the shape of the solid electrolyte layer may be polygonal in plan view instead of circular in plan view.
For example, the electrode body may be a stack of two or more electrodes instead of one.

1…電気化学セル、2…外装体、3A,3B,3C,3D,3E…電極体、10…固体電解質層、11,13…正極凹部、12,14…正極凸部、15,17…負極凹部、16,18…負極凸部、20…正極層、30…負極層 1... electrochemical cell, 2... outer casing, 3A, 3B, 3C, 3D, 3E... electrode assembly, 10... solid electrolyte layer, 11, 13... positive electrode recess, 12, 14... positive electrode protrusion, 15, 17... negative electrode recess, 16, 18... negative electrode protrusion, 20... positive electrode layer, 30... negative electrode layer

Claims (4)

正極活物質を含む正極層と、
負極活物質を含む負極層と、
固体電解質を含む固体電解質層と、を有し、
前記固体電解質層は、前記正極層と前記負極層との間に位置し、
前記固体電解質層は、前記正極層側に開口し、前記正極層の一部が入り込む正極凹部を複数有し、
前記固体電解質層は、前記負極層側に開口し、前記負極層の一部が入り込む負極凹部を複数有し、
前記正極凹部と、前記負極凹部とが、前記固体電解質層の面方向にずれている、電気化学セルの製造方法であって、
固体電解質層の一方の面に負極凹部を形成した後、前記固体電解質層の一方の面を覆うとともに前記負極凹部を埋める負極層を形成し、この後、
前記固体電解質層の他方の面に前記負極凹部とずらした位置に正極凹部を形成し、この後、前記固体電解質層の他方の面を覆うとともに前記正極凹部を埋める正極層を形成する電気化学セルの製造方法。
a positive electrode layer containing a positive electrode active material;
a negative electrode layer containing a negative electrode active material;
a solid electrolyte layer containing a solid electrolyte,
the solid electrolyte layer is located between the positive electrode layer and the negative electrode layer,
the solid electrolyte layer has a plurality of positive electrode recesses that are open to the positive electrode layer side and into which a portion of the positive electrode layer is inserted;
the solid electrolyte layer has a plurality of negative electrode recesses that are open to the negative electrode layer side and into which a portion of the negative electrode layer is inserted;
a method for manufacturing an electrochemical cell, wherein the positive electrode recess and the negative electrode recess are misaligned in a plane direction of the solid electrolyte layer,
After forming an anode recess on one surface of a solid electrolyte layer, an anode layer is formed to cover the one surface of the solid electrolyte layer and fill the anode recess, and then
a positive electrode recess formed on the other surface of the solid electrolyte layer at a position offset from the negative electrode recess, and then a positive electrode layer formed to cover the other surface of the solid electrolyte layer and fill the positive electrode recess.
面視において、前記固体電解質層の面方向で、前記正極凹部と、前記負極凹部とを、
交互に位置させる、請求項に記載の電気化学セルの製造方法。
In a plan view, the positive electrode recess and the negative electrode recess are arranged in a surface direction of the solid electrolyte layer,
The method for manufacturing an electrochemical cell according to claim 1 , wherein the electrodes are alternately positioned.
前記正極凹部の深さを前記固体電解質層の厚さの1/2よりも深くし、前記負極凹部の深さを前記固体電解質層の厚さの1/2よりも深くする、請求項又はに記載の電気化学セルの製造方法。 3. The method for manufacturing an electrochemical cell according to claim 1 , wherein the depth of the positive electrode recess is greater than half the thickness of the solid electrolyte layer, and the depth of the negative electrode recess is greater than half the thickness of the solid electrolyte layer. 前記固体電解質層の厚さと前記正極凹部の深さとの差と、
前記固体電解質層の厚さと前記負極凹部の深さとの差と、
前記固体電解質層の厚さ方向の断面視における前記正極凹部と前記負極凹部との距離と、を互いに等しくなるようにする、請求項1~3のいずれか一項に記載の電気化学セルの製造方法。
a difference between the thickness of the solid electrolyte layer and the depth of the positive electrode recess;
a difference between the thickness of the solid electrolyte layer and the depth of the negative electrode recess;
4. The method for manufacturing an electrochemical cell according to claim 1, wherein distances between the positive electrode recess and the negative electrode recess in a cross-sectional view in the thickness direction of the solid electrolyte layer are made equal to each other.
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