JP5812484B2 - Electrode manufacturing method and lithium ion secondary battery manufacturing method using the same - Google Patents

Electrode manufacturing method and lithium ion secondary battery manufacturing method using the same Download PDF

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JP5812484B2
JP5812484B2 JP2011206394A JP2011206394A JP5812484B2 JP 5812484 B2 JP5812484 B2 JP 5812484B2 JP 2011206394 A JP2011206394 A JP 2011206394A JP 2011206394 A JP2011206394 A JP 2011206394A JP 5812484 B2 JP5812484 B2 JP 5812484B2
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賢太 平松
賢太 平松
真田　雅和
雅和 真田
古市　考次
考次 古市
邦子 寺木
邦子 寺木
松田　健
健 松田
聖志 金村
聖志 金村
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Screen Holdings Co Ltd
Tokyo Metropolitan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Description

本発明は、電極の製造方法及びこれを用いたリチウムイオン二次電池の製造方法に関する。   The present invention relates to an electrode manufacturing method and a lithium ion secondary battery manufacturing method using the same.

正極、負極、電解質（電解液）及びセパレータ等で構成されているリチウムイオン二次電池は、軽量、大容量かつ高速充放電可能であるため、現在、ノートパソコンや携帯電話等のモバイル機器や自動車等の分野において広く普及しているが、更なる大容量化及び高速充放電のために、様々な研究がなされている。   Lithium ion secondary batteries composed of a positive electrode, negative electrode, electrolyte (electrolyte), separator, etc. are lightweight, large-capacity, and capable of high-speed charge / discharge. However, various researches have been made to further increase the capacity and charge / discharge at high speed.

この大容量化及び高速充放電のためには、正極及び負極にそれぞれ含まれる正極活物質及び負極活物質と電解質との反応が律速となるところ、電解質のリチウムイオン伝導度が低いため、正極と負極との間隔をできるだけ狭く、かつ、正極及び負極の電極面積をできるだけ大きくすること、特に正極活物質及び負極活物質と電解質との接触面積を増大させることが重要である。   In order to increase the capacity and charge / discharge at a high speed, the reaction between the positive electrode active material and the negative electrode active material contained in the positive electrode and the negative electrode, respectively, and the electrolyte is rate-limiting. It is important to make the distance from the negative electrode as narrow as possible and to increase the electrode areas of the positive electrode and the negative electrode as much as possible, particularly to increase the positive electrode active material and the contact area between the negative electrode active material and the electrolyte.

この点に着目し、例えば、特許文献１（特開２０１１−７０７８８号公報）においては、低コスト、高安全性、高エネルギー密度・高出力を実現する全固体電池構造を提供することを意図して、凹凸構造を有する活物質層を含む３次元構造の電極を有する全固体電池の製造方法が提案されている。   Focusing on this point, for example, Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2011-70788) intends to provide an all-solid-state battery structure that realizes low cost, high safety, high energy density, and high output. Thus, a method for manufacturing an all-solid battery having an electrode having a three-dimensional structure including an active material layer having an uneven structure has been proposed.

即ち、上記特許文献１においては、基材の表面に第１の活物質を含む塗布液を塗布して所定の凹凸パターンを有する第１活物質層を形成する第１活物質層形成工程と、前記第１活物質層形成工程の後に、前記基材の表面に前記第１活物質層が積層されてなる積層体の表面に高分子電解質を含む塗布液を塗布して、該積層体表面の前記凹凸パターンに略追従した凹凸を有する固体電解質層を形成する固体電解質層形成工程と、固体電解質層形成工程の後に、前記固体電解質層の表面に第２の活物質を含む塗布液を塗布して、前記固体電解質層と接する面と反対側の面が略平坦な第２活物質層を形成する第２活物質層形成工程とを備えることを特徴とする全固体電池の製造方法が提案されている（特許文献１、請求項１等を参照）。   That is, in the above-mentioned Patent Document 1, a first active material layer forming step of forming a first active material layer having a predetermined concavo-convex pattern by applying a coating liquid containing a first active material on the surface of a substrate; After the first active material layer forming step, a coating solution containing a polymer electrolyte is applied to the surface of the laminate in which the first active material layer is laminated on the surface of the base material, After the solid electrolyte layer forming step for forming the solid electrolyte layer having irregularities substantially following the irregular pattern, and the solid electrolyte layer forming step, a coating liquid containing a second active material is applied to the surface of the solid electrolyte layer. And a second active material layer forming step of forming a second active material layer in which the surface opposite to the surface in contact with the solid electrolyte layer is substantially flat is proposed. (See Patent Document 1, Claim 1 and the like).

そして、凹凸パターンを有する活物質層を形成については、具体的には、活物質を含む塗布液をノズルから吐出させて基材である集電体の表面に塗布して凹凸パターンを有する活物質層を形成する方法が提案されている。   And about formation of the active material layer which has an uneven | corrugated pattern, specifically, the active material which has an uneven | corrugated pattern by discharging the coating liquid containing an active material from a nozzle, and apply | coating to the surface of the collector which is a base material A method of forming a layer has been proposed.

このようなノズルディスペンス方式による塗布技術は研究が進んでおり、塗布液の組成を適宜調整した上で、基材表面に対してノズルを所定方向に相対移動させて、ライン状に塗布液を基材表面に塗布する。このような構成によれば、ラインの幅や高さの安定したパターンを形成することが可能であり、良好な性能を有する電池を安定して製造することができる。   Research into coating technology using such a nozzle dispensing method is advancing, and after adjusting the composition of the coating solution as appropriate, the nozzle is moved relative to the surface of the substrate in a predetermined direction to form the coating solution in a line. Apply to the material surface. According to such a configuration, it is possible to form a pattern with a stable line width and height, and it is possible to stably manufacture a battery having good performance.

特開２０１１−７０７８８号公報JP 2011-70788 A

しかしながら、上記のような特許文献１において得られる電池において、単位面積当たりの容量（Ａｈ／ｃｍ２）を向上させるには、単純に考えれば、塗布液の塗布量を増大させてライン（即ち、活物質層を構成する線状の活物質部）のアスペクト比を高め、ライン間の間隔（スペース）を狭めればよいが、本発明者は、間隔を狭め過ぎると隣接する線状の活物質部が接触してしまって表面積が小さくなり、また、隣接する線状の活物質間でイオンが拡散し易くなること等から、電池特性が低下するとの知見を見出した。 However, in the battery obtained in Patent Document 1 as described above, in order to improve the capacity per unit area (Ah / cm 2 ), if simply considered, the coating amount of the coating liquid is increased (that is, the line (that is, It is only necessary to increase the aspect ratio of the linear active material portion constituting the active material layer and narrow the space between the lines. However, if the space is too narrow, the present inventor will adjoin the linear active material. As a result, the surface area is reduced due to contact of the parts, and ions are easily diffused between adjacent linear active materials.

そこで、本発明の目的は、このような知見に基づき、最終的に得られる電池において、隣接する線状の活物質部の間隔の最適（下限）値を決定し、容量維持率を低下させることなく単位面積当たりの容量（Ａｈ／ｃｍ２）を向上させ得る電極の製造方法を提供することにある。更に本発明の目的は、かかる電極の製造方法を用いたリチウムイオン二次電池の製造方法を提供することにある。 Accordingly, the object of the present invention is to determine the optimum (lower limit) value of the interval between adjacent linear active material portions in the finally obtained battery based on such knowledge, and to reduce the capacity maintenance rate. An object of the present invention is to provide an electrode manufacturing method capable of improving the capacity per unit area (Ah / cm 2 ). Furthermore, the objective of this invention is providing the manufacturing method of a lithium ion secondary battery using the manufacturing method of this electrode.

上記課題を解決すべく、本発明者らは、
集電体及び前記集電体上に設けられた複数本の凸状の線状活物質部で形成された活物質層を有する電極の製造方法であって、
（１）集電体の面上に高さＨ及び幅Ｗを有する複数本の略平行な凸状の線状活物質部を間隔Ｓ１〜ｎ（ｎは２以上の整数）で形成して得た電極と、対極と、電解質層と、を積層した構造を有するテストセルｎ個を作製するテストセル作製工程と、
（２）前記工程（１）で作製した前記テストセルｎ個の容量維持率を測定し、測定結果に基づいて前記線状活物質部の最適間隔Ｓｘを決定する工程と、
（３）集電体の面上に複数本の略平行な凸状の線状第１活物質部を間隔Ｓｘで形成して電極を作製する工程と、
を有することを特徴とする電極の製造方法を提供する。

In order to solve the above problems, the present inventors have
A method for producing an electrode having an active material layer formed of a current collector and a plurality of convex linear active material portions provided on the current collector,
(1) On the surface of the current collector, a plurality of substantially parallel convex linear active material portions having a height H and a width W are formed at intervals S 1 to n (n is an integer of 2 or more). A test cell manufacturing step of manufacturing n test cells having a structure in which the obtained electrode, a counter electrode, and an electrolyte layer are stacked;
(2) measuring the capacity retention rate of the n test cells prepared in the step (1), and determining the optimum interval Sx of the linear active material parts based on the measurement results;
(3) forming a plurality of substantially parallel convex first active material portions with a spacing Sx on the surface of the current collector; and
An electrode manufacturing method is provided.

このような構成を有する本発明の電極の製造方法によれば、凸状の線状活物質部で構成された凹凸構造パターンの活物質層を有する電極において、線状活物質部の幅及び高さを変化させずに隣接する線状活物質部の間隔を最適化することにより、容量維持率を低下させずに単位面積当たりの容量を増大させることができる。かかる本発明の電極の製造方法は、線状活物質部の幅が規定されている場合に、規格容量に応じて隣接する線状活物質部の間隔を決定する方法として好適である。   According to the method for manufacturing an electrode of the present invention having such a configuration, in an electrode having an active material layer having a concavo-convex structure pattern composed of a convex linear active material portion, the width and height of the linear active material portion are By optimizing the interval between the adjacent linear active material portions without changing the thickness, the capacity per unit area can be increased without decreasing the capacity maintenance rate. Such an electrode manufacturing method of the present invention is suitable as a method for determining the interval between adjacent linear active material portions according to the standard capacity when the width of the linear active material portion is defined.

また、本発明は、上記本発明の電極の製造方法を用いた電池の製造方法にも関する。具体的には、本発明は、
上記本発明の電極の製造方法により第１電極を得る第１電極形成工程と、
第２集電体の面上に複数本の略平行な凸状の線状第２活物質部を形成して第２電極を得る第２電極形成工程と、
前記第１活物質部と前記第２活物質部とが対向するように、セパレータを介在させて前記第１電極と前記第２電極とを積層して積層体を得る積層体形成工程と、
前記第１電極と前記第２電極との間に電解液を充填するとともに前記セパレータに前記電解液を含浸させる電解液充填工程と、
を有すること、
を特徴とするリチウムイオン二次電池の製造方法を提供する。
Moreover, this invention relates also to the manufacturing method of the battery using the manufacturing method of the electrode of the said invention. Specifically, the present invention provides:
A first electrode forming step of obtaining the first electrode by the electrode manufacturing method of the present invention;
A second electrode forming step of obtaining a second electrode by forming a plurality of substantially parallel convex linear second active material portions on the surface of the second current collector;
A laminate forming step of obtaining a laminate by laminating the first electrode and the second electrode with a separator interposed therebetween so that the first active material portion and the second active material portion are opposed to each other;
An electrolyte filling step of impregnating the electrolyte in the separator to fill an electrolytic solution between said first electrode and the second electrodes,
Having
A method for producing a lithium ion secondary battery is provided.

このような構成を有する本発明のリチウムイオン二次電池の製造方法によれば、凸状の線状活物質部で構成された凹凸構造パターンの活物質層を有する電極において、線状活物質部の幅及び高さを変化させずに隣接する線状活物質部の間隔を最適化することにより、リチウムイオン二次電池の容量維持率を低下させずに単位面積当たりの容量を増大させることができる。かかる本発明のリチウムイオン二次電池の製造方法は、線状活物質部の幅が規定されている場合に、規格容量に応じて隣接する線状活物質部の間隔を決定する方法として好適である。   According to the method for manufacturing a lithium ion secondary battery of the present invention having such a configuration, in an electrode having an active material layer of a concavo-convex structure pattern composed of a convex linear active material portion, a linear active material portion By optimizing the spacing between adjacent linear active material parts without changing the width and height of the battery, the capacity per unit area can be increased without reducing the capacity maintenance rate of the lithium ion secondary battery. it can. Such a method for producing a lithium ion secondary battery according to the present invention is suitable as a method for determining the interval between adjacent linear active material portions according to the standard capacity when the width of the linear active material portion is specified. is there.

本発明によれば、最終的に得られる電池において、容量維持率が低下させることなく単位面積当たりの容量（Ａｈ／ｃｍ２）を向上させ得る電極の製造方法、及び当該電極の製造方法を用いたリチウムイオン二次電池の製造方法を得ることができる。 According to the present invention, in the battery finally obtained, the electrode manufacturing method capable of improving the capacity per unit area (Ah / cm 2 ) without reducing the capacity maintenance rate, and the electrode manufacturing method are used. The manufacturing method of the lithium ion secondary battery which was used can be obtained.

本発明の電極の製造方法の一実施形態において作製したコイン型のテストセルの構造を示す一部断面概略側面図である。It is a partial cross section schematic side view which shows the structure of the coin-type test cell produced in one Embodiment of the manufacturing method of the electrode of this invention. 図１に示すテストセル１において、ノズルディスペンス法により凸状負極活物質部１２ａからなる負極活物質層１２を形成して負極Ａを形成する様子を示す模式図である。In the test cell 1 shown in FIG. 1, it is a schematic diagram which shows a mode that the negative electrode active material layer 12 which consists of the convex negative electrode active material part 12a is formed by the nozzle dispensing method, and the negative electrode A is formed. テストセル１〜６を０．１Ｃから１０ＣまでのＣレートの範囲で充放電した場合の容量維持率（％）を示すグラフである。It is a graph which shows the capacity | capacitance maintenance factor (%) at the time of charging / discharging the test cells 1-6 in the range of C rate from 0.1C to 10C. 発明の電極の製造方法の一実施形態において最適間隔Ｓｘを求める方法の一例を説明するためのグラフである。It is a graph for demonstrating an example of the method of calculating | requiring the optimal space | interval Sx in one Embodiment of the manufacturing method of the electrode of invention.

以下、図面を参照しながら本発明の電極の製造方法の一実施形態について説明するが、本発明はこれらのみに限定されるものではない。なお、以下の説明では、同一又は相当部分には同一符号を付し、重複する説明は省略することもある。また、図面は、本発明を概念的に説明するためのものであるから、理解容易のために、必要に応じて寸法、比又は数を誇張又は簡略化して表している場合もある。   Hereinafter, although one Embodiment of the manufacturing method of the electrode of this invention is described, referring drawings, this invention is not limited only to these. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description may be omitted. Moreover, since the drawings are for conceptual description of the present invention, the dimensions, ratios, or numbers may be exaggerated or simplified as necessary for easy understanding.

本実施形態では、図１に示す構造のコイン型のリチウムイオン二次電池をテストセルとして複数個作製し、隣接する線状負極活物質部の最適間隔を決定し、この最適間隔で線状負極活物質部を有する負極を製造する場合について説明する。   In the present embodiment, a plurality of coin-type lithium ion secondary batteries having the structure shown in FIG. 1 are prepared as test cells, and the optimum interval between adjacent linear anode active material portions is determined, and the linear anode is determined at the optimum interval. The case where the negative electrode which has an active material part is manufactured is demonstrated.

（１）テストセル作製工程
本実施形態においては、図１に示すリチウムイオン二次電池からなるｎ（ｎは２以上の整数）個のテストセルを作製する。図１は、本発明の負極の製造方法の一実施形態において作製したコイン型のテストセル１の構造を示す一部断面概略側面図である。 (1) Test cell production process In this embodiment, n (n is an integer greater than or equal to 2) test cells made of the lithium ion secondary battery shown in FIG. 1 are produced. FIG. 1 is a partial cross-sectional schematic side view showing the structure of a coin-type test cell 1 manufactured in an embodiment of the negative electrode manufacturing method of the present invention.

このテストセル１を作製するためには、まず、負極集電体１０の面上に幅Ｗ及び高さＨを有する複数本の略平行な凸状の線状負極活物質部１２ａからなる負極活物質層１２を形成して得た負極Ａと、対極である正極Ｃと、を、セパレータ２０を介在させて積層し、負極Ａと正極Ｃとの間に電解液（図示せず）を充填するとともにセパレータ２０に電解液を含浸させて電解質層を形成する。これにより、負極Ａ、セパレータ２０を含む電解質層及び正極が積層された構成を有するテストセル１を作製する。   In order to produce the test cell 1, first, a negative electrode active material comprising a plurality of substantially parallel convex linear negative electrode active material portions 12a having a width W and a height H on the surface of the negative electrode current collector 10 is described. A negative electrode A obtained by forming the material layer 12 and a positive electrode C as a counter electrode are stacked with a separator 20 interposed therebetween, and an electrolyte solution (not shown) is filled between the negative electrode A and the positive electrode C. At the same time, the separator 20 is impregnated with an electrolytic solution to form an electrolyte layer. Thus, the test cell 1 having a configuration in which the negative electrode A, the electrolyte layer including the separator 20 and the positive electrode are stacked is manufactured.

負極Ａは、負極集電体１０の面上に、いわゆるノズルディスペンス法により、複数本の略平行な凸状の線状負極活物質部１２ａを間隔Ｓ１で形成して線状負極活物質部１２ａからなる負極活物質層１２を形成することによって得る。図２は、図１に示すテストセル１において、ノズルディスペンス法により凸状負極活物質部１２ａからなる負極活物質層１２を形成して負極Ａを形成する様子を示す模式図である。 Anode A is on the surface of the negative electrode current collector 10, the so-called nozzle dispense method, linear negative electrode active material portion to form a substantially parallel convex linear negative electrode active material 12a of the plurality of intervals S 1 It is obtained by forming a negative electrode active material layer 12 made of 12a. FIG. 2 is a schematic diagram showing how the negative electrode A is formed by forming the negative electrode active material layer 12 including the convex negative electrode active material portion 12a by the nozzle dispensing method in the test cell 1 shown in FIG.

図２の（ａ）は、ノズルディスペンス法によって負極活物質層１２を構成する線状負極活物質部１２ａが形成される様子を模式的に示す側面図（即ち、負極集電体１０の主面に対して略平行なＸ方向からみた場合にみえる図）であり、図２の（ｂ）は、ノズルディスペンス法によって負極活物質層１２を構成する線状負極活物質部１２ａが形成される様子を模式的に示す斜視図である。   FIG. 2A is a side view schematically showing how the linear negative electrode active material portion 12a constituting the negative electrode active material layer 12 is formed by the nozzle dispensing method (that is, the main surface of the negative electrode current collector 10). FIG. 2B shows a state in which the linear negative electrode active material portion 12a constituting the negative electrode active material layer 12 is formed by the nozzle dispensing method. FIG.

線状負極活物部１２ａは、図２に示すように、例えば（ア）負極活物質を含む負極活物質材料（塗布液）を間隔Ｓ１で線状に吐出するノズルを負極集電体１０に対して相対移動させ、負極集電体１０上に負極活物質材料からなる複数本の凸状の線状負極活物質部１２ａを形成する塗布工程（即ち、ノズルディスペンス法を用いた塗布工程）、及び、（イ）線状負極活物質部１２ａを乾燥させる乾燥工程により形成することができる。 As shown in FIG. 2, the linear negative electrode active material portion 12 a includes, for example, (a) a negative electrode current collector 10 that discharges a negative electrode active material material (coating liquid) containing a negative electrode active material linearly at an interval S 1. Coating process for forming a plurality of convex linear negative electrode active material portions 12a made of a negative electrode active material on the negative electrode current collector 10 (that is, a coating process using a nozzle dispensing method). And (a) It can be formed by a drying step of drying the linear negative electrode active material portion 12a.

より具体的には、上記（ア）の塗布工程では、図２の（ａ）に示すように、負極集電体１０を矢印Ｙ１の方向に搬送させることにより、ノズル４０を負極集電体１０に対して相対移動させる。搬送される負極集電体１０の表面には、ノズル４０から、ペースト状乃至はスラリー状の負極活物質材料が間隔Ｓ１で線状負極活物質部１２ａを形成するように吐出される。本実施形態においては、ノズル４０の位置は固定されており、負極集電体１０が搬送されることにより、ノズル４０が負極集電体１０に対して相対移動される。 More specifically, in the coating step (A), as shown in FIG. 2 (a), by transporting the negative electrode current collector 10 in the direction of arrow Y 1, the nozzle 40 anode current collector Move relative to 10. The anode current collector 10 surface of which is conveyed from the nozzle 40, pasty or is discharged as a slurry of the negative electrode active material to form a linear negative electrode active material portion 12a at intervals S 1. In the present embodiment, the position of the nozzle 40 is fixed, and the nozzle 40 is moved relative to the negative electrode current collector 10 by transporting the negative electrode current collector 10.

本実施形態では、塗布液である負極活物質材料を吐出するための吐出口が複数設けられたノズル４０を、負極集電体１０上方に配置し、その吐出口から一定量の負極活物質材料を吐出させながら、負極集電体１０をノズル４０に対して相対的に矢印Ｙ１の方向に一定速度で搬送させる。こうすることで、負極集電体１０上には、Ｙ方向に沿って負極活物質材料からなる複数本の線状の凸状活物質部１２ａが間隔Ｓ１で形成されてストライプ状のラインアンドスペースのパターン形状となるように塗布される。 In the present embodiment, a nozzle 40 provided with a plurality of discharge ports for discharging a negative electrode active material that is a coating liquid is disposed above the negative electrode current collector 10, and a certain amount of negative electrode active material is discharged from the discharge port. while discharging the so conveyed at a constant speed in a direction of the relative arrows Y 1 and negative electrode current collector 10 to the nozzle 40. In this way, on the negative electrode current collector 10, negative electrode active material a plurality of linear convex active material portion 12a made of are formed at intervals S 1 and striped line and along the Y-direction It is applied to form a space pattern.

ノズル４０に複数本の吐出口を間隔Ｓ１で設ければ一方向における一回の相対移動で複数本の線状の線状負極活物質部１２ａが形成されてストライプ状とすることができ、負極集電体１０の搬送を続けることにより、負極集電体１０の全面にストライプ状に線状の凸状負極活物質部１２ａを形成することができる。 By providing a plurality of ejection ports in the nozzle 40 at intervals S 1 can be a single relative movement plurality of linear linear negative electrode active material portion 12a is formed by and stripes in one direction, By continuing the conveyance of the negative electrode current collector 10, the linear convex negative electrode active material portion 12 a can be formed in a stripe shape on the entire surface of the negative electrode current collector 10.

上記のように形成された負極活物質材料からなる複数本の線状の線状活物質部１２ａは、まだ溶剤等を含むいわば塗布膜の状態であるため、線状活物質部１２ａが設けられた負極集電体１０は、例えば乾燥手段である送風機等の下側領域を通り抜けるように搬送され、ドライエアーによって乾燥工程が実施される。これにより、負極集電体１０と、負極集電体１０の表面に形成された線状活物質部１２ａからなる負極活物質層１２と、を含む負極Ａが得られる。   Since the plurality of linear linear active material portions 12a made of the negative electrode active material formed as described above are still in the state of a coating film containing a solvent or the like, the linear active material portions 12a are provided. The negative electrode current collector 10 is conveyed so as to pass through a lower region such as a blower as a drying means, and a drying process is performed by dry air. Thereby, the negative electrode A including the negative electrode current collector 10 and the negative electrode active material layer 12 including the linear active material portion 12a formed on the surface of the negative electrode current collector 10 is obtained.

乾燥工程の乾燥温度及び乾燥時間は、当業者であれば適宜選択することができる。乾燥温度は、線状活物質部１２ａを乾燥させてその形状を固定させ得る範囲であればよく、例えば５℃〜１５０℃の範囲内、好ましくは常温（２３℃）〜８０℃の範囲内の温度であればよい。また、乾燥時間は、負極集電体１０の搬送速度によって制御することもできる。   A person skilled in the art can appropriately select the drying temperature and drying time in the drying step. The drying temperature should just be the range which can dry the linear active material part 12a, and can fix the shape, For example, it exists in the range of 5 to 150 degreeC, Preferably it exists in the range of normal temperature (23 degreeC) to 80 degreeC. Any temperature is acceptable. Further, the drying time can be controlled by the conveyance speed of the negative electrode current collector 10.

このようにして形成する線状負極活物質部１２ａの幅Ｗは、作製しようとするリチウムイオン二次電池の規格にもよるが、例えば１０〜２００μｍであればよい。また、線状負極活物質部１２ａの高さＨは、後述する高さ変更（テストセル作製）工程で、種々の値に変化させるが、１０〜２００μｍであればよい。このような範囲であれば、線状負極活物質部１２ａの抵抗の増大及び充放電容量の低下を抑制することができる。   The width W of the linear negative electrode active material portion 12a thus formed may be, for example, 10 to 200 μm, although it depends on the standard of the lithium ion secondary battery to be produced. Moreover, although the height H of the linear negative electrode active material part 12a is changed into various values in the height change (test cell preparation) process mentioned later, what is necessary is just 10-200 micrometers. If it is such a range, the increase in resistance of the linear negative electrode active material part 12a and the fall of charging / discharging capacity | capacitance can be suppressed.

ここで、ペースト状乃至はスラリー状の負極活物質材料は、負極活物質と、導電助剤（任意）と、結着剤と、溶剤等と、を常法により攪拌・混合（混練）して得られる混合物で構成され、ノズル４０から吐出できる範囲で種々の粘度を有すればよい。本実施形態においては、例えば、せん断速度１ｓ−１で、下限１０Ｐａ・ｓ、上限１００００Ｐａ・ｓ程度であるのが好ましい。なお、各成分は溶剤に溶解していても分散していてもよい（一部が溶解して残部が分散している場合も含む。）。 Here, the paste-like or slurry-like negative electrode active material is prepared by stirring and mixing (kneading) a negative electrode active material, a conductive additive (optional), a binder, a solvent, and the like by a conventional method. What is necessary is just to have a various viscosity in the range comprised with the mixture obtained and discharged from the nozzle 40. FIG. In the present embodiment, for example, it is preferable that the shear rate is 1 s −1 and the lower limit is about 10 Pa · s and the upper limit is about 10000 Pa · s. Each component may be dissolved or dispersed in a solvent (including the case where a part is dissolved and the remainder is dispersed).

また、上記塗布工程に用いる負極活物質材料の固形分割合は、負極活物質材料がノズル４０から吐出できるように種々の固形分割合を有することができるが、前記混合物の湿潤点における固形分割合よりも小さな固形分割合を有しており、例えば６０質量％であるのが好ましい。   Further, the solid content ratio of the negative electrode active material used in the coating step can have various solid content ratios so that the negative electrode active material can be discharged from the nozzle 40, but the solid content ratio at the wet point of the mixture. It is preferable that it is 60 mass%, for example.

これらの粘度及び固形分割合は、負極活物質、導電助剤、結着材及び溶剤等の成分の種類や配合量、寸法又は形状等によっても異なるが、上記負極活物質と、上記導電助剤と、結着材と、溶剤等と、を常法により攪拌・混合（混練）する際の混練時間の長さによって、調整することができる。   These viscosities and solid content ratios vary depending on the types and blending amounts, dimensions, shapes, etc. of components such as the negative electrode active material, conductive auxiliary agent, binder and solvent, but the negative electrode active material and the conductive auxiliary agent. And the length of the kneading time when the binder, the solvent and the like are agitated and mixed (kneaded) by a conventional method.

ここで、線状負極活物質部１２ａに含まれる負極活物質としては、後述する電極作製工程において用いるものと同じものを用いる。この負極活物質としては、本発明の技術分野で常用されるものを使用でき、例えば、金属、金属繊維、炭素材料、酸化物、窒化物、珪素、珪素化合物、錫、錫化合物、各種合金材料等が挙げられる。これらのなかでも、容量密度の大きさ等を考慮すると、酸化物、炭素材料、珪素、珪素化合物、錫、錫化合物等が好ましい。酸化物としては、例えば、式：Ｌｉ４Ｔｉ５Ｏ１２で表されるチタン酸リチウム等が挙げられる。炭素材料としては、例えば、各種天然黒鉛（グラファイト）、コークス、黒鉛化途上炭素、炭素繊維、球状炭素、各種人造黒鉛、非晶質炭素等が挙げられる。珪素化合物としては、例えば、珪素含有合金、珪素含有無機化合物、珪素含有有機化合物、固溶体等が挙げられる。珪素化合物の具体例としては、例えば、ＳｉＯａ（０．０５＜ａ＜１．９５）で表される酸化珪素、珪素とＦｅ、Ｃｏ、Ｓｂ、Ｂｉ、Ｐｂ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇｅ、Ｉｎ、Ｓｎ及びＴｉから選ばれる少なくとも１種の元素とを含む合金、珪素、酸化珪素又は合金に含まれる珪素の一部がＢ、Ｍｇ、Ｎｉ、Ｔｉ、Ｍｏ、Ｃｏ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｍｎ、Ｎｂ、Ｔａ、Ｖ、Ｗ、Ｚｎ、Ｃ、Ｎ及びＳｎから選ばれる少なくとも１種の元素で置換された珪素化合物又は珪素含有合金、これらの固溶体等が挙げられる。錫化合物としては、例えば、ＳｎＯｂ（０＜ｂ＜２）、ＳｎＯ２、ＳｎＳｉＯ３、Ｎｉ２Ｓｎ４、Ｍｇ２Ｓｎ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、必要に応じて２種以上を組み合わせて用いてもよい。 Here, as the negative electrode active material contained in the linear negative electrode active material portion 12a, the same material as that used in the electrode manufacturing process described later is used. As this negative electrode active material, those commonly used in the technical field of the present invention can be used. For example, metals, metal fibers, carbon materials, oxides, nitrides, silicon, silicon compounds, tin, tin compounds, various alloy materials Etc. Of these, oxides, carbon materials, silicon, silicon compounds, tin, tin compounds and the like are preferable in view of the capacity density. Examples of the oxide include lithium titanate represented by the formula: Li 4 Ti 5 O 12 . Examples of the carbon material include various natural graphite (graphite), coke, graphitizing carbon, carbon fiber, spherical carbon, various artificial graphite, amorphous carbon, and the like. Examples of the silicon compound include a silicon-containing alloy, a silicon-containing inorganic compound, a silicon-containing organic compound, a solid solution, and the like. Specific examples of the silicon compound include, for example, silicon oxide represented by SiO a (0.05 <a <1.95), silicon and Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, An alloy containing at least one element selected from In, Sn, and Ti, silicon, silicon oxide, or a part of silicon contained in the alloy is B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Examples thereof include silicon compounds or silicon-containing alloys substituted with at least one element selected from Fe, Mn, Nb, Ta, V, W, Zn, C, N, and Sn, and solid solutions thereof. Examples of the tin compound include SnO b (0 <b <2), SnO 2 , SnSiO 3 , Ni 2 Sn 4 , Mg 2 Sn, and the like. A negative electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type as needed.

また、線状負極活物質部１２ａは、導電助剤を含んでいてもよい。導電助剤としては、本発明の技術分野で常用されるものを使用でき、例えば、天然黒鉛、人造黒鉛等のグラファイト類、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等のカーボンブラック類、炭素繊維、金属繊維等の導電性繊維類、フッ化カーボン、アルミニウム等の金属粉末類、酸化亜鉛等の導電性ウィスカー類、酸化チタン等の導電性金属酸化物、フェニレン誘導体等の有機導電性材料等が挙げられる。導電剤は１種を単独で使用でき又は必要に応じて２種以上を組み合わせて使用できる。   Moreover, the linear negative electrode active material part 12a may contain the conductive support agent. As the conductive auxiliary agent, those commonly used in the technical field of the present invention can be used. For example, natural graphite, graphite such as artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black Carbon blacks such as carbon fibers, conductive fibers such as carbon fibers and metal fibers, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide, conductive metal oxides such as titanium oxide, and phenylene derivatives Organic conductive materials such as A conductive agent can be used individually by 1 type, or can be used in combination of 2 or more type as needed.

結着剤としても、本発明の技術分野で常用されるものを使用でき、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリエチレン、ポリプロピレン、アラミド樹脂、ポリアミド、ポリイミド、ポリアミドイミド、ポリアクリルニトリル、ポリアクリル酸、ポリアクリル酸メチルエステル、ポリアクリル酸エチルエステル、ポリアクリル酸ヘキシルエステル、ポリメタクリル酸、ポリメタクリル酸メチルエステル、ポリメタクリル酸エチルエステル、ポリメタクリル酸ヘキシルエステル、ポリ酢酸ビニル、ポリビニルピロリドン、ポリエーテル、ポリエーテルサルホン、ポリヘキサフルオロプロピレン、スチレン−ブタジエンゴム、エチレン−プロピレンジエン共重合体、カルボキシメチルセルロース等が挙げられる。また、テトラフルオロエチレン、ヘキサフルオロプロピレン、パーフルオロアルキルビニルエーテル、フッ化ビニリデン、クロロトリフルオロエチレン、エチレン、プロピレン、ペンタフルオロプロピレン、フルオロメチルビニルエーテル、アクリル酸、ヘキサジエン等から選ばれるモノマー化合物の共重合体を結着剤として用いてもよい。結着剤は１種を単独で使用でき又は必要に応じて２種以上を組み合わせて使用できる。   As the binder, those commonly used in the technical field of the present invention can be used. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide , Polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, poly Vinyl acetate, polyvinyl pyrrolidone, polyether, polyether sulfone, polyhexafluoropropylene, styrene-butadiene rubber, ethylene-propylene diene copolymer, carboxymethyl cellulose And the like. Copolymers of monomer compounds selected from tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, hexadiene, etc. May be used as a binder. A binder can be used individually by 1 type, or can be used in combination of 2 or more type as needed.

溶剤としては、多くの電解液に含まれ得る六フッ化リン酸リチウム（ＬｉＰＦ６）等を分解しないように、水を除く有機溶媒を用いるのが好ましい。かかる有機溶媒としては、本発明の技術分野で常用されるものを使用でき、例えば、ジメチルホルムアミド、ジメチルアセトアミド、メチルホルムアミド、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルアミン、アセトン、シクロヘキサノン等が挙げられる。有機溶媒は１種を単独で使用でき又は２種以上を混合して使用できる。 As the solvent, it is preferable to use an organic solvent excluding water so as not to decompose lithium hexafluorophosphate (LiPF 6 ) or the like that can be contained in many electrolyte solutions. As the organic solvent, those commonly used in the technical field of the present invention can be used, and examples thereof include dimethylformamide, dimethylacetamide, methylformamide, N-methyl-2-pyrrolidone (NMP), dimethylamine, acetone, and cyclohexanone. Can be mentioned. An organic solvent can be used individually by 1 type, or can mix and use 2 or more types.

また、負極集電体１０としては、本発明の属する技術分野において公知の材料を用いることができるが、例えばアルミニウム箔等の金属膜であればよい。また、図示しないが、この負極集電体１０は、絶縁性の基材の表面に形成されていてもよい。このような基材としては絶縁性材料で形成された平板状部材を用いればよく、かかる絶縁性材料としては、例えば樹脂、ガラス又はセラミックス等が挙げられる。また、基材は可撓性を有するフレキシブル基板であってもよい。   The negative electrode current collector 10 may be made of a known material in the technical field to which the present invention belongs, and may be a metal film such as an aluminum foil. Although not shown, the negative electrode current collector 10 may be formed on the surface of an insulating base material. As such a base material, a flat plate member formed of an insulating material may be used. Examples of such an insulating material include resin, glass, ceramics, and the like. The base material may be a flexible flexible substrate.

次に、正極Ｃとしては、上記の負極Ａを負極集電体上に線状負極活物質部からなる負極活物質層を形成したのと同様に、正極集電体上に正極活物質材料を含む凸状の線状正極活物質部からなる正極活物質層が設けて形成してもよいが、本実施形態においては、正極Ｃとして、リチウム金属からなる正極Ｃを用いる。   Next, as the positive electrode C, the positive electrode active material is formed on the positive electrode current collector in the same manner as the negative electrode active material layer formed of the linear negative electrode active material part is formed on the negative electrode current collector. Although a positive electrode active material layer including a convex linear positive electrode active material portion may be provided, the positive electrode C made of lithium metal is used as the positive electrode C in the present embodiment.

なお、正極集電体と凸状の線状正極活物質部からなる正極活物質層とで正極Ｃを構成する場合、正極集電体としては、本発明の属する技術分野において公知の材料を用いることができ、例えば銅箔等の金属膜で挙げられる。また、負極集電体１０と同様に、正極集電体は、絶縁性の基材の表面に形成されていてもよい。このような基材としては絶縁性材料で形成された平板状部材を用いればよく、かかる絶縁性材料としては、例えば樹脂、ガラス又はセラミックス等が挙げられる。また、基材は可撓性を有するフレキシブル基板であってもよい。   In the case where the positive electrode C is composed of the positive electrode current collector and the positive electrode active material layer formed of the convex linear positive electrode active material part, a material known in the technical field to which the present invention belongs is used as the positive electrode current collector. For example, a metal film such as a copper foil is used. Similarly to the negative electrode current collector 10, the positive electrode current collector may be formed on the surface of an insulating base material. As such a base material, a flat plate member formed of an insulating material may be used. Examples of such an insulating material include resin, glass, ceramics, and the like. The base material may be a flexible flexible substrate.

また、正極集電体と凸状の線状正極活物質部からなる正極活物質層とで正極Ｃを構成する場合、線状正極活物質部が含む正極活物質（粉末）としては、例えば、リチウム含有複合金属酸化物、カルコゲン化合物、二酸化マンガン等が挙げられる。リチウム含有複合金属酸化物は、リチウムと遷移金属とを含む金属酸化物又は該金属酸化物中の遷移金属の一部が異種元素によって置換された金属酸化物である。ここで、異種元素としては、例えば、Ｎａ、Ｍｇ、Ｓｃ、Ｙ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｌ、Ｃｒ、Ｐｂ、Ｓｂ、Ｂ等が挙げられ、Ｍｎ、Ａｌ、Ｃｏ、Ｎｉ、Ｍｇ等が好ましい。異種元素は１種でも又は２種以上でもよい。これらのなかでも、リチウム含有複合金属酸化物を好ましく使用できる。リチウム含有複合金属酸化物としては、例えば、ＬｉｘＣｏＯ２、ＬｉｘＮｉＯ２、ＬｉｘＭｎＯ２、ＬｉｘＣｏｙＮｉ１−ｙＯ２、ＬｉｘＣｏｙＭ１−ｙＯｚ、ＬｉｘＮｉ１−ｙＭｙＯｚ、ＬｉｘＭｎ２Ｏ４、ＬｉｘＭｎ２−ｙＭｙＯ４、ＬｉＭＰＯ４、Ｌｉ２ＭＰＯ４Ｆ（前記各式中、例えば、ＭはＮａ、Ｍｇ、Ｓｃ、Ｙ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｌ、Ｃｒ、Ｐｂ、Ｓｂ、Ｖ及びＢよりなる群から選ばれる少なくとも１種。０＜ｘ≦１．２、０＜ｙ≦０．９、２．０≦ｚ≦２．３）、ＬｉＭｅＯ２（式中、Ｍｅ＝ＭｘＭｙＭｚ;Ｍｅ及びＭは遷移金属、ｘ＋ｙ＋ｚ＝１）等が挙げられる。リチウム含有複合金属酸化物の具体例としては、例えば、ＬｉＮｉ１／３Ｍｎ１／３Ｃｏ１／３Ｏ２、ＬｉＮｉ０．８Ｃｏ０．１５Ａｌ０．０５Ｏ２等が挙げられる。ここで、上記各式中リチウムのモル比を示すｘ値は、充放電により増減する。また、カルコゲン化合物としては、例えば二硫化チタン、二硫化モリブデン等が挙げられる。正極活物質は１種を単独で使用でき２種以上を併用してもよい。正極活物質層１６には、負極活物質層１２に関して上記に記載した導電助剤を含めてもよい。 Further, when the positive electrode C is composed of a positive electrode current collector and a positive electrode active material layer composed of a convex linear positive electrode active material part, as the positive electrode active material (powder) included in the linear positive electrode active material part, for example, Examples include lithium-containing composite metal oxides, chalcogen compounds, and manganese dioxide. The lithium-containing composite metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is substituted with a different element. Here, examples of the different elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B, and Mn, Al, Co, Ni, Mg and the like are preferable. One kind or two or more kinds of different elements may be used. Among these, lithium-containing composite metal oxides can be preferably used. The lithium-containing composite metal oxide, for example, Li x CoO 2, Li x NiO 2, Li x MnO 2, Li x Co y Ni 1-y O 2, Li x Co y M 1-y O z, Li x Ni 1-y M y O z , Li x Mn 2 O 4, Li x Mn 2-y M y O 4, LiMPO 4, Li 2 MPO 4 F ( in the respective formulas, for example, M is Na, Mg, Sc , Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, V and B. At least one selected from the group consisting of 0 <x ≦ 1.2 and 0 <y ≦ 0. 9, 2.0 ≦ z ≦ 2.3), LiMeO 2 (wherein Me = MxMyMz; Me and M are transition metals, x + y + z = 1), and the like. Specific examples of the lithium-containing composite metal oxide include LiNi 1/3 Mn 1/3 Co 1/3 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 . Here, x value which shows the molar ratio of lithium in each said formula increases / decreases by charging / discharging. Examples of the chalcogen compound include titanium disulfide and molybdenum disulfide. A positive electrode active material can be used individually by 1 type, and may use 2 or more types together. The positive electrode active material layer 16 may include the conductive additive described above with respect to the negative electrode active material layer 12.

次に、上記のようにして作製した負極Ａと、正極Ｃと、を、セパレータ２０を介在させて積層した状態で、有底円筒形で開口部が内側に湾曲した、例えばステンレス製の金属容器２２内に挿入する。このとき、負極Ａと正極Ｃとの間に密閉空間を形成され得るように、金属容器２２の外周側面部にはガスケット２６を押し込んでおく。そして、金属容器２２内において負極Ａと正極Ｃとの間に電解液（図示せず）を充填し、電解液はセパレータ２０に含浸される。   Next, the negative electrode A and the positive electrode C produced as described above are laminated with the separator 20 interposed therebetween, and have a bottomed cylindrical shape with an opening curved inward, for example, a stainless steel metal container. 22 is inserted. At this time, the gasket 26 is pushed into the outer peripheral side surface portion of the metal container 22 so that a sealed space can be formed between the negative electrode A and the positive electrode C. In the metal container 22, an electrolytic solution (not shown) is filled between the negative electrode A and the positive electrode C, and the separator 20 is impregnated with the electrolytic solution.

ここで、セパレータ２０としては、優れた高率放電性能を示す多孔膜や不織布等を、単独又は併用することができる。セパレータ２０を構成する材料としては、例えばポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−パーフルオロビニルエーテル共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−トリフルオロエチレン共重合体、フッ化ビニリデン−フルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロアセトン共重合体、フッ化ビニリデン−エチレン共重合体、フッ化ビニリデン−プロピレン共重合体、フッ化ビニリデン−トリフルオロプロピレン共重合体、フッ化ビニリデン−テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、フッ化ビニリデン−エチレン−テトラフルオロエチレン共重合体等を挙げることができる。   Here, as the separator 20, a porous film or a nonwoven fabric exhibiting excellent high rate discharge performance can be used alone or in combination. Examples of the material constituting the separator 20 include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride. Perfluorovinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-fluoroethylene copolymer, vinylidene fluoride-hexafluoroacetone copolymer, Vinylidene fluoride-ethylene copolymer, vinylidene fluoride-propylene copolymer, vinylidene fluoride-trifluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hex Hexafluoropropylene copolymers, vinylidene fluoride - ethylene - can be mentioned tetrafluoroethylene copolymer.

また、セパレータ２０には、例えばアクリロニトリル、エチレンオキシド、プロピレンオキシド、メチルメタアクリレート、ビニルアセテート、ビニルピロリドン、ポリフッ化ビニリデン等のポリマーと電解質とで構成されるポリマーゲルを用いてもよい。   For the separator 20, for example, a polymer gel composed of a polymer such as acrylonitrile, ethylene oxide, propylene oxide, methyl methacrylate, vinyl acetate, vinyl pyrrolidone, and polyvinylidene fluoride and an electrolyte may be used.

電解液としては、リチウム塩と有機溶媒とを含む従来公知の電解液を用いることができる。リチウム塩としては、例えば六フッ化リン酸リチウム（ＬｉＰＦ６）、過塩素酸リチウム（ＬｉＣｌＯ４）及びリチウムビストリフルオロメタンスルホニルイミド（ＬｉＴＦＳＩ）等が挙げられる。また、有機溶媒としては、例えば、エチレンカーボネート、ジエチレンカーボネート及びエチルメチルカーボネート等が挙げられ、これらの混合物を用いることもできる。 As the electrolytic solution, a conventionally known electrolytic solution containing a lithium salt and an organic solvent can be used. Examples of the lithium salt include lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), and lithium bistrifluoromethanesulfonylimide (LiTFSI). Examples of the organic solvent include ethylene carbonate, diethylene carbonate, and ethyl methyl carbonate, and a mixture thereof can also be used.

ガスケット２６としては、例えばポリプロピレン又はブチルゴム等の絶縁体で構成された従来公知のガスケットを用いればよい。   As the gasket 26, a conventionally known gasket made of an insulator such as polypropylene or butyl rubber may be used.

上記のように電解液を金属容器２２内に充填した後、例えばステンレス製の金属蓋２４を、ガスケット２６の内側において負極Ａ上に被せ、金属容器２２の開口部周辺部を内側にカシメ処理することにより内部封止し、このようにしてコイン型のテストセル１を作製する。   After filling the electrolytic solution into the metal container 22 as described above, for example, a stainless steel metal lid 24 is placed on the negative electrode A inside the gasket 26, and the periphery of the opening of the metal container 22 is crimped inside. Thus, the inside is sealed, and thus the coin-type test cell 1 is manufactured.

次に、隣接する線状負極活物質部１２ａの間隔Ｓ１を異なる（ｎ−１）個の値に変更する以外は、上記と同様の方法及び条件で、複数のテストセルを作製し、異なる間隔Ｓを有する線状負極活物質部１２ａを具備する（ｎ−１）個のテストセルを作製し、隣接する線状負極活物質部１２ａの間隔がＳ１〜ｎ（ｎは２以上の整数）の合計ｎ個のテストセルを作製する。 Then, except for changing the spacing S 1 between adjacent linear negative electrode active material portion 12a to a different (n-1) number of values, the same method and conditions as above to prepare a plurality of test cells, different (N-1) test cells having a linear negative electrode active material portion 12a having a spacing S are prepared, and the interval between adjacent linear negative electrode active material portions 12a is S 1 to n (n is an integer of 2 or more). N test cells in total.

（２）最適間隔決定工程
ついで、上記工程（１）で作製した種々の間隔Ｓ１〜ｎで線状負極活物質部１２ａを有するテストセルｎ個について、容量維持率を測定し、その測定結果に基づいて、間隔Ｓ１〜ｎのうちから最適（下限）間隔Ｓｘを決定する。この最適間隔Ｓｘを決定は、例えばレート特性図における間隔Ｓ１〜ｎと容量維持率との関係から、容量維持率が急激に低下する間隔の手前の間隔を最適間隔Ｓｘと決定すればよい。例えば、間隔Ｓ＝１１５μｍの容量維持率を基準とし、容量維持率が０．７５以上である場合の間隔Ｓを最適間隔Ｓｘと決定する（例えば図４の基準線Ｌを参照）。 (2) Optimal interval determination step Next, the capacity retention rate was measured for n test cells having the linear negative electrode active material portions 12a at various intervals S1 to n produced in the above step (1), and the measurement results were obtained. The optimum (lower limit) interval Sx is determined from the intervals S1 to n . The optimum interval Sx may be determined by determining, for example, the interval immediately before the interval at which the capacity maintenance rate rapidly decreases as the optimum interval Sx from the relationship between the intervals S1 to Sn in the rate characteristic diagram and the capacity maintenance rate. For example, on the basis of the capacity maintenance rate of the interval S = 115 μm, the interval S when the capacity maintenance rate is 0.75 or more is determined as the optimum interval Sx (see, for example, the reference line L in FIG. 4).

ここで、容量維持率の測定は、定電流充放電測定法により行うことができる。定電流充放電測定法は、Ｃレートを含めて種々の条件で行うことができる。なお、Ｃレートの「１Ｃ」とは、負極活物質の質量に対応した理論容量より予測した電池容量（Ａｈ）を１時間で放電できる電流量を意味し、例えば「２Ｃ」は２倍の３０分間（＝１／２時間）で放電できる電流量を、「５Ｃ」は５倍の１２分間（＝１/５時間）で放電できる電流量を、それぞれ意味する。   Here, the capacity retention rate can be measured by a constant current charge / discharge measurement method. The constant current charge / discharge measurement method can be performed under various conditions including the C rate. The C rate “1C” means the amount of current that can discharge the battery capacity (Ah) predicted from the theoretical capacity corresponding to the mass of the negative electrode active material in one hour. For example, “2C” is 30 times the amount. The amount of current that can be discharged in one minute (= 1/2 hour), and “5C” means the amount of current that can be discharged in five times 12 minutes (= 1/5 hour).

このようにして、上記工程（１）で作製したｎ個のテストセル１から、幅Ｗ及び高さＨを有する線状負極活物質部１２ａにとって最適な間隔Ｓｘを決定することができる。   In this manner, the optimum interval Sx for the linear negative electrode active material portion 12a having the width W and the height H can be determined from the n test cells 1 produced in the step (1).

（３）負極作製工程
本実施形態においては、上記工程（１）で作製したテストセル１を構成する線状負極活物質部１２ａと同じ組成を有し、かつ、例えば幅Ｗ及び高さＨを有する複数本の略平行な凸状の線状負極活物質部を、負極集電体上に最適間隔Ｓｘで形成し、負極を作製する。ここではアスペクト比は限定されないが、負極活物質材料の組成やそのアスペクト比に依存する可能性があるため、テストセルの構成に合わせてもよい。 (3) Negative electrode manufacturing process In this embodiment, it has the same composition as the linear negative electrode active material part 12a which comprises the test cell 1 manufactured at the said process (1), and has width W and height H, for example. A plurality of substantially parallel convex linear negative electrode active material portions are formed on the negative electrode current collector at an optimum interval Sx to produce a negative electrode. Although the aspect ratio is not limited here, the aspect ratio may depend on the composition of the negative electrode active material and the aspect ratio thereof, so that the aspect ratio may be adjusted.

この負極の作製は、従来公知の方法で作製することができ、例えば上記工程（１）及び工程（２）でテストセルの負極Ａを作製したのと同様に、ノズルディスペンス法により作製してもよく、また、その他のスピンコート法やスプレーコート法によって線状負極活物質部を形成してもよい。   The negative electrode can be produced by a conventionally known method. For example, the negative electrode A of the test cell can be produced by the nozzle dispensing method in the same manner as the negative electrode A of the test cell in the above steps (1) and (2). In addition, the linear negative electrode active material portion may be formed by other spin coating methods or spray coating methods.

このようにして得られる本実施形態の負極は、凸状の線状負極活物質部で構成された凹凸構造パターンの負極活物質層を有し、容量維持率を低下させずに単位面積当たりの容量を増大させたものである。かかる本実施形態の負極の製造方法は、線状負極活物質部の幅及び高さと、複数本の線状負極活物質部を形成できるスペースと、が規定されている場合に、規格容量に応じて隣接する線状負極活物質部の間隔を決定する方法として好適である。   The negative electrode of the present embodiment obtained in this way has a negative electrode active material layer having a concavo-convex structure pattern composed of convex linear negative electrode active material portions, and does not decrease the capacity retention rate per unit area. The capacity is increased. The negative electrode manufacturing method according to this embodiment is in accordance with the standard capacity when the width and height of the linear negative electrode active material part and the space in which a plurality of linear negative electrode active material parts can be formed are defined. It is suitable as a method for determining the interval between adjacent linear negative electrode active material portions.

以上の実施形態の電極製造で得られた負極を用い、リチウムイオン二次電池を作製することができる。このリチウムイオン二次電池は、電池の容量維持率を低下させずに単位面積当たりの容量を増大させたものである。このリチウムイオン二次電池は、上記の実施形態の電極製造で得られた負極を用いる以外は、従来公知の方法により作製すればよい。   A lithium ion secondary battery can be produced using the negative electrode obtained in the electrode production of the above embodiment. This lithium ion secondary battery has an increased capacity per unit area without reducing the capacity maintenance rate of the battery. This lithium ion secondary battery may be produced by a conventionally known method except that the negative electrode obtained in the electrode production of the above embodiment is used.

以上、本発明の電極の製造方法の一実施形態について説明したが、本発明はこれらのみに限定されるものではない。   As mentioned above, although one Embodiment of the manufacturing method of the electrode of this invention was described, this invention is not limited only to these.

例えば、上記実施形態においては、テストセルによって隣接する線状負極活物質部の最適な間隔を決定する場合について説明したが、隣接する線状正極活物質部の最適な間隔を決定する場合にも適用することができる。その場合、負極としては一定の組成及び寸法のものを用い、正極として一定の幅及び高さ並びに異なる間隔を有する線状正極活物質部を有する複数の正極を用い、複数のテストセルを作製すればよい。そうすれば、最適な間隔を有する線状負極活物質部を含む負極及び最適な間隔を有する線状正極活物質部を含む正極を得ることができ、当該負極及び正極を有するリチウムイオン二次電池を得ることができる。   For example, in the above-described embodiment, the case where the optimum interval between the adjacent linear negative electrode active material portions is determined by the test cell has been described, but also when the optimum interval between the adjacent linear positive electrode active material portions is determined. Can be applied. In that case, use a negative electrode having a certain composition and size, and use a plurality of positive electrodes having a linear positive electrode active material portion having a certain width and height and different intervals as the positive electrode, to produce a plurality of test cells. That's fine. Then, a negative electrode including a linear negative electrode active material portion having an optimal interval and a positive electrode including a linear positive electrode active material portion having an optimal interval can be obtained, and a lithium ion secondary battery including the negative electrode and the positive electrode Can be obtained.

また、上記実施形態においては、テストセルを、負極集電体の面上に幅Ｗ及び高さＨを有する複数本の略平行な凸状の線状負極活物質部を間隔Ｓ１〜ｎで形成して得た負極と、対極である正極と、を、セパレータを介在させて積層し、負極と正極との間に電解液を充填するとともにセパレータに電解液を含浸させ、電解質層にセパレータが含まれるような構造を有するテストセルを作製したが、セパレータの無い全固体電池型のテストセルを作製してもよい。 In the above-described embodiment, the test cell includes a plurality of substantially parallel convex linear negative electrode active material portions having a width W and a height H on the surface of the negative electrode current collector at intervals S 1 to n . The negative electrode obtained and the positive electrode as a counter electrode are stacked with a separator interposed therebetween, and an electrolyte solution is filled between the negative electrode and the positive electrode, and the separator is impregnated with the electrolyte solution. Although the test cell having the structure to be included was produced, an all-solid battery type test cell without a separator may be produced.

また、上記実施形態においては、コイン型セルを作製する場合について説明したが、テストセルとしては種々の形態のセルを作製してもよい。例えば、角型セルであっても円筒型セルであってもよい。したがって、本発明により得られるリチウムイオン二次電池も種々の形態を有し得る。また、上記実施形態においては、テストセルの対極としてリチウム金属のみからなる正極を用いたが、正極集電体と正極活物質層とで構成された正極を用いてもよく、この正極活物質層は、上記実施形態の負極活物質層と同様に、複数の凸状の線状正極活物質部で構成されていてもよい。   Moreover, although the case where a coin-type cell was produced was demonstrated in the said embodiment, you may produce a cell of a various form as a test cell. For example, it may be a square cell or a cylindrical cell. Therefore, the lithium ion secondary battery obtained by the present invention can have various forms. In the above embodiment, a positive electrode made of only lithium metal is used as the counter electrode of the test cell. However, a positive electrode composed of a positive electrode current collector and a positive electrode active material layer may be used. Like the negative electrode active material layer of the said embodiment, you may be comprised by the some convex-shaped linear positive electrode active material part.

以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらのみに限定されるものではない。   Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

（１）テストセル作製工程
質量比８：１：１の割合で、負極活物質であるチタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２、石原産業（株）製）、導電助剤であるアセチレンブラック及び結着剤であるポリフッ化ビニリデンを混合し、更に、溶剤であるＮ−メチル−２−ピロリドンを混合し、５０質量％以上の固形分濃度のスラリー状の負極活物質材料を調製した。
得られた負極活物質材料を、負極集電体であるアルミニウム箔上にノズルディスペンス法を採用したマイクロ印刷装置（大日本スクリーン製造（株）製）を用いて塗布し、８０℃で５時間以上真空乾燥することにより乾燥し、図２に示すような態様で、幅Ｗが１００μｍで高さＨが５０μｍの凸状の線状負極活物質部を間隔１１５μｍで形成し、凹凸構造を有する負極を作製した。なお、線状負極活物質部の幅Ｗ及び高さＨは、レーザー顕微鏡及び走査型電子顕微鏡を用いて観察して測定した。
上記負極と、対極であるリチウム金属からなる正極と、エチレンカーボネート及びジエチレンカーボネートの１：１（質量比）混合溶媒にＬｉＰＦ６を１ｍｏｌ／ｄｍ−３溶解させた電解液と、ポリプロピレン製のセパレータと、を用い、上記実施形態で述べた方法により図１に示す構造を有するコイン型のテストセル１を作製した。 (1) Test cell production process In a mass ratio of 8: 1: 1, lithium titanate (Li 4 Ti 5 O 12 , manufactured by Ishihara Sangyo Co., Ltd.) as a negative electrode active material, acetylene black as a conductive auxiliary agent, and Polyvinylidene fluoride as a binder was mixed, and further N-methyl-2-pyrrolidone as a solvent was mixed to prepare a slurry-like negative electrode active material having a solid content concentration of 50% by mass or more.
The obtained negative electrode active material was applied onto an aluminum foil as a negative electrode current collector using a micro printing apparatus (Dainippon Screen Mfg. Co., Ltd.) employing a nozzle dispensing method, and at 80 ° C. for 5 hours or more. A negative electrode having a concavo-convex structure is formed by drying by vacuum drying and forming convex linear negative electrode active material portions having a width W of 100 μm and a height H of 50 μm at intervals of 115 μm in the manner shown in FIG. Produced. In addition, the width W and height H of the linear negative electrode active material part were observed and measured using a laser microscope and a scanning electron microscope.
A negative electrode, a positive electrode made of lithium metal as a counter electrode, an electrolytic solution in which 1 mol / dm −3 of LiPF 6 is dissolved in a 1: 1 (mass ratio) mixed solvent of ethylene carbonate and diethylene carbonate, a polypropylene separator, The coin type test cell 1 having the structure shown in FIG. 1 was produced by the method described in the above embodiment.

次に、凸状の線状負極活物質部の間隔Ｓを、７５μｍ、５０μｍ、３０μｍ、２５μｍ又は１５μｍに変更した以外は、上記工程（１）と同様にして、コイン型のテストセル２〜６を作製した。   Next, coin-type test cells 2 to 6 are formed in the same manner as in the above step (1) except that the interval S between the convex linear negative electrode active material portions is changed to 75 μm, 50 μm, 30 μm, 25 μm, or 15 μm. Was made.

（２）最適間隔決定工程
次に、上記工程（１）で作製したテストセル１〜６の容量維持率を定電流充放電測定法により測定した。本実施例においては、充電及び放電ともに、０．１Ｃから１０ＣまでのＣレートの範囲で行い、カットオフ電圧を、充電時３Ｖ、放電時１Ｖとすることによって行った。その結果を図３のグラフに示した。図３のグラフにおいて、縦軸は容量維持率（％）を示し、横軸はＣレートを示すものとした。
本実施形態においては、図３に示すグラフに基づき、容量維持率が低下し過ぎていない範囲で最も狭い線状負極活物質部の間隔Ｓを有するテストセル４の間隔３０μｍを最適（下限）間隔Ｓｘと決定した。 (2) Optimal interval determination process Next, the capacity maintenance rate of the test cells 1 to 6 produced in the above process (1) was measured by a constant current charge / discharge measurement method. In this example, both charging and discharging were performed in a C rate range from 0.1 C to 10 C, and the cut-off voltage was set to 3 V during charging and 1 V during discharging. The results are shown in the graph of FIG. In the graph of FIG. 3, the vertical axis represents the capacity retention rate (%), and the horizontal axis represents the C rate.
In the present embodiment, based on the graph shown in FIG. 3, the optimum (lower limit) interval is set to 30 μm between the test cells 4 having the smallest interval S between the linear negative electrode active material portions in a range where the capacity retention rate does not decrease excessively. Sx was determined.

（３）負極作製工程
ついで、上記工程（１）と同様にして、負極活物質材料を負極集電体であるアルミニウム箔上に塗布、乾燥し、幅Ｗが１００μｍで高さＨが５０μｍの凸状の線状負極活物質部を間隔３０μｍで形成し、本実施例の負極を作製した。 (3) Negative electrode manufacturing step Next, in the same manner as in the above step (1), the negative electrode active material is coated on an aluminum foil as a negative electrode current collector and dried, and a convex having a width W of 100 μm and a height H of 50 μm. A linear negative electrode active material portion was formed at an interval of 30 μm to produce a negative electrode of this example.

本発明は上記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限りにおいて上述したもの以外に種々の変更を行うことが可能である。例えば、各工程において適用する塗布方法は上記に限定されるものではなく、当該工程の目的に適うものであれば他の塗布方法を適用してもよい。   The present invention is not limited to the above-described embodiment, and various modifications other than those described above can be made without departing from the spirit of the present invention. For example, the coating method applied in each step is not limited to the above, and other coating methods may be applied as long as they meet the purpose of the step.

１・・・テストセル、
Ａ・・・負極、
１０・・・負極集電体、
１２・・・負極活物質層、
１２ａ・・・線状負極活物質部、
Ｃ・・・正極、
１６・・・正極活物質層、
１６ａ・・・線状正極活物質部、
１８・・・正極集電体、
２２・・・金属蓋、
２４・・・金属容器、
２６・・・ガスケット
４０・・・ノズル。
1 ... Test cell,
A ... negative electrode,
10 ... negative electrode current collector,
12 ... negative electrode active material layer,
12a ... linear negative electrode active material part,
C: positive electrode,
16 ... positive electrode active material layer,
16a ... linear positive electrode active material part,
18 ... positive electrode current collector,
22 ... Metal lid,
24 ... Metal container,
26 ... Gasket 40 ... Nozzle.

Claims (2)

集電体及び前記集電体上に設けられた複数本の凸状の線状活物質部で形成された活物質層を有する電極の製造方法であって、
（１）集電体の面上に高さＨ及び幅Ｗを有する複数本の略平行な凸状の線状活物質部を間隔Ｓ１〜ｎ（ｎは２以上の整数）で形成して得た電極と、対極と、電解質層と、を積層した構造を有するテストセルｎ個を作製するテストセル作製工程と、
（２）前記工程（１）で作製した前記テストセルｎ個の容量維持率を測定し、測定結果に基づいて前記線状活物質部の最適間隔Ｓｘを決定する工程と、
（３）集電体の面上に複数本の略平行な凸状の線状第１活物質部を間隔Ｓｘで形成して電極を作製する工程と、
を有することを特徴とする電極の製造方法。 A method for producing an electrode having an active material layer formed of a current collector and a plurality of convex linear active material portions provided on the current collector,
(1) On the surface of the current collector, a plurality of substantially parallel convex linear active material portions having a height H and a width W are formed at intervals S 1 to n (n is an integer of 2 or more). A test cell manufacturing step of manufacturing n test cells having a structure in which the obtained electrode, a counter electrode, and an electrolyte layer are stacked;
(2) measuring the capacity retention rate of the n test cells prepared in the step (1), and determining the optimum interval Sx of the linear active material parts based on the measurement results;
(3) forming a plurality of substantially parallel convex first active material portions with a spacing Sx on the surface of the current collector; and
A method for producing an electrode, comprising: 請求項１に記載の電極の製造方法により第１電極を得る第１電極形成工程と、
第２集電体の面上に複数本の略平行な凸状の線状第２活物質部を形成して第２電極を得る第２電極形成工程と、
前記第１活物質部と前記第２活物質部とが対向するように、セパレータを介在させて前記第１電極と前記第２電極とを積層して積層体を得る積層体形成工程と、
前記第１電極と前記第２電極との間に電解液を充填するとともに前記セパレータに前記電解液を含浸させる電解液充填工程と、
を有すること、
を特徴とするリチウムイオン二次電池の製造方法。 A first electrode forming step of obtaining a first electrode by the electrode manufacturing method according to claim 1;
A second electrode forming step of obtaining a second electrode by forming a plurality of substantially parallel convex linear second active material portions on the surface of the second current collector;
A laminate forming step of obtaining a laminate by laminating the first electrode and the second electrode with a separator interposed therebetween so that the first active material portion and the second active material portion are opposed to each other;
An electrolyte filling step of filling an electrolyte between the first electrode and the second electrode and impregnating the separator with the electrolyte;
Having
A method for producing a lithium ion secondary battery.
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