JP6351963B2 - Secondary battery and manufacturing method thereof - Google Patents

Secondary battery and manufacturing method thereof Download PDF

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JP6351963B2
JP6351963B2 JP2013254836A JP2013254836A JP6351963B2 JP 6351963 B2 JP6351963 B2 JP 6351963B2 JP 2013254836 A JP2013254836 A JP 2013254836A JP 2013254836 A JP2013254836 A JP 2013254836A JP 6351963 B2 JP6351963 B2 JP 6351963B2
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oxide semiconductor
electrode
secondary battery
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JP2015115130A (en
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省三 出雲
省三 出雲
友和 齋藤
友和 齋藤
中澤　明
明 中澤
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Micronics Japan Co Ltd
Guala Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Description

本発明は二次電池及びその製造方法に関し、例えば、金属酸化物の光励起構造変化を利用して、バンドキャップ中に新たなエネルギー準位を形成して電子を捕獲する動作原理に基づく二次電池（以下、「量子電池」と呼ぶこともある）に適用し得る。   The present invention relates to a secondary battery and a manufacturing method thereof, for example, a secondary battery based on an operation principle of capturing a new energy level in a band cap by using a photoexcitation structure change of a metal oxide to capture electrons. (Hereinafter also referred to as “quantum battery”).

二次電池としては、ニッケル水素電池（Ｎｉ−ＭＨ）やリチウムイオン二次電池（ＬＩＢ）などが知られている。一方、近年、小型でかつ大容量の電池が求められている。そのため、単独で二次電池として機能する単位（以下、単位セルと呼ぶ）を、複数重ねるようなことが行われている。   Known secondary batteries include nickel metal hydride batteries (Ni-MH) and lithium ion secondary batteries (LIB). On the other hand, in recent years, a battery having a small size and a large capacity has been demanded. Therefore, a plurality of units (hereinafter referred to as unit cells) that function as a secondary battery independently are stacked.

非特許文献１の３１９頁〜３２０頁には、図１及び図２に示すような円筒型及び角型のニッケル水素電池（Ｎｉ−ＭＨ）の構造が記載されている。円筒型電池１Ａは、所定形状の薄板状の正極２及び負極３を、セパレータ４を介して渦巻状に巻き取り（渦巻は単位セルを重ねたと見ることができる）、円筒型のケース５に挿入し、電解液を注入後に密閉して電池として完成させている。角型電池１Ｂは、所定形状の薄板状の正極２及び負極３間にセパレータ４を介した構造を積層し、角型のケース５に挿入し、電解液を注入後に密閉して電池として完成させている。   Non-Patent Document 1 pages 319 to 320 describe the structures of cylindrical and prismatic nickel metal hydride batteries (Ni-MH) as shown in FIGS. Cylindrical battery 1A has a thin plate-like positive electrode 2 and negative electrode 3 of a predetermined shape wound in a spiral shape via a separator 4 (the spiral can be seen as a stack of unit cells) and inserted into a cylindrical case 5 Then, after injecting the electrolyte, the battery is sealed to complete the battery. A prismatic battery 1B has a structure in which a separator 4 is stacked between a thin plate-like positive electrode 2 and a negative electrode 3 having a predetermined shape, and is inserted into a rectangular case 5 and sealed after injecting an electrolytic solution to complete a battery. ing.

特許文献１には、図３に示すような角型のリチウムイオン二次電池の内部構造（極板群）が記載されている。ジグザグに折り曲げられたセパレータ４の連続体の谷溝内に正極板２と負極板３とを交互に挿入して、ジグザグ方向に押圧して扁平にした極板群１Ｃが記載されている。このような極板群が、角型の外装缶に挿入され、電解液が注入された後に密閉されて角型電池として完成される。   Patent Document 1 describes the internal structure (electrode plate group) of a rectangular lithium ion secondary battery as shown in FIG. The electrode plate group 1C is described in which the positive electrode plate 2 and the negative electrode plate 3 are alternately inserted into valley grooves of a continuous body of the separator 4 bent in a zigzag, and pressed flat in a zigzag direction. Such an electrode plate group is inserted into a rectangular outer can and sealed after an electrolytic solution is injected to complete a rectangular battery.

また、近年、固体薄膜化して構成される全固体型の二次電池が研究、開発されており、小型化を実現する二次電池として期待されている。図４には、全固体型の二次電池の構成を示す斜視図及び断面図を示している。図４は、正極端子及び負極端子などの端子部材、外装部材や被覆部材などの実装部材などを省略している。全固体型の二次電池１Ｄは、負極層３と正極層２との間に充放電時に内部変化を起こす固体の層（以下、蓄電層と呼ぶ）６を有するものである。全固体型の二次電池１Ｄとしては、上述した量子電池や、全固体型のリチウムイオン二次電池などがある。量子電池の場合、負極層３と正極層２との間に、充電動作で電子を蓄積（捕獲）し、放電動作で蓄積した電子を放出する層（後述するようにこの層を充電層と呼ぶ）が設けられており、この充電層が蓄電層６に該当する。また、全固体型のリチウムイオン二次電池の場合、負極層３と正極層２との間に、固体電解質層が設けられており、この固体電解質層が蓄電層６に該当する。なお、図４に示す構造を単位セルとして積層するような場合には、蓄電層６の周囲などに、負極層３と正極層２とを絶縁したり、蓄電層６の周囲を保護したりするシール７を設けることが好ましい（但し、シール７は必須の構成要素ではない）。   In recent years, an all-solid-state secondary battery configured by forming a solid thin film has been researched and developed, and is expected as a secondary battery that realizes downsizing. FIG. 4 shows a perspective view and a cross-sectional view showing the configuration of the all solid state secondary battery. In FIG. 4, terminal members such as a positive electrode terminal and a negative electrode terminal, and mounting members such as an exterior member and a covering member are omitted. The all-solid-state secondary battery 1 </ b> D includes a solid layer (hereinafter referred to as a power storage layer) 6 that causes an internal change between the negative electrode layer 3 and the positive electrode layer 2 during charge and discharge. Examples of the all-solid-type secondary battery 1D include the above-described quantum battery and an all-solid-type lithium ion secondary battery. In the case of a quantum battery, a layer that accumulates (captures) electrons in a charging operation and discharges electrons accumulated in a discharging operation between the negative electrode layer 3 and the positive electrode layer 2 (this layer is referred to as a charging layer as will be described later). ), And this charge layer corresponds to the electricity storage layer 6. In the case of an all solid-state lithium ion secondary battery, a solid electrolyte layer is provided between the negative electrode layer 3 and the positive electrode layer 2, and this solid electrolyte layer corresponds to the power storage layer 6. When the structure shown in FIG. 4 is stacked as a unit cell, the negative electrode layer 3 and the positive electrode layer 2 are insulated around the power storage layer 6 or the like, or the periphery of the power storage layer 6 is protected. It is preferable to provide the seal 7 (however, the seal 7 is not an essential component).

全固体型の二次電池１Ｄも、周知のように、単位セルを直列に積層することで端子電圧を高めることができ、単位セルを並列に積層することでエネルギー密度を大きくすることができる。   As is well known, the all-solid-state secondary battery 1D can also increase the terminal voltage by stacking unit cells in series, and can increase the energy density by stacking unit cells in parallel.

図５は、二次電池１Ｄを単位セルとし、複数の単位セルを並列に接続した、容易に考えられる二次電池１Ｅを示す断面図である。二次電池１Ｅにおける各単位セル（１Ｄ）はそれぞれ、負極端子板８及び正極端子板９に挟持されており、ある単位セルに係る正極端子板９と、その上段の単位セルに係る負極端子板８との間には絶縁層１０が設けられている。複数の負極端子板８は負極端子連結部８ｂによって連結されており、複数の正極端子板９は正極端子連結部９ｂによって連結されており、負極端子連結部８ｂ及び正極端子連結部９ｂはそれぞれ、図示しない実装部材の外部に負極端子、正極端子を露出させるための延長部８ａ、９ａを有している。二次電池１Ｄの端子電圧がＶｏ、エネルギー密度がＩｏであり、二次電池１Ｄの積層数（並列接続数）をＮとすると、二次電池１Ｅの端子電圧Ｖｏであり、容量はＮ×Ｉｏ（例えば、積層数が６であれば６×Ｉｏ）となる。   FIG. 5 is a cross-sectional view showing an easily conceivable secondary battery 1E in which the secondary battery 1D is a unit cell and a plurality of unit cells are connected in parallel. Each unit cell (1D) in the secondary battery 1E is sandwiched between the negative electrode terminal plate 8 and the positive electrode terminal plate 9, and the positive electrode terminal plate 9 related to a certain unit cell and the negative electrode terminal plate related to the upper unit cell. Insulating layer 10 is provided between 8 and 8. The plurality of negative electrode terminal plates 8 are connected by a negative electrode terminal connecting portion 8b, the plurality of positive electrode terminal plates 9 are connected by a positive electrode terminal connecting portion 9b, and the negative electrode terminal connecting portion 8b and the positive electrode terminal connecting portion 9b are respectively Extension portions 8a and 9a for exposing the negative electrode terminal and the positive electrode terminal are provided outside a mounting member (not shown). When the terminal voltage of the secondary battery 1D is Vo and the energy density is Io, and the number of stacked secondary batteries 1D (the number of parallel connections) is N, the terminal voltage Vo of the secondary battery 1E is N × Io. (For example, if the number of stacked layers is 6, 6 × Io).

高い端子電圧で大きなエネルギー密度の二次電池を実現するには、単位セルの直列積層と並列積層とを組み合わせれば良い。例えば、図５の負極端子板８及び正極端子板９に挟持されている単位セル（１Ｄ）の部分を、複数の単位セルを直列的に積層したものと置き換えることにより、高い端子電圧で大きなエネルギー密度の二次電池を構成することができる。   In order to realize a secondary battery having a high energy density and a high terminal voltage, it is only necessary to combine a series stack and a parallel stack of unit cells. For example, by replacing the portion of the unit cell (1D) sandwiched between the negative electrode terminal plate 8 and the positive electrode terminal plate 9 in FIG. 5 with a plurality of unit cells stacked in series, a large energy can be obtained with a high terminal voltage. A secondary battery having a high density can be formed.

特開２００９−１４０７０７JP2009-140707

電気化学会 電池技術委員会編、「電池ハンドブック」、株式会社オーム社、平成２２年２月発行The Electrochemical Society, Battery Technical Committee, “Battery Handbook”, published by Ohm Co., Ltd., February 2010

図１〜図３に示す従来の二次電池では、隣接する単位セルの正極と負極とを絶縁させるためにセパレータを配置させることが必要であり、また、電解液の収容空間を確保するため、電池の全容積を小さくすることが困難であった。また、図１〜図３に示す二次電池では、化学反応を利用しているために、充放電性能が劣化したり、寿命が低下したりする。また、電解液を使用しているので液漏れのリスクを伴っている。さらに、リチウムイオン型の二次電池では、過充電、充放電により信頼性が低下したり、電解液を使用しているため電極間が短絡する恐れがあったりする。   In the conventional secondary battery shown in FIG. 1 to FIG. 3, it is necessary to arrange a separator to insulate the positive electrode and the negative electrode of adjacent unit cells, and in order to secure a storage space for the electrolyte, It was difficult to reduce the total volume of the battery. Moreover, in the secondary battery shown in FIGS. 1-3, since chemical reaction is utilized, charging / discharging performance deteriorates or a lifetime falls. Moreover, since the electrolytic solution is used, there is a risk of liquid leakage. Furthermore, in a lithium ion type secondary battery, reliability may be reduced due to overcharging and charging / discharging, and the use of an electrolyte may cause a short circuit between electrodes.

電解液を利用することに伴う不都合は、全固体型の二次電池によりかなりの部分が解決される。   The disadvantages associated with the use of the electrolytic solution can be solved to a great extent by the all-solid-state secondary battery.

上述したように、複数の単位セルを並列接続させることにより、二次電池のエネルギー密度を大きくすることができる。しかし、このような二次電池１Ｅは、図５に示すように、隣接する単位セルの負極端子板８及び正極端子板９との間に絶縁層１０を設けなければならず、また、単位セルの負極層３の数だけ負極端子板８を設けると共に、単位セルの正極層２の数だけ正極端子板９を設けなければならず、二次電池１Ｅの容積が大きくなる。   As described above, the energy density of the secondary battery can be increased by connecting a plurality of unit cells in parallel. However, in such a secondary battery 1E, as shown in FIG. 5, an insulating layer 10 must be provided between the negative electrode terminal plate 8 and the positive electrode terminal plate 9 of adjacent unit cells, and the unit cell As many negative electrode terminals 8 as the number of negative electrode layers 3 must be provided, and as many positive electrode terminals 9 as the number of positive electrode layers 2 of the unit cell must be provided, which increases the volume of the secondary battery 1E.

一般的に、電池の容積効率は、電池の全容積に対する電池の実効容積の割合で求められる。二次電池の充電周期を考慮すると、二次電池のエネルギー密度を大きくすることが求められるが、エネルギー密度を大きくしても電池の全容積が小さいことが好ましい。また、電池の全容積が小さくなれば、二次電池の小型化にもつながる。負極端子板８及び正極端子板９は電池の構成上必要なものであるが、絶縁層１０は充電に直接寄与しないためエネルギー密度向上の阻害要因となっている。   In general, the volumetric efficiency of a battery is determined by the ratio of the effective volume of the battery to the total volume of the battery. Considering the charging cycle of the secondary battery, it is required to increase the energy density of the secondary battery, but it is preferable that the total volume of the battery is small even if the energy density is increased. Moreover, if the total volume of the battery is reduced, the secondary battery can be reduced in size. The negative electrode terminal plate 8 and the positive electrode terminal plate 9 are necessary for the configuration of the battery, but the insulating layer 10 does not contribute directly to charging, and thus is an obstacle to improving the energy density.

所望するエネルギー密度が大きくなればなるほど、並列接続する単位セルの積層数を増大させれば良い。しかし、積層数の増大に伴い、絶縁層１０の数も増えてしまい（負極端子板８や正極端子板９の数も増える）、全容積を一段と大きくする。   As the desired energy density increases, the number of stacked unit cells connected in parallel may be increased. However, as the number of laminated layers increases, the number of insulating layers 10 also increases (the number of negative electrode terminal plates 8 and positive electrode terminal plates 9 also increases), and the total volume is further increased.

並列接続でも直列接続でも、複数の単位セルを積層する二次電池では、各単位セルの位置合わせの要求が高い。図５に示す二次電池１Ｅの場合、負極端子連結部８ｂや正極端子連結部９ｂが単位セル１Ｄに近い方（図５の隙間Ｌが短い方）が全容積の軽減の観点から好ましい。例えば、いずれかの単位セルが図５の右にずれて積層され、その単位セルの負極層３が正極端子連結部９ｂに接した場合には短絡経路が形成されてしまう。そのため、各単位セルの位置合わせの要求が高く、製造効率の低下を招く可能性もある。   In a secondary battery in which a plurality of unit cells are stacked, both in parallel connection and in series connection, there is a high demand for alignment of each unit cell. In the case of the secondary battery 1E shown in FIG. 5, it is preferable from the viewpoint of reducing the total volume that the negative electrode terminal connecting portion 8b and the positive electrode terminal connecting portion 9b are closer to the unit cell 1D (the one having the short gap L in FIG. 5). For example, when one of the unit cells is stacked with being shifted to the right in FIG. 5 and the negative electrode layer 3 of the unit cell is in contact with the positive terminal connecting portion 9b, a short circuit path is formed. Therefore, there is a high demand for alignment of each unit cell, which may cause a reduction in manufacturing efficiency.

また、積層工程では、積層数だけの単位セルを積層処理しなければならず、製造工数が多いものとなっていた。   Further, in the stacking process, unit cells as many as the number of stacks have to be stacked, resulting in a large number of manufacturing steps.

そのため、蓄電層を正極層と負極層とで挟んだ全固体型の二次電池であって、エネルギー密度が高く、製造プロセスの少ない二次電池及びその製造方法が望まれている。   Therefore, there is a demand for an all-solid-state secondary battery in which a power storage layer is sandwiched between a positive electrode layer and a negative electrode layer, which has a high energy density and a small manufacturing process, and a manufacturing method thereof.

かかる課題を解決するため、第１の本発明の二次電池は、（１）第１電極としての機能と基材としての機能とを発揮するシート状の第１電極兼用基材と、（２）上記第１電極兼用基材の表面側に設けられた表面側充電層と、（３）上記表面側充電層に積層された表面側第２電極層と、（４）上記第１電極兼用基材の裏面側に設けられた裏面側充電層と、（５）上記裏面側充電層に積層された裏面側第２電極層と、（６）上記第１電極兼用基材と上記表面側充電層との間に設けられた表面側第１酸化物半導体層と、（７）上記第１電極兼用基材と上記裏面側充電層との間に設けられた裏面側第１酸化物半導体層と、（８）上記表面側充電層と上記表面側第２電極層との間に設けられた表面側第２酸化物半導体層と、（９）上記裏面側充電層と上記裏面側第２電極層との間に設けられた裏面側第２酸化物半導体層とを備え、（１０）上記第１電極兼用基材の少なくとも一部の端面に、上記表面側第２電極層及び上記裏面側第２電極層と、上記第１電極との短絡を防止する基材端面絶縁部を設け、（１１）第１電極兼用基材の端部における表面及び裏面の基材端面絶縁部のそれぞれの厚みが、表面側第１酸化物半導体層及び裏面側第１酸化物半導体層のそれぞれの厚みと同程度であることを特徴とする。 In order to solve such a problem, the secondary battery of the first aspect of the present invention includes: (1) a sheet-like first electrode-use base material that exhibits a function as a first electrode and a function as a base material; ) A surface side charging layer provided on the surface side of the first electrode combined substrate; (3) a surface side second electrode layer laminated on the surface side charging layer; and (4) the first electrode combined base. A back side charge layer provided on the back side of the material, (5) a back side second electrode layer laminated on the back side charge layer, and (6) the first electrode combined substrate and the front side charge layer. And (7) a back side first oxide semiconductor layer provided between the first electrode combined substrate and the back side charge layer, and (8) a surface-side second oxide semiconductor layer provided between the surface-side charging layer and the surface-side second electrode layer; and (9) the back-side charging layer and the top A back-side second oxide semiconductor layer provided between the back-side second electrode layer and (10) the front-side second electrode layer on at least a part of the end surface of the first electrode combined substrate. And the base-material end surface insulation part which prevents the short circuit with the said back side 2nd electrode layer and the said 1st electrode is provided, (11) The base-material end surface insulation part of the surface in the edge part of a 1st electrode combined use base material and a back surface The thicknesses of the first and second oxide layers are approximately the same as the thicknesses of the first oxide semiconductor layer on the front surface side and the first oxide semiconductor layer on the rear surface side.

第２の本発明の二次電池の製造方法は、（１）第１電極としての機能と基材としての機能とを発揮するシート状の第１電極兼用基材の少なくとも一部の端面に、基材端面絶縁部を形成する第１工程と、（２）第１電極兼用基材の表面側及び裏面側のそれぞれに、第１電極兼用基材の表面及び裏面における基材端面絶縁部のそれぞれと同程度の厚みで第１酸化物半導体層を積層する第２工程と、（３）表面側の上記第１酸化物半導体層に表面側充電層を積層する第３工程と、（４）裏面側の上記第１酸化物半導体層に裏面側充電層を積層する第４工程と、（５）上記表面側充電層及び上記裏面側充電層に紫外線を照射する第５工程と、（６）上記表面側充電層に第２酸化物半導体層及び第２電極層を積層する第６工程と、（７）上記裏面側充電層に第２酸化物半導体層及び第２電極層を積層する第７工程とを含むことを特徴とする。 The manufacturing method of the secondary battery according to the second aspect of the present invention includes (1) at least a part of the end surface of the sheet-like first electrode-use base material that exhibits the function as the first electrode and the function as the base material, A first step of forming a base material end surface insulating portion; and (2) a base material end surface insulating portion on the front surface and the back surface of the first electrode combined base material on each of the front surface side and the back surface side of the first electrode combined base material. A second step of laminating the first oxide semiconductor layer with the same thickness as (3), (3) a third step of laminating the surface-side charging layer on the first oxide semiconductor layer on the surface side, and (4) back surface A fourth step of laminating a back-side charging layer on the first oxide semiconductor layer on the side, (5) a fifth step of irradiating the front-side charging layer and the back-side charging layer with ultraviolet rays, and (6) the above-mentioned A sixth step of laminating the second oxide semiconductor layer and the second electrode layer on the front side charging layer; and (7) the back side charging. Characterized in that it comprises a seventh step of laminating a second oxide semiconductor layer and the second electrode layer.

本発明の二次電池及びその製造方法は、１つの第１電極層（第１電極兼用基材）がそれに対して互いに反対側に形成された２つの単位セルの第１電極層を兼ねるため、基材としての強度を維持しながら、実効的に第１電極層の厚みを半減できる点でエネルギー密度向上に寄与する。また、１回の第１電極層（第１電極兼用基材）の製造により２つの単位セルが形成できるから、製造プロセス削減効果も有する。   In the secondary battery and the manufacturing method of the present invention, one first electrode layer (first electrode combined base material) also serves as the first electrode layer of two unit cells formed on the opposite sides to each other, While maintaining the strength as a base material, it contributes to the improvement of energy density in that the thickness of the first electrode layer can be effectively halved. Moreover, since two unit cells can be formed by manufacturing the first electrode layer (first electrode combined base material) once, the manufacturing process can be reduced.

さらに、１つの第１電極層（第１電極兼用基材）がそれに対して互いに反対側に形成された２つの単位セルの第１電極層を兼ねることは、２つの単位セルの並列接続するような場合に、第１電極層同士の接続プロセスを省略でき、これにより、当該プロセスの際の熱処理による積層済部分の酸化を防止する効果も有する。   Furthermore, the fact that one first electrode layer (first electrode combined substrate) serves also as the first electrode layer of two unit cells formed on the opposite sides of the first electrode layer seems to connect two unit cells in parallel. In this case, the connection process between the first electrode layers can be omitted, and this also has an effect of preventing oxidation of the stacked portion due to heat treatment in the process.

従来の円筒型のニッケル水素電池（Ｎｉ−ＭＨ）の内部構造を一部破断して示す斜視図である。It is a perspective view which fractures | ruptures and shows the internal structure of the conventional cylindrical nickel hydride battery (Ni-MH). 従来の角型のニッケル水素電池（Ｎｉ−ＭＨ）の内部構造を一部破断して示す斜視図である。It is a perspective view which fractures | ruptures and shows the internal structure of the conventional square nickel hydride battery (Ni-MH). 特許文献１に記載の角型のリチウムイオン二次電池の内部構造（極板群）を示す斜視図である。6 is a perspective view showing an internal structure (electrode plate group) of a square lithium ion secondary battery described in Patent Document 1. FIG. 全固体型の二次電池の構成を示す斜視図及び断面図を示している。The perspective view and sectional drawing which show the structure of the all-solid-type secondary battery are shown. 全固体型の二次電池を単位セルとし、複数の単位セルを並列に接続した、考えられる二次電池の構成を示す断面図である。It is sectional drawing which shows the structure of the considered secondary battery which made the all-solid-type secondary battery the unit cell, and connected the several unit cell in parallel. 第１の実施形態の二次電池の構成を示す断面図である。It is sectional drawing which shows the structure of the secondary battery of 1st Embodiment. 第１の実施形態の二次電池の製造方法を示す説明図である。It is explanatory drawing which shows the manufacturing method of the secondary battery of 1st Embodiment. 第１の実施形態の二次電池の実装構造例を示す説明図である。It is explanatory drawing which shows the example of mounting structure of the secondary battery of 1st Embodiment. 第１の実施形態の二次電池における端面絶縁部材に係る変形実施形態を示す説明図である。It is explanatory drawing which shows the deformation | transformation embodiment which concerns on the end surface insulating member in the secondary battery of 1st Embodiment.

（Ａ）第１の実施形態
以下、本発明による二次電池及びその製造方法の第１の実施形態について、図面を参照しながら説明する。第１の実施形態の二次電池は量子電池である。 (A) First Embodiment Hereinafter, a first embodiment of a secondary battery and a method for manufacturing the same according to the present invention will be described with reference to the drawings. The secondary battery of the first embodiment is a quantum battery.

（Ａ−１）第１の実施形態の二次電池の基本構造
図６は、第１の実施形態に係る二次電池２０の構成を示す断面図であり、上述した図４（Ｂ）と同様な方向から見た断面図である。図６は、面方向の寸法より厚み方向の寸法を強調して示している。 (A-1) Basic Structure of Secondary Battery of First Embodiment FIG. 6 is a cross-sectional view showing the configuration of the secondary battery 20 according to the first embodiment, which is the same as FIG. 4B described above. It is sectional drawing seen from the various directions. FIG. 6 shows the dimension in the thickness direction with emphasis on the dimension in the plane direction.

図６において、第１の実施形態の二次電池２０は、シート状負極兼用基材２１、表面側のｎ型金属酸化物半導体層２２Ｆ、表面側の充電層２３Ｆ、表面側のｐ型金属酸化物半導体層２４Ｆ、表面側の正極層２５Ｆ、裏面側のｎ型金属酸化物半導体層２２Ｒ、裏面側の充電層２３Ｒ、裏面側のｐ型金属酸化物半導体層２４Ｒ、裏面側の正極層２５Ｒ及び基材端面絶縁部２６を有する。 In FIG. 6, the secondary battery 20 of the first embodiment includes a sheet-like negative electrode substrate 21, a surface-side n-type metal oxide semiconductor layer 22 </ b> F, a surface-side charging layer 23 </ b> F, and a surface-side p-type metal oxide. The semiconductor layer 24F, the positive electrode layer 25F on the front surface side, the n-type metal oxide semiconductor layer 22R on the back surface side, the charging layer 23R on the back surface side , the p-type metal oxide semiconductor layer 24R on the back surface side, the positive electrode layer 25R on the back surface side, The substrate end face insulating portion 26 is provided.

シート状負極兼用基材２１、表面側のｎ型金属酸化物半導体層２２Ｆ、表面側の充電層２３Ｆ、表面側のｐ型金属酸化物半導体層２４Ｆ及び表面側の正極層２５Ｆで、表面側の単位二次電池（単位セル）が構成され、シート状負極兼用基材２１、裏面側のｎ型金属酸化物半導体層２２Ｒ、裏面側の充電層２３Ｒ、裏面側のｐ型金属酸化物半導体層２４Ｒ及び裏面側の正極層２５Ｒで、裏面側の単位二次電池（単位セル）が構成されている。   The sheet-like negative electrode combined substrate 21, the surface side n-type metal oxide semiconductor layer 22F, the surface side charging layer 23F, the surface side p-type metal oxide semiconductor layer 24F, and the surface side positive electrode layer 25F, A unit secondary battery (unit cell) is configured, and the sheet-like negative electrode serving base material 21, the back side n-type metal oxide semiconductor layer 22 </ b> R, the back side charge layer 23 </ b> R, and the back side p-type metal oxide semiconductor layer 24 </ b> R. The back side positive electrode layer 25R constitutes a back side unit secondary battery (unit cell).

二次電池２０は、基材の両面共に、単位セルが形成されていることを特徴とするものであり、両面のいずれの面が表面ということができないものであるが、以下の説明では、便宜上、図６における上側の面を表面、図６における下側の面を裏面と呼ぶこととする。また、以下では、二次電池２０が、短辺と長辺の差が大きい概ね矩形のシート状のものであるとして説明する（後述する図７参照）。適宜、図６における左右方向を幅方向、図６紙面の法線方向を長尺方向と呼ぶこととする。   The secondary battery 20 is characterized in that unit cells are formed on both surfaces of the base material, and any surface of both surfaces cannot be referred to as a surface. The upper surface in FIG. 6 is referred to as the front surface, and the lower surface in FIG. 6 is referred to as the back surface. In the following description, it is assumed that the secondary battery 20 is a substantially rectangular sheet having a large difference between the short side and the long side (see FIG. 7 described later). As appropriate, the horizontal direction in FIG. 6 is referred to as the width direction, and the normal direction of the paper surface of FIG. 6 is referred to as the long direction.

シート状負極兼用基材２１は、薄膜形成処理時のシート状基材として機能すると共に、負極本体として機能するものである。上述した従来の二次電池（量子電池）１Ｄを示す図４は、基材上に対する各種の薄膜形成処理を経て得られた後、基材から取り外した二次電池を示している。この従来の二次電池（量子電池）１Ｄに比較すると、第１の実施形態の二次電池２０は、１つの負極層（シート状負極兼用基材２１）がそれに対して面対称な２つの単位セルの負極層を兼ねていることを特徴とする。シート状負極兼用基材２１の幅方向（図６の左右方向）の一方の端部（図６では左側の端部）２１ａは、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒ、充電層２３Ｆ、２３Ｒ、ｐ型金属酸化物半導体層２４Ｆ、２４Ｒ、正極層２５Ｆ、２５Ｒが被覆されておらず、負極の引き出し部として機能するようになされている。 The sheet-like negative electrode serving substrate 21 functions as a sheet-shaped substrate at the time of the thin film forming process and also functions as a negative electrode body. FIG. 4 showing the above-described conventional secondary battery (quantum battery) 1D shows the secondary battery removed from the base material after being obtained through various thin film forming processes on the base material. Compared to the conventional secondary battery (quantum battery) 1D, the secondary battery 20 of the first embodiment includes two units in which one negative electrode layer (sheet-like negative electrode substrate 21) is plane-symmetric with respect to it. It also serves as the negative electrode layer of the cell. One end portion (left end portion in FIG. 6) 21a in the width direction (left-right direction in FIG. 6) of sheet-like negative electrode serving base material 21 is n-type metal oxide semiconductor layers 22F and 22R, charging layers 23F and 23R. The p-type metal oxide semiconductor layers 24F and 24R and the positive electrode layers 25F and 25R are not covered and function as a lead portion for the negative electrode.

シート状負極兼用基材２１は、１種類の導電性材質で形成されているものであっても良く、また、導体若しくは絶縁体の表面に、スパッタリングやメッキなどによって導電性薄膜を付着させて形成されているものであっても良い。シート状負極兼用基材２１として、例えば、ステンレス鋼シート（ＳＵＳシート）を適用することができる。   The sheet-like negative electrode combined substrate 21 may be formed of one type of conductive material, and is formed by attaching a conductive thin film to the surface of a conductor or an insulator by sputtering or plating. It may be what is being done. For example, a stainless steel sheet (SUS sheet) can be applied as the sheet-like negative electrode combined base material 21.

各面の充電層２３Ｆ、２３Ｒは、充電動作で電子を蓄え、放電動作で蓄電電子を放出し、充放電がなされていない状態で電子を保持（蓄電）している層である。充電層がこのような機能を持つためには、例えば、国際公開ＷＯ２００８／０５３５６１に開示されているように、光励起構造変化にもとづく充電層中のバンドギャップへのトラップ準位の形成を行えば良い。すなわち、所定値以上のバンドギャップを持つ半導体であって透光性をもつ金属酸化物が絶縁被覆された微粒子状態のものが層をなした充電層を形成し、そこに紫外線照射を行って価電子帯にあった電子を伝導帯に励起させると、一部の電子が絶縁皮膜によって形成されたエネルギー障壁から負電極に移動する。この間に充電層中の電子の抜けた部位の原子間距離が変化する構造変化により、電子の抜けた空乏準位がバンドギャップ中に移動してトラップ準位となる。十分な量の光照射により、バンドギャップ内にトラップ準位を多数発生させた後、充電層に対して負電極の反対側に絶縁物等によるエネルギー障壁を介して正電極を設置し、両電極間に電圧を印加すると、このトラップ準位への電子の捕獲、放出によって充放電ができる。これが量子電池における充電層の働きである。   The charge layers 23F and 23R on each surface are layers that store electrons in a state where the electrons are stored in the charge operation, discharge the stored electrons in the discharge operation, and are not charged or discharged. In order for the charging layer to have such a function, for example, as disclosed in International Publication WO2008 / 053561, a trap level may be formed in the band gap in the charging layer based on the photoexcitation structure change. . In other words, a charged layer in which a semiconductor having a band gap of a predetermined value or more and having a light-transmitting metal oxide insulatively coated with a fine particle is formed into a layer, and irradiated with ultraviolet rays to form a charged layer. When electrons in the electron band are excited to the conduction band, some electrons move from the energy barrier formed by the insulating film to the negative electrode. During this time, due to the structural change in which the interatomic distance of the site where electrons are removed in the charge layer, the depletion level from which electrons are removed moves into the band gap and becomes a trap level. After generating a large number of trap levels in the band gap by irradiation with a sufficient amount of light, a positive electrode is installed on the opposite side of the negative electrode from the charging layer through an energy barrier such as an insulator. When a voltage is applied between them, charge and discharge can be performed by trapping and releasing electrons into the trap level. This is the function of the charge layer in the quantum battery.

各面のｎ型金属酸化物半導体層２２Ｆ、２２Ｒは、充電層２３Ｆ、２３Ｒにおいて、金属酸化物のまわりの絶縁層と同様、エネルギー障壁となる機能を有し、何らかの原因で金属酸化物が絶縁層を介さずに直接負電極と接することでエネルギー障壁が存在しない部分ができることを防止できる。ｎ型金属酸化物半導体層２２Ｆ、２２Ｒを構成する材質は限定されるものではないが、例えば、二酸化チタン（ＴｉＯ２）を適用することができる。 The n-type metal oxide semiconductor layers 22F and 22R on each surface have a function as an energy barrier in the charge layers 23F and 23R, like the insulating layers around the metal oxide, and the metal oxide is insulated for some reason. It can be prevented that a portion without an energy barrier is formed by directly contacting the negative electrode without passing through a layer. n-type metal oxide semiconductor layer 22F, but not the material is limited to constitute the 22R, for example, can be applied titanium dioxide (TiO 2).

量子電池を、一般的な二次電池と同様に、電気エネルギーを保持する部分と、２つの電極とで構成されていると見た場合、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒは、負極の要素と見ることができる。   When the quantum battery is considered to be composed of a portion for holding electric energy and two electrodes, like a general secondary battery, the n-type metal oxide semiconductor layers 22F and 22R are formed of a negative electrode. It can be seen as an element.

各面の正極層２５Ｆ、２５Ｒは、導電層として形成されたものであれば良い。正極層２５Ｆ、２５Ｒの材質は問われないが、例えば、アルミニウム（Ａｌ）を適用することができる。量子電池の場合、正極層２５Ｆ、２５Ｒから充電層２３Ｆ、２３Ｒへの不必要な電子の注入を防止するために、充電層２３Ｆ、２３Ｒに接するようにｐ型金属酸化物半導体層２４Ｆ、２４Ｒを有している。ｐ型金属酸化物半導体層２４Ｆ、２４Ｒの材質は限定されないが、例えば、酸化ニッケル（ＮｉＯ）を適用できる。   The positive electrode layers 25F and 25R on each surface may be formed as a conductive layer. The material of the positive electrode layers 25F and 25R is not limited, but for example, aluminum (Al) can be applied. In the case of a quantum battery, in order to prevent unnecessary injection of electrons from the positive electrode layers 25F and 25R into the charging layers 23F and 23R, the p-type metal oxide semiconductor layers 24F and 24R are in contact with the charging layers 23F and 23R. Have. Although the material of the p-type metal oxide semiconductor layers 24F and 24R is not limited, for example, nickel oxide (NiO) can be applied.

基材端面絶縁部２６は、負極として機能するシート状負極兼用基材２１と、正極層２５Ｆ、２５Ｒとの間の、充電層２３Ｆ、２３Ｒが設けられていないシート状負極兼用基材２１の一方の端部での短絡を防止するために設けられたものである。基材端面絶縁部２６の材質は問われないが、例えば、ゴム系材料、ポリオレフィン製材料、フッ素樹脂等を用いることができ、また、アルミナ（Ａｌ２Ｏ３）やシリカ（ＳｉＯ２）を適用することができる。なお、基材端面絶縁部２６は、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒより前に形成されても良く、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒの形成後であって充電層２３Ｆ、２３Ｒより前に形成されても良く、充電層２３Ｆ、２３Ｒより後に形成されても良い。充電層２３Ｆ、２３Ｒの形成時には高温処理も行われるので、充電層より前に形成する場合には、基材端面絶縁部２６の材質として耐熱性の材質を適用することが好ましい。 The substrate end face insulating portion 26 is one of the sheet-like negative electrode-use base material 21 that is not provided with the charge layers 23F, 23R between the sheet-like negative electrode-use base material 21 that functions as a negative electrode and the positive electrode layers 25F, 25R. This is provided in order to prevent a short circuit at the end portion. The material of the substrate end face insulating portion 26 is not limited, but, for example, a rubber material, a polyolefin material, a fluororesin, or the like can be used, and alumina (Al 2 O 3 ) or silica (SiO 2 ) is applied. can do. The substrate end face insulating portion 26 may be formed before the n-type metal oxide semiconductor layers 22F and 22R, and after the formation of the n-type metal oxide semiconductor layers 22F and 22R, the charging layers 23F and 23R. It may be formed before or after the charge layers 23F and 23R. Since the high temperature treatment is also performed at the time of forming the charge layers 23F and 23R, it is preferable to apply a heat resistant material as the material of the substrate end face insulating portion 26 when forming before the charge layer.

図６の例では、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒ及び充電層２３Ｆ、２３Ｒが、シート状負極兼用基材２１の一方の端面から少し手前まで形成され、断面コ字状に基材端面絶縁部２６が形成された例を示している。シート状負極兼用基材２１の表面及び裏面の基材端面絶縁部２６の厚みは、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒの厚み程度である。また、充電層２３Ｆ、２３Ｒの基材端面絶縁部２６側の縁とｎ型金属酸化物半導体層２２Ｆ、２２Ｒの基材端面絶縁部２６側の縁とはほぼ揃っている。その結果、基材端面絶縁部２６の表面、裏面と、充電層２３Ｆ、２３Ｒとの縁部とには段差が生じる。図６の例では、基材端面絶縁部２６の表面及び裏面上にも、ｐ型金属酸化物半導体層２４Ｆ、２４Ｒ及び正極層２５Ｆ、２５Ｒが積層されている。その結果、シート状負極兼用基材２１の一方の端部側において、正極層２５Ｆ、２５Ｒ自体が段差を有するものとなっている。   In the example of FIG. 6, the n-type metal oxide semiconductor layers 22F and 22R and the charging layers 23F and 23R are formed from one end surface of the sheet-like negative electrode serving base material 21 to a little closer to the front, The example in which the insulation part 26 was formed is shown. The thicknesses of the substrate end surface insulating portions 26 on the front and back surfaces of the sheet-like negative electrode serving substrate 21 are about the thicknesses of the n-type metal oxide semiconductor layers 22F and 22R. Further, the edges of the charging layers 23F and 23R on the base material end face insulating portion 26 side and the edges of the n-type metal oxide semiconductor layers 22F and 22R on the base end face insulating portion 26 side are substantially aligned. As a result, a step is generated between the front and back surfaces of the base material end face insulating portion 26 and the edge portions of the charging layers 23F and 23R. In the example of FIG. 6, p-type metal oxide semiconductor layers 24 </ b> F and 24 </ b> R and positive electrode layers 25 </ b> F and 25 </ b> R are also laminated on the front surface and the back surface of the substrate end surface insulating portion 26. As a result, the positive electrode layers 25F and 25R themselves have a step on one end side of the sheet-like negative electrode serving base material 21.

基材端面絶縁部２６が設けられていないシート状負極兼用基材２１の幅方向の端部においては、シート状負極兼用基材２１が所定長さだけ外部に露出しており（引き出し部２１ａ）、表面及び裏面共に、端面までの距離は、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒが最も短く、充電層２３Ｆ、２３Ｒが次に短く、ｐ型金属酸化物半導体層２４Ｆ、２４Ｒ及び正極層２５Ｆ、２５Ｒが最も長くなっている。このような段差構造により、シート状負極兼用基材２１と正極層２５Ｆ、２５Ｒとの短絡を防止するようになされている。   At the end portion in the width direction of the sheet-like negative electrode serving substrate 21 where the substrate end face insulating portion 26 is not provided, the sheet-shaped negative electrode serving substrate 21 is exposed to the outside by a predetermined length (drawing portion 21a). The distances to the end surfaces of both the front and back surfaces are the shortest in the n-type metal oxide semiconductor layers 22F and 22R, the shortest in the charge layers 23F and 23R, and the p-type metal oxide semiconductor layers 24F and 24R and the positive electrode layer 25F. 25R is the longest. By such a step structure, a short circuit between the sheet-like negative electrode serving base material 21 and the positive electrode layers 25F and 25R is prevented.

なお、基板端部の構造は正極層２５Ｆ、２５Ｒの短絡を防止できる構造であればこれに限らない。   Note that the structure of the end portion of the substrate is not limited to this as long as the positive electrode layers 25F and 25R can be prevented from being short-circuited.

図６では、基材端面絶縁部２６の端面（表面及び裏面でない面）が外部に露出しているものを示したが、基材端面絶縁部２６の端面をもｐ型金属酸化物半導体層や正極層で覆うようにしても良い。この場合において、表面及び裏面のｐ型金属酸化物半導体層２４Ｆ及び２４Ｒを、被覆したｐ型金属酸化物半導体層が連絡すると共に、表面及び裏面の正極層２５Ｆ及び２５Ｒを、被覆した正極層が連絡するようにしても良い。   In FIG. 6, although the end surface (surface which is not a surface and a back surface) of the base material end surface insulating portion 26 is exposed to the outside, the end surface of the base material end surface insulating portion 26 is also formed of a p-type metal oxide semiconductor layer or You may make it cover with a positive electrode layer. In this case, the p-type metal oxide semiconductor layers 24F and 24R on the front surface and the back surface are in communication with the coated p-type metal oxide semiconductor layers, and the positive electrode layers that cover the positive electrode layers 25F and 25R on the front surface and the back surface are connected. You may contact them.

また、図６では、基材端面絶縁部２６の表面側部分及び裏面側部分がシート状負極兼用基材２１の端部側を覆うもの（言い換えると、シート状負極兼用基材２１の端部側に積層されたもの）を示したが、シート状負極兼用基材２１上に形成されたｎ型金属酸化物半導体層２２Ｆ、２２Ｒの端部側を覆うようにしても良い。   Moreover, in FIG. 6, the surface side part and back surface side part of the base-material end surface insulating part 26 cover the end part side of the sheet-like negative electrode serving substrate 21 (in other words, the end side of the sheet-like negative electrode serving substrate 21) However, the end portions of the n-type metal oxide semiconductor layers 22F and 22R formed on the sheet-like negative electrode serving substrate 21 may be covered.

以上では、シート状負極兼用基材２１の幅方向の一方の端部における短絡防止構成について説明した。なお、第１の実施形態の特徴から離れるが、シート状負極兼用基材２１の長尺方向の一方若しくは両方の端部にも、上述と同様な短絡防止構成を適用しても良い。また、シート状負極兼用基材２１の長尺方向の一方若しくは両方の端部にも、上述した引き出し部２１ａと同じような処理を行っても良い。   In the above, the short circuit prevention structure in one edge part of the width direction of the sheet-like negative electrode combined use base material 21 was demonstrated. In addition, although away from the characteristics of the first embodiment, the same short-circuit prevention configuration as described above may be applied to one or both ends of the sheet-like negative electrode / substrate 21 in the longitudinal direction. Moreover, you may perform the process similar to the drawer | drawing-out part 21a mentioned above also to the edge part of the elongate direction of the sheet-like negative electrode combined use base material 21 or both.

（Ａ−２）第１の実施形態の二次電池の製造方法
次に、図６に示す構造を有する第１の実施形態の二次電池２０の製造方法を説明する。図７は、第１の実施形態の二次電池の製造方法を示す説明図である。図７（Ａ１）〜（Ａ４）が概略斜視図であり、図７（Ｂ１）〜（Ｂ４）が断面図である。図７（Ｂ１）〜（Ｂ４）の断面図は、上述した図６に示す断面図に比較し、二次電池の中間形成状態や完成品を時計方向に９０度だけ回転した断面図である。 (A-2) Manufacturing Method of Secondary Battery of First Embodiment Next, a manufacturing method of the secondary battery 20 of the first embodiment having the structure shown in FIG. 6 will be described. FIG. 7 is an explanatory diagram illustrating a method for manufacturing the secondary battery according to the first embodiment. 7A1 to 7A4 are schematic perspective views, and FIGS. 7B1 to 7B4 are cross-sectional views. The cross-sectional views of FIGS. 7B1 to 7B4 are cross-sectional views obtained by rotating the intermediate formed state of the secondary battery and the finished product by 90 degrees clockwise compared to the cross-sectional view shown in FIG.

最初に、図７（Ａ１）及び（Ｂ１）に示すように、シート状負極兼用基材２１の幅方向の一辺近傍に、基材端面絶縁部２６を形成させる。形成方法にもよるが、この形成時には、非形成領域をマスキングしておく。例えば、シート状負極兼用基材２１としてＳＵＳシートを適用し、その一端部に基材端面絶縁部２６を形成する。例えば、基材端面絶縁部２６の材質が樹脂の場合には、一般的な樹脂被膜の成膜方法（例えば、吹き掛け塗装）により基材端面絶縁部２６を形成する。また例えば、基材端面絶縁部２６の材質がアルミナ（Ａｌ２Ｏ３）やシリカ（ＳｉＯ２）等の場合には、スパッタリング法、蒸着法、ＣＶＤ法（化学気相成長法）、塗布熱分解法等により基材端面絶縁部２６を形成（成膜）する。 First, as shown in FIGS. 7A1 and 7B1, the base end surface insulating portion 26 is formed in the vicinity of one side in the width direction of the sheet-like negative electrode serving base 21. Depending on the formation method, the non-formation region is masked during this formation. For example, a SUS sheet is applied as the sheet-like negative electrode combined base material 21, and the base material end surface insulating portion 26 is formed at one end thereof. For example, when the material of the substrate end surface insulating portion 26 is resin, the substrate end surface insulating portion 26 is formed by a general resin film forming method (for example, spray coating). Further, for example, when the material of the substrate end face insulating portion 26 is alumina (Al 2 O 3 ), silica (SiO 2 ), or the like, sputtering method, vapor deposition method, CVD method (chemical vapor deposition method), coating pyrolysis The base material end surface insulating portion 26 is formed (film formation) by a method or the like.

次に、図７（Ａ２）及び（Ｂ２）に示すように、シート状負極兼用基材２１における引き出し部２１ａを確保し、かつ、基材端面絶縁部２６上には積層しないように適宜マスキングをして、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒを形成する。例えば、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒの材質として二酸化チタン（ＴｉＯ２）を適用し、スパッタリング法、蒸着法、ＣＶＤ法、塗布熱分解法等により、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒを形成する。ここで、表面及び裏面のｎ型金属酸化物半導体層２２Ｆ及び２２Ｒを同時に形成するようにしても良く、また、片面ずつ形成するようにしても良い。 Next, as shown in FIGS. 7A2 and 7B2, appropriate masking is performed so as to secure the lead-out portion 21a in the sheet-like negative electrode combined base material 21 and not to be laminated on the base material end surface insulating portion 26. Then, the n-type metal oxide semiconductor layers 22F and 22R are formed. For example, titanium dioxide (TiO 2 ) is applied as the material of the n-type metal oxide semiconductor layers 22F and 22R, and the n-type metal oxide semiconductor layer 22F, 22R is formed. Here, the n-type metal oxide semiconductor layers 22F and 22R on the front surface and the back surface may be formed simultaneously, or may be formed on each side.

なお、図６に示す第１の実施形態の二次電池２０の場合、基材端面絶縁部２６と、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒとは積層関係にないので、上述とは異なり、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒの形成（成膜）後に、基材端面絶縁部２６を形成するようにしても良い。   In the case of the secondary battery 20 of the first embodiment shown in FIG. 6, the base material end face insulating portion 26 and the n-type metal oxide semiconductor layers 22F and 22R are not in a stacked relationship. The substrate end face insulating portion 26 may be formed after the formation (film formation) of the n-type metal oxide semiconductor layers 22F and 22R.

次に、図７（Ａ３）及び（Ｂ３）に示すように、シート状負極兼用基材２１における引き出し部２１ａをｎ型金属酸化物半導体層２２Ｆ、２２Ｒの一部が露出するように確保し、かつ、基材端面絶縁部２６上には積層しないように適宜マスキングをして、充電層２３Ｆ及び２３Ｒを形成する。充電層２３Ｆ、２３Ｒの形成方法の詳細は、国際公開ＷＯ２０１２／０４６３２５に記載されている。ここで、表面及び裏面の充電層２３Ｆ及び２３Ｒを同時に形成するようにしても良く、また、片面ずつ形成するようにしても良い。   Next, as shown in FIGS. 7A3 and 7B3, the lead-out portion 21a in the sheet-like negative electrode combined base material 21 is secured so that a part of the n-type metal oxide semiconductor layers 22F and 22R is exposed, And it masks suitably so that it may not laminate | stack on the base-material end surface insulation part 26, and charge layer 23F and 23R are formed. Details of the method of forming the charge layers 23F and 23R are described in International Publication WO2012 / 046325. Here, the charging layers 23F and 23R on the front surface and the back surface may be formed at the same time, or may be formed on each side.

次に、図７（Ａ４）及び（Ｂ４）に示すように、シート状負極兼用基材２１における引き出し部２１ａをｎ型金属酸化物半導体層２２Ｆ、２２Ｒの一部と充電層２３Ｆ、２３Ｒの一部とが露出するように確保し、かつ、基材端面絶縁部２６の端面にｐ型金属酸化物半導体層や正極層を形成しないように適宜マスキングをして、ｐ型金属酸化物半導体層２４Ｆ及び２４Ｒを形成し、その後、正極層２５Ｆ及び２５Ｒを形成する。なお、図７（Ａ４）及び（Ｂ４）は、正極層２５Ｆ及び２５Ｒが形成された後の状態を示している。例えば、ｐ型金属酸化物半導体層２４Ｆ、２４Ｒの材質として酸化ニッケル（ＮｉＯ）を適用し、スパッタリング法、蒸着法、ＣＶＤ法、塗布熱分解法等により、ｐ型金属酸化物半導体層２４Ｆ、２４Ｒを形成した後、正極層２５Ｆ、２５Ｒの材質としてアルミニウム（Ａｌ）を適用し、スパッタリング法、蒸着法、ＣＶＤ法、塗布熱分解法等により、正極層２５Ｆ、２５Ｒを形成する。ここで、表面及び裏面のｐ型金属酸化物半導体層２４Ｆ及び２４Ｒを同時に形成するようにしても良く、また、片面ずつ形成するようにしても良い。また、表面及び裏面の正極層２５Ｆ及び２５Ｒを同時に形成するようにしても良く、また、片面ずつ形成するようにしても良い。   Next, as shown in FIGS. 7A4 and 7B4, the lead-out portion 21a in the sheet-like negative electrode serving base material 21 is part of the n-type metal oxide semiconductor layers 22F and 22R and the charging layers 23F and 23R. The p-type metal oxide semiconductor layer 24F is appropriately masked so that the p-type metal oxide semiconductor layer and the positive electrode layer are not formed on the end face of the substrate end face insulating part 26. And 24R are formed, and then positive electrode layers 25F and 25R are formed. 7A4 and 7B4 show a state after the positive electrode layers 25F and 25R are formed. For example, nickel oxide (NiO) is applied as the material of the p-type metal oxide semiconductor layers 24F and 24R, and the p-type metal oxide semiconductor layers 24F and 24R are formed by sputtering, vapor deposition, CVD, coating pyrolysis, or the like. Then, aluminum (Al) is applied as a material of the positive electrode layers 25F and 25R, and the positive electrode layers 25F and 25R are formed by a sputtering method, a vapor deposition method, a CVD method, a coating pyrolysis method, or the like. Here, the p-type metal oxide semiconductor layers 24F and 24R on the front surface and the back surface may be formed at the same time, or may be formed on each side. Further, the positive and negative electrode layers 25F and 25R on the front surface and the back surface may be formed at the same time, or may be formed on each side.

以上の工程を経て、図６に示す構造を有する第１の実施形態の二次電池２０が形成される。   Through the above steps, the secondary battery 20 of the first embodiment having the structure shown in FIG. 6 is formed.

以上では、ｎ型金属酸化物半導体層２２Ｆ、２２Ｒ、充電層２３Ｆ、２３Ｒ、ｐ型金属酸化物半導体層２４Ｆ、２４Ｒ、正極層２５Ｆ、２５Ｒの形成に関し、シート状負極兼用基材２１の両面の処理を並行的に行うものを示したが、例えば、表面側の形成処理をまとめて行い、表面側の形成処理が終了した後に、裏面側の形成処理を行うようにしても良い。すなわち、基材端面絶縁部２６が形成されたシート状負極兼用基材２１に対し、表面側のｎ型金属酸化物半導体層２２Ｆ、充電層２３Ｆ、ｐ型金属酸化物半導体層２４Ｆ、正極層２５Ｆを順次形成し、その後、裏面側のｎ型金属酸化物半導体層２２Ｒ、充電層２３Ｒ、ｐ型金属酸化物半導体層２４Ｒ、正極層２５Ｒを順次形成するようにしても良い。   In the above, regarding the formation of the n-type metal oxide semiconductor layers 22F and 22R, the charge layers 23F and 23R, the p-type metal oxide semiconductor layers 24F and 24R, and the positive electrode layers 25F and 25R, Although the processing performed in parallel is shown, for example, the front surface side forming processing may be performed collectively, and after the front surface side forming processing is completed, the back surface side forming processing may be performed. That is, the n-type metal oxide semiconductor layer 22F, the charge layer 23F, the p-type metal oxide semiconductor layer 24F, and the positive electrode layer 25F on the surface side of the sheet-like negative electrode combined substrate 21 on which the substrate end face insulating portion 26 is formed. Then, the n-type metal oxide semiconductor layer 22R, the charging layer 23R, the p-type metal oxide semiconductor layer 24R, and the positive electrode layer 25R on the back surface side may be sequentially formed.

第１の実施形態の二次電池２０の実装構造に合わせて、上記工程における処理を一部変更するようにしても良い。   Depending on the mounting structure of the secondary battery 20 of the first embodiment, a part of the processing in the above process may be changed.

例えば、製造された第１の実施形態の二次電池２０を、長尺方向に所定長さずつに切り分けて実装に供する場合であれば、切断位置では、シート状負極兼用基材２１を幅方向に露出させるようにしても良い。   For example, in the case where the manufactured secondary battery 20 of the first embodiment is cut into predetermined lengths in the longitudinal direction and used for mounting, the sheet-like negative electrode combined substrate 21 is arranged in the width direction at the cutting position. You may make it expose to.

また例えば、製造された第１の実施形態の二次電池２０を蛇腹状に折り曲げてケースに収容するような場合であれば、折り曲げた際に内側になる折り曲げ部分の所定種類の薄膜を形成しないようにして折り曲げ時の応力を軽減するようにしても良い。例えば、折り曲げ部分には正極層２５Ｆ、２５Ｒを形成しないようにしても良く、また、折り曲げ部分には正極層２５Ｆ、２５Ｒとｐ型金属酸化物半導体層２４Ｆ、２４Ｒと、充電層２３Ｆ、２３Ｒとを形成しないようにしても良い。あるいは折り曲げ部の薄膜を形成後にレーザー等で選択的に除去することで折り曲げ時の応力を軽減するようにしても良い。   In addition, for example, if the manufactured secondary battery 20 of the first embodiment is folded in a bellows shape and accommodated in a case, a predetermined type of thin film is not formed in a bent portion that becomes an inner side when folded. In this way, the stress during bending may be reduced. For example, the positive electrode layers 25F and 25R may not be formed in the bent portions, and the positive electrode layers 25F and 25R, the p-type metal oxide semiconductor layers 24F and 24R, and the charge layers 23F and 23R are formed in the bent portions. May not be formed. Or you may make it reduce the stress at the time of bending by selectively removing with a laser etc. after forming the thin film of a bending part.

（Ａ−３）第１の実施形態の二次電池の実装構造
次に、図６に示す構造を有する第１の実施形態の二次電池２０の実装構造の一例を説明する。 (A-3) Secondary Battery Mounting Structure of First Embodiment Next, an example of a mounting structure of the secondary battery 20 of the first embodiment having the structure shown in FIG. 6 will be described.

図６に示す構造を有する第１の実施形態の二次電池２０の実装方法は任意であって良い。例えば、平面シート状のまま、二次電池２０を必要とする装置の電源部として貼付するようにしても良い。また例えば、製造された二次電池２０を、長尺方向に所定長さずつに切り分けて実装に供するようにしても良い。   The mounting method of the secondary battery 20 of the first embodiment having the structure shown in FIG. 6 may be arbitrary. For example, you may make it stick as a power supply part of the apparatus which requires the secondary battery 20 with a flat sheet form. Further, for example, the manufactured secondary battery 20 may be cut into a predetermined length in the long direction and used for mounting.

ここで、両面のそれぞれに二次電池として機能する構造が形成されたシート状であるという特徴を反映すると、図８に示すような実装構造を挙げることができる。   Here, a mounting structure as shown in FIG. 8 can be given, reflecting the feature of being in the form of a sheet in which a structure that functions as a secondary battery is formed on each of both surfaces.

すなわち、図８（Ａ）のイメージ的な平面図に示すように、円筒状の芯材３０に第１の実施形態の二次電池２０を巻き取り、二次電池２０の巻取りロール３１を形成させる。巻取りロール３１の形成後において、芯材３０をそのまま残しておいても良く、また、芯材３０を除去するようにしても良い。電極に適用可能な導電性材質が表面に付着したものを芯材３０として適用し、芯材３０が外部の正極部材として機能するものであっても良い。図８（Ｂ）は、図８（Ａ）のVIIIB−VIIIB線に沿った断面を多少上側から見たイメージ的な斜視図を表している。なお、以下の実装構造の説明においては、図８（Ｂ）の上下方向に従って上下に言及している。図８（Ａ）及び（Ｂ）は、二次電池２０の層構造を省略して描いている。   That is, as shown in the image plan view of FIG. 8A, the secondary battery 20 of the first embodiment is wound around a cylindrical core member 30 to form a winding roll 31 of the secondary battery 20. Let me. After the winding roll 31 is formed, the core material 30 may be left as it is, or the core material 30 may be removed. A material in which a conductive material applicable to the electrode adheres to the surface may be applied as the core material 30, and the core material 30 may function as an external positive electrode member. FIG. 8B shows an image-like perspective view of a section taken along line VIIIB-VIIIB in FIG. In the following description of the mounting structure, reference is made vertically according to the vertical direction of FIG. 8A and 8B are drawn with the layer structure of the secondary battery 20 omitted.

巻取りロール３１において、あるターン数の二次電池部分の表面側の正極層２５Ｆが、それより１だけ多いターン数の二次電池部分の裏面側の正極層２５Ｒに接し、巻き取ることによって、正極層が他の層に接することはない。   In the winding roll 31, the positive electrode layer 25F on the front surface side of the secondary battery portion with a certain number of turns is in contact with the positive electrode layer 25R on the back surface side of the secondary battery portion with the number of turns one more than that, and is wound. The positive electrode layer does not contact other layers.

巻取りロール３１におけるシート状負極兼用基材２１の引き出し部２１ａ側は、外部の負極端子が接触される、導電性材質でなる露出負極部材３２（上蓋と見ることができる）によって被蓋される。露出負極部材３２は、円形の天板と、その周縁から下方に垂設されている、引き出し部２１ａの幅方向の長さと同様な長さを有する円筒部材とを有する。露出負極部材３２の内部には、ターンが異なる引き出し部２１ａ間の隙間に入り込んで引き出し部２１ａに接触するような導電性部材が、円形天板の内面から下方に垂設されていても良い。このような導電性部材は、シート状のものに限定されず、不織布状やブラシ状のものであっても良い。   The lead-out portion 21a side of the sheet-like negative electrode substrate 21 in the winding roll 31 is covered with an exposed negative electrode member 32 (which can be seen as an upper lid) made of a conductive material with which an external negative electrode terminal is brought into contact. . The exposed negative electrode member 32 has a circular top plate and a cylindrical member that is provided below the periphery of the top plate and has a length similar to the length in the width direction of the lead portion 21a. Inside the exposed negative electrode member 32, a conductive member that enters the gap between the lead portions 21 a with different turns and contacts the lead portion 21 a may be suspended downward from the inner surface of the circular top plate. Such a conductive member is not limited to a sheet-like member, and may be a nonwoven fabric or a brush-like member.

巻取りロール３１における引き出し部２１ａの反対側の端部は、外部の正極端子が接触される、導電性材質でなる露出正極部材３３（下蓋と見ることができる）によって被蓋される。露出正極部材３３は、円形の底板と、その周縁から上方に垂設されている、正極層２５Ｆ、２５Ｒの段によって低くなっている部分の幅方向の長さと同様な長さを有する円筒部材とを有する。露出正極部材３３の内部には、ターンが異なる正極層２５Ｆ、２５Ｒの低段部分間の隙間に入り込んで低段部分に接触するような導電性部材が、円形底板の内面から上方に垂設されていても良い。このような導電性部材は、シート状のものに限定されず、不織布状やブラシ状のものであっても良い。   The end of the winding roll 31 on the opposite side of the lead-out portion 21a is covered with an exposed positive electrode member 33 (which can be seen as a lower lid) made of a conductive material with which an external positive electrode terminal is brought into contact. The exposed positive electrode member 33 includes a circular bottom plate, and a cylindrical member having a length similar to the length in the width direction of the portion of the positive electrode layer 25F, 25R that is lowered from the periphery of the bottom plate. Have Inside the exposed positive electrode member 33, a conductive member that enters the gap between the low-stage portions of the positive electrode layers 25F and 25R with different turns and comes into contact with the low-stage portions is suspended upward from the inner surface of the circular bottom plate. May be. Such a conductive member is not limited to a sheet-like member, and may be a nonwoven fabric or a brush-like member.

図８（Ｃ）は、露出負極部材３２及び露出正極部材３３を、巻取りロール３１に取り付けた状態を示している。このほぼ円筒状の状態の側面を、図８（Ｄ）に示すように、シート状の絶縁部材３４で覆って実用に供する二次電池３５を完成させる。   FIG. 8C shows a state where the exposed negative electrode member 32 and the exposed positive electrode member 33 are attached to the take-up roll 31. As shown in FIG. 8D, the substantially cylindrical side surface is covered with a sheet-like insulating member 34 to complete a secondary battery 35 for practical use.

以上では、露出負極部材３２及び露出正極部材３３を取り付けた後にシート状の絶縁部材３４を取り付ける手順を説明したが、シート状の絶縁部材３４を取り付けた後に露出負極部材３２及び露出正極部材３３を取り付ける手順で二次電池３５を完成させるようにしても良い。   The procedure for attaching the sheet-like insulating member 34 after attaching the exposed negative electrode member 32 and the exposed positive electrode member 33 has been described above. However, the exposed negative electrode member 32 and the exposed positive electrode member 33 are attached after the sheet-like insulating member 34 is attached. The secondary battery 35 may be completed by the attaching procedure.

上記では、１枚の二次電池２０を巻き取る場合を説明したが、複数枚の二次電池２０を重ね合わせた状態で巻き取るようにしても良い。ここで、幅方向は一致するが、長尺方向にずれて重ね合されていても良い。   Although the case where one secondary battery 20 is wound up has been described above, a plurality of secondary batteries 20 may be wound in a stacked state. Here, although the width direction is coincident, they may be shifted in the longitudinal direction and overlapped.

（Ａ−４）第１の実施形態の二次電池の効果
第１の実施形態の二次電池２０によれば、以下の効果を奏することができる。 (A-4) Effects of Secondary Battery of First Embodiment According to the secondary battery 20 of the first embodiment, the following effects can be achieved.

負極は、外部の電極部材（例えば露出負極部材３２）と接触するための意図的な引き出し部２１ａを有する。正極についても、成膜する領域を幅方向の端面に向かって増大させて外部の電極部材（例えば露出正極部材３３）と接触する部分を形成しているので、外部の電極部材と接触する部分を薄く形成でき、かつ、形成するための工数も少なくて済む。   The negative electrode has an intentional lead portion 21a for contacting an external electrode member (for example, the exposed negative electrode member 32). The positive electrode also has a portion that contacts the external electrode member (for example, the exposed positive electrode member 33) by increasing the film forming region toward the end face in the width direction. It can be formed thin and requires less man-hours for forming.

ロール状の実装方法を採用した場合には、正極２５Ｆ、２５Ｒがロール状に巻き取られた棒状の引出部となる。これにより、簡便で低抵抗の電気接続が可能で、充放電時のロスが少なくなる。また、正極、負極に引出電極を外付けする工法に比べると製造工数を少なくできる。   When the roll-shaped mounting method is adopted, the positive electrodes 25F and 25R become rod-shaped lead portions wound up in a roll shape. Thereby, a simple and low-resistance electrical connection is possible, and loss during charging and discharging is reduced. Further, the number of manufacturing steps can be reduced as compared with a method in which an extraction electrode is externally attached to the positive electrode and the negative electrode.

第１の実施形態の二次電池２０は、シート状負極兼用基材２１の両面共に単位セル（単位二次電池）を構成しているので、エネルギー密度を向上させることができる。例えば、基材（但し、負極兼用基材であっても良い）上に構成された基材が残ったままの従来の二次電池を２つ用い、基材の背面同士を接着して両面に単位セルを構成した二次電池を比較対象とすると、第１の実施形態の二次電池２０は、基材の厚さを比較対象の二次電池の半分程度とすることができ、これによりエネルギー密度を高めることができる。 The secondary battery 20 of the first embodiment, since the configuration of the unit cell (unit battery) on both sides of a sheet-like negative electrode combined substrate 21, thereby improving the energy density. For example, two conventional secondary batteries with the base material remaining on the base material (which may also be a negative electrode base material) remain, and the back surfaces of the base materials are bonded to both sides. When the secondary battery that constitutes the unit cell is a comparison target, the secondary battery 20 of the first embodiment can make the thickness of the base material about half that of the secondary battery to be compared. The density can be increased.

第１の実施形態の二次電池２０では、シート状負極兼用基材２１を２つの単位セルが共用して２つの単位セルが並列接続されている。別体の２つの単位セルで第１の実施形態の二次電池２０と同じような物理量を実現しようとした場合、別体の２つの単位セルを並列接続させるための構成要素が必要となり、この分、第１の実施形態の二次電池２０は構造及び製造工程が簡単になっているということができる。   In the secondary battery 20 of the first embodiment, the two unit cells are connected in parallel with the two unit cells sharing the sheet-like negative electrode serving base material 21. When a physical quantity similar to that of the secondary battery 20 of the first embodiment is to be realized with two separate unit cells, a component for connecting the two separate unit cells in parallel is required. Therefore, it can be said that the structure and the manufacturing process of the secondary battery 20 of the first embodiment are simplified.

充電層２３Ｆ、２３Ｒの形成など、製造工程中に熱処理が含まれている。シート状負極兼用基材２１は早い段階で両面共にｎ型金属酸化物半導体層２２Ｆ、２２Ｒで被覆されるため、熱処理時における酸化等の問題は、従来の二次電池に比べて小さくなっている。   Heat treatment is included in the manufacturing process such as formation of the charge layers 23F and 23R. Since both sides of the sheet-like negative electrode substrate 21 are covered with the n-type metal oxide semiconductor layers 22F and 22R at an early stage, problems such as oxidation during heat treatment are smaller than those of the conventional secondary battery. .

第１の実施形態の二次電池２０は、シート状負極兼用基材２１における引き出し部２１ａを除けば露出している大半が正極層２５Ｆ、２５Ｒである。そのため、複数の二次電池２０は重ね合わせても、１枚又は複数の二次電池２０を巻き取っても折り曲げても接触するのは正極層同士である。これにより、絶縁部材等を用いることなく、多様な実装構造をとることができるようになっている。   In the secondary battery 20 of the first embodiment, most of the exposed portions excluding the lead portion 21a in the sheet-like negative electrode serving base material 21 are the positive electrode layers 25F and 25R. Therefore, it is the positive electrode layers that are in contact with each other even when the plurality of secondary batteries 20 are overlaid, or when one or more secondary batteries 20 are wound or folded. Thereby, various mounting structures can be taken without using an insulating member or the like.

（Ｂ）他の実施形態
上記第１の実施形態の説明においても、種々変形実施形態に言及したが、さらに、以下に例示するような変形実施形態を挙げることができる。 (B) Other Embodiments Also in the description of the first embodiment, various modified embodiments have been mentioned, and further modified embodiments as exemplified below can be given.

（Ｂ−１）第１の実施形態では、負極が基材と兼用のものを示したが、逆に、正極が基材と兼用するものであっても良い。この場合には、正極兼用基材上に、ｐ型金属酸化物半導体層、充電層、ｎ型金属酸化物半導体層、負極層を順次成膜することとなる。若しくは、ｐ型金属酸化物半導体層が既に形成されている正極兼用基材上に、充電層、ｎ型金属酸化物半導体層、負極層を順次成膜するようにする。 (B-1) In the first embodiment, the negative electrode is also used as the base material. Conversely, the positive electrode may be used as the base material. In this case, a p-type metal oxide semiconductor layer, a charge layer, an n-type metal oxide semiconductor layer, and a negative electrode layer are sequentially formed on the positive electrode substrate. Alternatively, a charging layer, an n-type metal oxide semiconductor layer, and a negative electrode layer are sequentially formed on a positive electrode substrate on which a p-type metal oxide semiconductor layer has already been formed.

第１の実施形態の二次電池とこの変形実施形態の二次電池とを重ねた場合には、単層二次電池の直列接続を実現でき、端子電圧を増大させることができる。   When the secondary battery of the first embodiment and the secondary battery of this modified embodiment are stacked, a single-layer secondary battery can be connected in series, and the terminal voltage can be increased.

（Ｂ−２）第１の実施形態では、二次電池のベースとなっている負極兼用基材が短辺と長辺との差が大きい矩形のシート状のものを示したが、負極兼用基材は、第１の実施形態のものに限定されない。例えば、縦横の長さが同程度の矩形のものであっても良く、円形や六角形等の他の形状であっても良い。円形や六角形の場合には、基本形状に引き出し部に相当する部分を付け加えた形状にすることが好ましい。 (B-2) In the first embodiment, the negative electrode combined base material which is the base of the secondary battery is a rectangular sheet having a large difference between the short side and the long side. The material is not limited to that of the first embodiment. For example, it may be a rectangle having the same length in the vertical and horizontal directions, or may be another shape such as a circle or a hexagon. In the case of a circle or hexagon, it is preferable to add a portion corresponding to the lead portion to the basic shape.

また例えば、負極兼用基材を円筒状に形成し、円筒側面（底がある場合には、底面を含んでも良い）の外面と内面の両面に対して、第１の実施形態と同様な単位セルを構成するようにしても良い。   Also, for example, the negative electrode combined substrate is formed in a cylindrical shape, and the same unit cell as in the first embodiment is formed on both the outer and inner surfaces of the cylindrical side surface (which may include the bottom surface if there is a bottom). You may make it comprise.

（Ｂ−３）第１の実施形態では、負極兼用基材２１の両面共に、負極の引き出し部２１ａとして機能する部分を確保したものを示したが、一方の面（例えば裏面）には引き出し部２１ａとして機能する部分を設けずに、裏面のほぼ全面を単位セルとして機能させるようにしても良い。 (B-3) In the first embodiment, both surfaces of the negative electrode serving base material 21 are provided with a portion that functions as the negative electrode extraction portion 21a. However, the extraction portion is provided on one surface (for example, the back surface). Instead of providing a portion that functions as 21a, almost the entire back surface may function as a unit cell.

また、負極兼用基材２１が帯状の場合において、長尺方向の一方若しくは両方の端部に引き出し部２１ａを設け、幅方向については両方の端部共に、引き出し部２１ａとして機能する部分を設けないようにしても良い。   In the case where the negative electrode combined base material 21 is in the form of a strip, a lead portion 21a is provided at one or both ends in the longitudinal direction, and no portion that functions as the lead portion 21a is provided at both ends in the width direction. You may do it.

（Ｂ−４）第１の実施形態では、負極の引き出し部２１ａが平板状のものを示したが、これに限定されない。例えば、負極の引き出し部２１ａが櫛歯状や鋸歯状であっても良い。また、円筒若しくは円棒が嵌合する開口を負極の引き出し部２１ａが有していても良い。 (B-4) In the first embodiment, the negative electrode lead portion 21a is a flat plate, but the present invention is not limited to this. For example, the lead-out portion 21a of the negative electrode may have a comb shape or a sawtooth shape. Moreover, the lead-out part 21a of the negative electrode may have an opening in which a cylinder or a rod is fitted.

（Ｂ−５）第１の実施形態では、基材端面絶縁部２６を薄膜形成処理等によって積極的に形成したものを示したが、他の方法によって基材端面絶縁部２６を形成するようにしても良い。例えば、シート状負極兼用基材２１が、絶縁体の表面に、スパッタリングやメッキによって導電性薄膜を付着させて形成されるものである場合には、基材端面絶縁部２６になる領域に対する導電性薄膜の付着を阻止することによって基材端面絶縁部２６を構成するようにしても良い。 (B-5) In the first embodiment, the substrate end surface insulating portion 26 is positively formed by a thin film forming process or the like. However, the substrate end surface insulating portion 26 is formed by another method. May be. For example, when the sheet-like negative electrode combined base material 21 is formed by depositing a conductive thin film on the surface of the insulator by sputtering or plating, the conductivity to the region that becomes the base material end surface insulating portion 26 is obtained. You may make it comprise the base-material end surface insulation part 26 by preventing adhesion of a thin film.

（Ｂ−６）第１の実施形態では、基材端面絶縁部２６が断面コ字状に設けられたものを示したが、基材端面絶縁部２６の付着の方法はこれに限定されない。また、基板の端面近傍において正極層と負極層との絶縁を確保できるのであれば、基材端面絶縁部２６を設けないようにしても良い。図９（Ａ）は、シート状負極兼用基材２１の表面や裏面側に設けずにシート状負極兼用基材２１の端面だけを覆うように基材端面絶縁部２６を設けた場合を示している。図９（Ｂ）は、シート状負極兼用基材２１の端面にも、表面から裏面に連続するように、ｎ型金属酸化物半導体層、充電層、ｐ型金属酸化物半導体層及び正極層を設けることにより基材端面絶縁部２６を不要とした場合を示している。 (B-6) In the first embodiment, the substrate end surface insulating portion 26 is provided in a U-shaped cross section, but the method of attaching the substrate end surface insulating portion 26 is not limited to this. Further, the base material end face insulating portion 26 may not be provided as long as the insulation between the positive electrode layer and the negative electrode layer can be secured in the vicinity of the end face of the substrate. FIG. 9A shows a case where the base end face insulating portion 26 is provided so as to cover only the end face of the sheet negative electrode serving base material 21 without being provided on the front surface or the back surface side of the sheet negative electrode serving base material 21. Yes. FIG. 9B shows an n-type metal oxide semiconductor layer, a charge layer, a p-type metal oxide semiconductor layer, and a positive electrode layer on the end face of the sheet-like negative electrode serving base material 21 so as to continue from the front surface to the back surface. The case where the base-material end surface insulating part 26 is made unnecessary by providing is shown.

（Ｂ−７）第１の実施形態の二次電池２０の実装構造は、上述したように限定されるものでない。上述した巻取りロール以外の実装構造を、数例挙げると以下の通りである。 (B-7) The mounting structure of the secondary battery 20 of the first embodiment is not limited as described above. Several examples of mounting structures other than the winding roll described above are as follows.

二次電池２０の長尺方向の中心位置で２つ折りにして実装に供しても良く、また、２つ折りにしたものを幅方向にしかも正極と負極とが短絡しないように折り曲げた４つ折りにしたものをケース等に実装するようにしても良い。さらに、折り曲げ方向を交互に変えて蛇腹状したものをケース等に実装するようにしても良く、折り曲げ毎の折り曲げ方向が同じである反物状にしたものをケース等に実装するようにしても良い。蛇腹状や反物状にする場合において、細い円筒若しくは円棒を利用して折り曲げ、この円筒若しくは円棒として電極に利用されるような導電性材質を適用し、正極層と外部の正極部材とを電気的に連絡する機能を担うようにさせても良い。また、長尺方向に対して９０度以外の所定角度（例えば４５度）で折り曲げて、水平方向に沿って延びていたものを途中から他の方向に延びるように変更したものを実装に供するようにしても良い。二次電池２０の長尺方向の両端を物理的に連結し（電気的に連結されていても良く、電気的には絶縁状態で連結されたものであっても良い）、このエンドレスな状態で実装に供するようにしても良い。複数の細い円筒若しくは円棒で、このエンドレスベルト状の二次電池に張力を付与し、各円筒若しくは円棒が、上述したのと同様に、正極層と外部の正極部材とを電気的に連絡する機能を担うようにしても良い。   The secondary battery 20 may be folded into two at the center in the longitudinal direction for mounting, and the folded two are folded in the width direction so that the positive electrode and the negative electrode are not short-circuited. You may make it mount a thing in a case etc. Furthermore, the bellows-like shape may be mounted on a case or the like by alternately changing the folding direction, and the reverse shape having the same folding direction for each folding may be mounted on the case or the like. . In the case of a bellows shape or a fabric shape, bend using a thin cylinder or rod, and apply a conductive material used for the electrode as this cylinder or rod, and connect the positive electrode layer and the external positive electrode member. You may make it bear the function to contact electrically. Also, the one that is bent at a predetermined angle (for example, 45 degrees) other than 90 degrees with respect to the longitudinal direction and is changed along the horizontal direction so as to extend in the other direction is provided for mounting. Anyway. In the endless state, both ends of the secondary battery 20 in the longitudinal direction are physically connected (which may be electrically connected or electrically connected in an insulated state). You may make it use for mounting. A plurality of thin cylinders or rods apply tension to the endless belt-like secondary battery, and each cylinder or rod electrically communicates the positive electrode layer and the external positive electrode member in the same manner as described above. You may make it bear the function to do.

（Ｂ−８）実装に際して、絶縁シートや絶縁板等を適宜介在させるようにしても良い。また、正極層２５Ｆ、２５Ｒと露出正極部材とを連絡する正極連結部材を、実装で利用するようにしても良い。 (B-8) In mounting, an insulating sheet, an insulating plate, or the like may be appropriately interposed. Moreover, you may make it utilize the positive electrode connection member which connects the positive electrode layers 25F and 25R and an exposed positive electrode member by mounting.

（Ｂ−９）第１の実施形態では、単位セルが量子電池であるものを示したが、量子電池に限定されるものではなく、シート状（平行平板状）の二次電池であれば良い。例えば、固体リチウムイオン二次電池も、負極兼用基材又は正極兼用基材の両面に設ける単位セルとすることができる。 (B-9) In the first embodiment, the unit cell is a quantum battery. However, the unit cell is not limited to a quantum battery, and may be a sheet-like (parallel plate-like) secondary battery. . For example, the solid lithium ion secondary battery can also be a unit cell provided on both surfaces of the negative electrode substrate or the positive electrode substrate.

Claims (6)

第１電極としての機能と基材としての機能とを発揮するシート状の第１電極兼用基材と、
上記第１電極兼用基材の表面側に設けられた表面側充電層と、
上記表面側充電層に積層された表面側第２電極層と、
上記第１電極兼用基材の裏面側に設けられた裏面側充電層と、
上記裏面側充電層に積層された裏面側第２電極層と、
上記第１電極兼用基材と上記表面側充電層との間に設けられた表面側第１酸化物半導体層と、
上記第１電極兼用基材と上記裏面側充電層との間に設けられた裏面側第１酸化物半導体層と、
上記表面側充電層と上記表面側第２電極層との間に設けられた表面側第２酸化物半導体層と、
上記裏面側充電層と上記裏面側第２電極層との間に設けられた裏面側第２酸化物半導体層と
を備え、
上記第１電極兼用基材の少なくとも一部の端面に、上記表面側第２電極層及び上記裏面側第２電極層と、上記第１電極との短絡を防止する基材端面絶縁部を設け、
上記第１電極兼用基材の表面及び裏面における上記基材端面絶縁部のそれぞれの厚みが、上記表面側第１酸化物半導体層及び裏面側第１酸化物半導体層のそれぞれの厚みと同程度である
ことを特徴とする二次電池。 A sheet-shaped first electrode combined substrate that exhibits the function as the first electrode and the function as the substrate;
A surface-side charging layer provided on the surface side of the first electrode combined substrate;
A surface-side second electrode layer laminated on the surface-side charging layer;
A back side charging layer provided on the back side of the first electrode combined substrate;
A back-side second electrode layer laminated on the back-side charging layer;
A surface-side first oxide semiconductor layer provided between the first electrode combined substrate and the surface-side charging layer;
A back-side first oxide semiconductor layer provided between the first electrode combined substrate and the back-side charging layer;
A surface side second oxide semiconductor layer provided between the surface side charging layer and the surface side second electrode layer;
A back side second oxide semiconductor layer provided between the back side charge layer and the back side second electrode layer;
A base material end face insulating portion for preventing a short circuit between the first electrode and the front side second electrode layer and the back side second electrode layer is provided on at least a part of the end face of the first electrode combined base material,
Each of the thickness of the base end surface insulating portion of the surface and the back surface of the first electrode combined substrate, the same extent and thickness of each of the surface-side first oxide semiconductor layer and the back surface-side first oxide semiconductor layer A secondary battery characterized by that. 上記表面側充電層及び上記裏面側充電層はそれぞれ、酸化物半導体が、バンドギャップ内に電子不在のエネルギー準位が多数発生する光励起構造変化を起こし、エネルギー準位に電子を捕獲させることで充電し、捕獲した電子を放出させることで放電する充電層でなることを特徴とする請求項１に記載の二次電池。   Each of the front side charging layer and the back side charging layer is charged by causing the oxide semiconductor to undergo a photoexcited structural change in which a number of energy levels in the absence of electrons are generated in the band gap, and to capture electrons at the energy level. The secondary battery according to claim 1, wherein the secondary battery comprises a charge layer that discharges by releasing the captured electrons. 上記表面側充電層及び上記表面側第２電極層が設けられていない領域、及び、上記裏面側充電層及び上記裏面側第２電極層が設けられていない領域の少なくとも一方を、上記第１電極を外部の第１電極部材と接続する領域として有することを特徴とする請求項１又は２に記載の二次電池。   At least one of the region where the surface side charging layer and the surface side second electrode layer are not provided and the region where the back side charging layer and the back side second electrode layer are not provided is the first electrode. The secondary battery according to claim 1, wherein the secondary battery has a region connected to an external first electrode member. 上記表面側第１酸化物半導体層及び上記裏面側第１酸化物半導体層はｎ型金属酸化物半導体で、上記表面側第２酸化物半導体層及び上記裏面側第２酸化物半導体層はｐ型金属酸化物半導体であることを特徴とする請求項１〜３のいずれかに記載の二次電池。   The front surface side first oxide semiconductor layer and the back surface side first oxide semiconductor layer are n-type metal oxide semiconductors, and the front surface side second oxide semiconductor layer and the back surface side second oxide semiconductor layer are p-type. The secondary battery according to claim 1, wherein the secondary battery is a metal oxide semiconductor. 上記表面側第１酸化物半導体層及び上記裏面側第１酸化物半導体層はｐ型金属酸化物半導体で、上記表面側第２酸化物半導体層及び上記裏面側第２酸化物半導体層はｎ型金属酸化物半導体であることを特徴とする請求項１〜３のいずれかに記載の二次電池。   The front surface side first oxide semiconductor layer and the back surface side first oxide semiconductor layer are p-type metal oxide semiconductors, and the front surface side second oxide semiconductor layer and the back surface side second oxide semiconductor layer are n type. The secondary battery according to claim 1, wherein the secondary battery is a metal oxide semiconductor. 第１電極としての機能と基材としての機能とを発揮するシート状の第１電極兼用基材の少なくとも一部の端面に、基材端面絶縁部を形成する第１工程と、
上記第１電極兼用基材の表面側及び裏面側のそれぞれに、上記第１電極兼用基材の表面及び裏面における上記基材端面絶縁部のそれぞれと同程度の厚みで第１酸化物半導体層を積層する第２工程と、
表面側の上記第１酸化物半導体層に表面側充電層を積層する第３工程と、
裏面側の上記第１酸化物半導体層に裏面側充電層を積層する第４工程と、
上記表面側充電層及び上記裏面側充電層に紫外線を照射する第５工程と、
上記表面側充電層に第２酸化物半導体層及び第２電極層を積層する第６工程と、
上記裏面側充電層に第２酸化物半導体層及び第２電極層を積層する第７工程と
を含むことを特徴とする二次電池の製造方法。 A first step of forming a base material end face insulating portion on at least a part of the end face of the sheet-like base material serving also as the first electrode and the base material serving as a base;
A first oxide semiconductor layer is formed on each of the surface side and the back surface side of the first electrode combined substrate with the same thickness as each of the substrate end surface insulating portions on the surface and the back surface of the first electrode combined substrate. A second step of stacking;
A third step of laminating a surface-side charging layer on the first oxide semiconductor layer on the surface side;
A fourth step of laminating a backside charge layer on the first oxide semiconductor layer on the backside;
A fifth step of irradiating the front side charging layer and the back side charging layer with ultraviolet rays;
A sixth step of laminating the second oxide semiconductor layer and the second electrode layer on the surface-side charging layer;
And a seventh step of laminating a second oxide semiconductor layer and a second electrode layer on the backside charging layer.
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