JP2014078318A - Method of manufacturing lithium ion secondary battery - Google Patents

Method of manufacturing lithium ion secondary battery Download PDF

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JP2014078318A
JP2014078318A JP2012223752A JP2012223752A JP2014078318A JP 2014078318 A JP2014078318 A JP 2014078318A JP 2012223752 A JP2012223752 A JP 2012223752A JP 2012223752 A JP2012223752 A JP 2012223752A JP 2014078318 A JP2014078318 A JP 2014078318A
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active material
material layer
carbon compound
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paste
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JP5835181B2 (en
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Toshihiko Mihashi
利彦 三橋
Akihiro Ochiai
章浩 落合
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Toyota Motor Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a battery capable of preventing a first active material layer on the electrode foil side from being exposed to the surface of a negative electrode active material layer, having a first active material layer and a second active material layer of different negative electrode active material, while improving the conductivity between the first and second active material layers.SOLUTION: A method of manufacturing a lithium ion secondary battery 10 includes a step for forming a first active material layer 45z by applying a first paste 80 on an electrode foil 42 and then drying it, a step for forming a carbon compound layer 46x on the first active material layer 45z, a step for forming a second active material layer 47z by applying a second paste 86 on the carbon compound layer 46x and then drying it, and a step for subsequently carbonizing the carbon compound 85 of the carbon compound layer 46x.

Description

本発明は、電極箔とこの電極箔上に形成された負極活物質層とを有する電極板を備える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 a method for manufacturing a lithium ion secondary battery including an electrode plate having an electrode foil and a negative electrode active material layer formed on the electrode foil.

特許文献１には、リチウムイオン二次電池の負極板として、負極活物質が互いに異なる２層の活物質層を重ねて負極活物質層を形成したものが開示されている。具体的には、集電体（負極電極箔）の上に黒鉛を含む第１層（第１活物質層）を形成し、更にこの上にチタン酸リチウムを含む第２層（第２活物質層）を形成して、負極活物質層を構成する。このようにすることで、電池の端子間電圧を高くできると共に、電池の使用時や保存時に負極活物質層の表面にリチウムが析出することを抑制できる。   Patent Document 1 discloses a negative electrode plate of a lithium ion secondary battery in which a negative electrode active material layer is formed by stacking two active material layers having different negative electrode active materials. Specifically, a first layer (first active material layer) containing graphite is formed on a current collector (negative electrode electrode foil), and a second layer (second active material) containing lithium titanate is further formed thereon. Layer) to form a negative electrode active material layer. By doing in this way, while the voltage between terminals of a battery can be made high, it can suppress that lithium precipitates on the surface of a negative electrode active material layer at the time of use of a battery, and a preservation | save.

国際公開第２０１１／１１４６４１号International Publication No. 2011/114641

しかしながら、２層の活物質層を重ねて負極活物質層を形成するにあたり、２層目（第２活物質層）を形成するための第２ペーストの固形分濃度（ＮＶ）を高くし過ぎると、第２ペーストを第１活物質層上に均一な厚みに塗布するのが難しい。特に第２活物質層を薄く形成したい場合に、第２ペーストを均一かつ薄く塗布するのが難しい。
一方、第２ペーストの固形分濃度を低くし過ぎると、塗布した第２ペーストが先に形成した第１活物質層の中に染み込み易い。このため、第１活物質層全体が第２活物質層に覆われずに、第１活物質層の一部が負極活物質層の表面に露出する場合がある。すると、電池の使用時や保存時にこの露出部分においてリチウムの析出が生じ易くなる。
このように従来の電池では、電極箔上に第１活物質層を塗工し、更にこの上に第２活物質層を塗工して負極活物質層を形成する場合に、第１活物質層の一部が負極活物質層の表面に露出するのを十分に防止し難かった。 However, when forming the negative electrode active material layer by stacking two active material layers, if the solid content concentration (NV) of the second paste for forming the second layer (second active material layer) is too high, It is difficult to apply the second paste on the first active material layer in a uniform thickness. In particular, when it is desired to form the second active material layer thinly, it is difficult to apply the second paste uniformly and thinly.
On the other hand, if the solid content concentration of the second paste is too low, the applied second paste is likely to penetrate into the first active material layer formed earlier. For this reason, the entire first active material layer may not be covered with the second active material layer, and a part of the first active material layer may be exposed on the surface of the negative electrode active material layer. Then, when the battery is used or stored, lithium is liable to precipitate in the exposed portion.
Thus, in the conventional battery, when the first active material layer is applied on the electrode foil and the second active material layer is further applied thereon to form the negative electrode active material layer, the first active material is formed. It was difficult to sufficiently prevent a part of the layer from being exposed on the surface of the negative electrode active material layer.

本発明は、かかる現状に鑑みてなされたものであって、負極活物質が異なる第１活物質層及び第２活物質層を有する負極活物質層において、電極箔側の第１活物質層が負極活物質層の表面に露出するのを防止でき、しかも、第１活物質層と第２活物質層との間の導電性を改善できる電池の製造方法を提供することを目的とする。   This invention is made | formed in view of this present condition, Comprising: In the negative electrode active material layer which has the 1st active material layer and 2nd active material layer from which a negative electrode active material differs, the 1st active material layer by the side of an electrode foil is It is an object of the present invention to provide a method for manufacturing a battery that can prevent exposure to the surface of a negative electrode active material layer and can improve the conductivity between the first active material layer and the second active material layer.

上記課題を解決するための本発明の一態様は、電極箔とこの電極箔上に形成された負極活物質層とを有する電極板を備え、前記負極活物質層は、前記電極箔上に形成され、第１負極活物質を含む第１活物質層と、前記第１活物質層上に形成され、前記第１活物質よりもリチウムイオンに対する電位が高い第２負極活物質を含む第２活物質層と、を有するリチウムイオン二次電池の製造方法であって、前記電極箔上に前記第１負極活物質を含む第１ペーストを塗布し、これを乾燥させて、前記第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活物質層上に、炭素化合物からなる炭素化合物層を形成する炭素化合物層形成工程と、前記炭素化合物層上に前記第２負極活物質を含む第２ペーストを塗布し、これを乾燥させて、前記第２活物質層を形成する第２活物質層形成工程と、前記第２活物質層形成工程の後、前記炭素化合物層の前記炭素化合物を炭化させる炭化工程と、備えるリチウムイオン二次電池の製造方法である。   One embodiment of the present invention for solving the above problems includes an electrode plate having an electrode foil and a negative electrode active material layer formed on the electrode foil, and the negative electrode active material layer is formed on the electrode foil. A first active material layer including a first negative electrode active material, and a second active material formed on the first active material layer and including a second negative electrode active material having a higher potential with respect to lithium ions than the first active material. And a first paste containing the first negative electrode active material is applied to the electrode foil and dried to form the first active material layer. A first active material layer forming step of forming a carbon compound layer, a carbon compound layer forming step of forming a carbon compound layer made of a carbon compound on the first active material layer, and the second negative electrode active material on the carbon compound layer A second paste containing, and then drying the second paste. A second active material layer forming step for forming a porous layer; a carbonizing step for carbonizing the carbon compound of the carbon compound layer after the second active material layer forming step; and a method for producing a lithium ion secondary battery. is there.

このリチウムイオン二次電池の製造方法によれば、電極箔上に第１活物質層を形成した後、第２活物質層を形成するに先立って、第１活物質層上に炭素化合物からなる炭素化合物層を形成する。このため、第２活物質層は、炭素化合物層を介して第１活物質層と互いに分離して形成されるので、第２活物質層内において下層の第１活物質層が部分的に露出するのを防止できる。加えて、第１活物質層と第２活物質層との間の炭素化合物層（炭素化合物）を炭化させてできた炭は、第１活物質層と第２活物質層との間の導電性を改善できる。   According to this method for manufacturing a lithium ion secondary battery, after forming the first active material layer on the electrode foil, prior to forming the second active material layer, the first active material layer is made of a carbon compound. A carbon compound layer is formed. For this reason, since the second active material layer is formed separately from the first active material layer via the carbon compound layer, the lower first active material layer is partially exposed in the second active material layer. Can be prevented. In addition, the carbon produced by carbonizing the carbon compound layer (carbon compound) between the first active material layer and the second active material layer is conductive between the first active material layer and the second active material layer. Can improve sex.

なお、「電極板」は、負極電極箔に、負極活物質を含む負極活物質層を形成した負極板でもよいし、電極箔の一方の主面に正極活物質を含む正極活物質層を形成すると共に、他方の主面に負極活物質を含む負極活物質層を形成した双極電極板（バイポーラ電極板）でもよい。
また、「リチウムイオン二次電池」は、例えば、各々帯状をなす正極板及び負極板をセパレータを介して互いに重ねて捲回してなる捲回型の電極体を備えるものでもよいし、各々所定形状（例えば矩形状など）をなす複数の正極板及び複数の負極板をセパレータを介して交互に複数積層してなる積層型の電極体を備えるものでもよい。 The “electrode plate” may be a negative electrode plate in which a negative electrode active material layer including a negative electrode active material is formed on a negative electrode foil, or a positive electrode active material layer including a positive electrode active material is formed on one main surface of the electrode foil. In addition, a bipolar electrode plate (bipolar electrode plate) in which a negative electrode active material layer containing a negative electrode active material is formed on the other main surface may be used.
In addition, the “lithium ion secondary battery” may include, for example, a wound-type electrode body in which a positive electrode plate and a negative electrode plate each having a band shape are wound on each other via a separator, and each has a predetermined shape. A plurality of positive electrode plates (for example, a rectangular shape) and a plurality of negative electrode plates may be provided with a stacked electrode body in which a plurality of layers are alternately stacked via separators.

「炭素化合物」は、真空中や不活性雰囲気下での加熱（蒸し焼き）等により炭化させ得る化合物であり、炭素（Ｃ）のほか、水素（Ｈ）、窒素（Ｎ）、酸素（Ｏ）などを含む有機物が挙げられる。具体的には、カルボキシメチルセルロース（ＣＭＣ）、ポリエチレンオキサイド（ＰＥＯ）、ポリアクリル酸、ポリアクリル酸ナトリウムなどが挙げられる。なお、炭素化合物は、第１ペーストまたは第２ペーストに含まれる化合物を用いるのが好ましい。   “Carbon compound” is a compound that can be carbonized by heating (steaming) in a vacuum or in an inert atmosphere, and in addition to carbon (C), hydrogen (H), nitrogen (N), oxygen (O), etc. Organic substances containing Specific examples include carboxymethyl cellulose (CMC), polyethylene oxide (PEO), polyacrylic acid, and sodium polyacrylate. The carbon compound is preferably a compound contained in the first paste or the second paste.

なお、「炭素化合物層」は、例えば、後述するように、炭素化合物を含む炭素化合物ペーストを第１活物質層上に塗布し、これを乾燥させることにより形成できる。また、炭素化合物層は、粉体塗装や静電塗装などの手法で形成してもよい。   The “carbon compound layer” can be formed, for example, by applying a carbon compound paste containing a carbon compound on the first active material layer and drying it, as will be described later. The carbon compound layer may be formed by a technique such as powder coating or electrostatic coating.

更に、上記のリチウムイオン二次電池の製造方法であって、前記第１ペーストは、第１結着剤を含み、前記第２ペーストは、第２結着剤を含み、前記炭化工程は、前記第１結着剤及び前記第２結着剤のいずれの分解温度よりも低い温度で、前記炭素化合物を炭化させる工程であるリチウムイオン二次電池の製造方法とすると良い。   Furthermore, in the method for manufacturing the lithium ion secondary battery, the first paste includes a first binder, the second paste includes a second binder, and the carbonization step includes the steps of: A method for producing a lithium ion secondary battery, which is a step of carbonizing the carbon compound at a temperature lower than any decomposition temperature of the first binder and the second binder, is preferable.

このリチウムイオン二次電池の製造方法に係る炭化工程では、第１ペースト（第１活物質層）及び第２ペースト（第２活物質層）に含まれる第１結着剤及び第２結着剤のいずれの分解温度よりも低い温度で、炭素化合物層の炭素化合物を炭化させる。このため、炭化工程において第１結着剤及び第２結着剤が分解するのを防止し、第１活物質層及び第２活物質層での第１結着剤及び第２結着剤の結着作用を維持できる。   In the carbonization step according to the method for manufacturing the lithium ion secondary battery, the first binder and the second binder contained in the first paste (first active material layer) and the second paste (second active material layer). The carbon compound of the carbon compound layer is carbonized at a temperature lower than any of the decomposition temperatures. For this reason, the first binder and the second binder are prevented from being decomposed in the carbonization step, and the first binder and the second binder in the first active material layer and the second active material layer are prevented. The binding action can be maintained.

更に、上記のリチウムイオン二次電池の製造方法であって、前記第１結着剤及び前記第２結着剤は、いずれもスチレンブタジエンゴムであり、前記炭化工程は、２５０℃以下の温度で前記炭素化合物を炭化させる工程であるリチウムイオン二次電池とすると良い。   Furthermore, in the method for manufacturing a lithium ion secondary battery, the first binder and the second binder are both styrene butadiene rubber, and the carbonization step is performed at a temperature of 250 ° C. or less. A lithium ion secondary battery which is a step of carbonizing the carbon compound is preferable.

スチレンブタジエンゴム（ＳＢＲ）は、入手や取り扱いが容易であり、また、結着材としての結着作用や耐久性等が良好であることから、負極活物質層の結着剤として好適である。ＳＢＲは、３００℃で分解し始め、完全に分解する温度は５００℃以上である。これに対し、上記の製造方法では、炭化工程を２５０℃以下の温度で行うので、第１活物質層及び第２活物質層中のＳＢＲが分解するのを確実に防止できる。   Styrene butadiene rubber (SBR) is suitable as a binder for the negative electrode active material layer because it is easily available and handled, and has good binding action and durability as a binder. SBR begins to decompose at 300 ° C., and the complete decomposition temperature is 500 ° C. or higher. On the other hand, in said manufacturing method, since a carbonization process is performed at the temperature of 250 degrees C or less, it can prevent reliably that SBR in a 1st active material layer and a 2nd active material layer decomposes | disassembles.

更に、上記のいずれかに記載のリチウムイオン二次電池の製造方法であって、前記炭素化合物は、カルボキシメチルセルロースであり、前記炭化工程は、１７０℃以上の温度で前記カルボキシメチルセルロースを炭化させる工程であるリチウムイオン二次電池の製造方法とすると良い。   Furthermore, in the method for producing a lithium ion secondary battery according to any one of the above, the carbon compound is carboxymethyl cellulose, and the carbonizing step is a step of carbonizing the carboxymethyl cellulose at a temperature of 170 ° C. or higher. A method of manufacturing a certain lithium ion secondary battery is preferable.

カルボキシメチルセルロース（ＣＭＣ）は、入手や取り扱いが容易であるため、炭素化合物層を形成する材料として好適である。また、ＣＭＣは、水等の溶媒に分散させることで適切な粘度のペーストを容易に作成できるので、この炭素化合物ペーストを第１活物質層上に塗布し乾燥させることで、容易に炭素化合物層を形成できる。また、ＣＭＣは、１７０℃以上の温度で炭化させることができるので、炭化工程を容易に行うことができる。
特に、前述のように第１活物質層及び第２活物質層にＳＢＲを結着剤として用いたときに、このＳＢＲの分解温度よりも低い温度でＣＭＣを炭化させ得るので、ＳＢＲを結着剤に用いる場合に都合が良い。 Carboxymethyl cellulose (CMC) is suitable as a material for forming the carbon compound layer because it is easily available and handled. In addition, since CMC can easily create a paste having an appropriate viscosity by dispersing in a solvent such as water, the carbon compound layer can be easily applied by applying the carbon compound paste on the first active material layer and drying it. Can be formed. Moreover, since CMC can be carbonized at a temperature of 170 ° C. or higher, the carbonization process can be easily performed.
In particular, as described above, when SBR is used as a binder in the first active material layer and the second active material layer, CMC can be carbonized at a temperature lower than the decomposition temperature of the SBR. It is convenient when used as an agent.

更に、上記のいずれかに記載のリチウムイオン二次電池の製造方法であって、前記炭素化合物層形成工程は、前記第１活物質層上に前記炭素化合物を含む炭素化合物ペーストを塗布し、これを乾燥させて、前記炭素化合物層を形成する工程であり、前記炭素化合物ペーストの粘度は、６０００〜８０００ｍＰａ・ｓであるリチウムイオン二次電池の製造方法とすると良い。   Furthermore, in the method for producing a lithium ion secondary battery according to any one of the above, the carbon compound layer forming step includes applying a carbon compound paste containing the carbon compound on the first active material layer, The carbon compound layer is formed by drying, and the viscosity of the carbon compound paste is preferably a method for producing a lithium ion secondary battery having a viscosity of 6000 to 8000 mPa · s.

このリチウムイオン二次電池の製造方法では、第１活物質層上に炭素化合物を含む炭素化合物ペーストを塗布し、これを乾燥させて、炭素化合物層を形成するので、容易に炭素化合物層を形成できる。しかも、炭素化合物ペーストの粘度を、６０００〜８０００ｍＰａ・ｓとしているので、この炭素化合物ペーストを用いて、容易に均一な厚みの炭素化合物層を形成できる。   In this method of manufacturing a lithium ion secondary battery, a carbon compound paste containing a carbon compound is applied on the first active material layer and dried to form a carbon compound layer. Therefore, the carbon compound layer is easily formed. it can. Moreover, since the carbon compound paste has a viscosity of 6000 to 8000 mPa · s, a carbon compound layer having a uniform thickness can be easily formed using this carbon compound paste.

更に、上記のいずれかに記載のリチウムイオン二次電池の製造方法であって、前記第２ペーストの粘度は、６０００〜８０００ｍＰａ・ｓであるリチウムイオン二次電池の製造方法とすると良い。   Furthermore, it is a manufacturing method of the lithium ion secondary battery according to any one of the above, wherein the viscosity of the second paste is 6000 to 8000 mPa · s.

このリチウムイオン二次電池の製造方法では、第２ペーストの粘度を、６０００〜８０００ｍＰａ・ｓとしているので、この第２ペーストを用いて、容易に均一な厚みの第２活物質層を形成できる。   In this method for manufacturing a lithium ion secondary battery, the second paste has a viscosity of 6000 to 8000 mPa · s. Therefore, the second active material layer having a uniform thickness can be easily formed using the second paste.

更に、上記のいずれかに記載のリチウムイオン二次電池の製造方法であって、前記第１負極活物質は、黒鉛であり、前記第２負極活物質は、チタン酸リチウムであるリチウムイオン二次電池の製造方法とすると良い。   Furthermore, in the method for producing a lithium ion secondary battery according to any one of the above, the first negative electrode active material is graphite, and the second negative electrode active material is lithium titanate. A battery manufacturing method is preferable.

この電池の製造方法では、第１負極活物質を黒鉛としているので、特に電池容量を大きくできる。一方、第２負極活物質をチタン酸リチウム（リチウムとチタンを含む複合酸化物、以下、ＬＴＯとも言う）としているので、電池の使用時や保存時に負極活物質層の表面にリチウムが析出するのを効果的に抑制できる。   In this battery manufacturing method, since the first negative electrode active material is graphite, the battery capacity can be particularly increased. On the other hand, since the second negative electrode active material is lithium titanate (a composite oxide containing lithium and titanium, hereinafter also referred to as LTO), lithium is deposited on the surface of the negative electrode active material layer when the battery is used or stored. Can be effectively suppressed.

実施形態に係り、リチウムイオン二次電池の斜視図である。1 is a perspective view of a lithium ion secondary battery according to an embodiment. 実施形態に係り、リチウムイオン二次電池の縦断面図である。1 is a longitudinal sectional view of a lithium ion secondary battery according to an embodiment. 実施形態に係り、正極板及び負極板をセパレータを介して互いに重ねた状態を示す、電極体の展開図である。It is an expanded view of an electrode body which concerns on embodiment and shows the state which mutually accumulated the positive electrode plate and the negative electrode plate through the separator. 実施形態に係り、負極板の断面図である。It is sectional drawing of a negative electrode plate concerning embodiment. 実施形態に係り、負極電極箔上に第１活物質層を形成した様子を示す説明図である。It is explanatory drawing which shows a mode that it concerns on embodiment and the 1st active material layer was formed on negative electrode foil. 実施形態に係り、第１活物質層上に炭素化合物層を形成した様子を示す説明図である。It is explanatory drawing which shows a mode that it concerns on embodiment and the carbon compound layer was formed on the 1st active material layer. 実施形態に係り、炭素化合物層上に第２活物質層を形成した様子を示す説明図である。It is explanatory drawing which shows a mode that it concerns on embodiment and the 2nd active material layer was formed on the carbon compound layer.

以下、本発明の実施の形態を、図面を参照しつつ説明する。図１及び図２に、リチウムイオン二次電池１０（以下、単に電池１０とも言う）を示す。また、図３に、電極体３０を示し、図４に、負極板（電極板）４１を示す。なお、以下では、電池１０の厚み方向ＢＨ、幅方向ＣＨ、高さ方向ＤＨを、図１及び図２に示す方向と定めて説明する。また、図１及び図２における上方を電池１０の上側、下方を電池１０の下側として説明する。
この電池１０は、ハイブリッド自動車や電気自動車等の車両に搭載される角型の密閉型電池である。この電池１０は、直方体状の電池ケース２０と、この電池ケース２０内に収容された扁平状捲回型の電極体３０と、電池ケース２０に支持された正極端子６０及び負極端子７０等から構成されている。また、電池ケース２０内には、非水系の電解液２７が保持されている。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. 1 and 2 show a lithium ion secondary battery 10 (hereinafter also simply referred to as battery 10). 3 shows an electrode body 30, and FIG. 4 shows a negative electrode plate (electrode plate) 41. In the following description, the thickness direction BH, the width direction CH, and the height direction DH of the battery 10 are defined as the directions shown in FIGS. 1 and 2. 1 and 2 will be described as the upper side of the battery 10 and the lower side as the lower side of the battery 10.
The battery 10 is a square sealed battery mounted on a vehicle such as a hybrid vehicle or an electric vehicle. The battery 10 includes a rectangular parallelepiped battery case 20, a flat wound electrode body 30 accommodated in the battery case 20, a positive terminal 60 and a negative terminal 70 supported by the battery case 20, and the like. Has been. Further, a non-aqueous electrolyte solution 27 is held in the battery case 20.

このうち電極体３０は、その軸線（捲回軸）が電池１０の幅方向ＣＨと平行となるように横倒しにした状態で、電池ケース２０内に収容されている（図２参照）。この電極体３０は、帯状の正極板３１と帯状の負極板４１とを、樹脂製の多孔質膜からなる帯状の２枚のセパレータ５１，５１を介して互いに重ねて（図３参照）、軸線周りに捲回し、扁平状に圧縮したものである。正極板３１の幅方向の一部は、セパレータ５１，５１から軸線方向の一方側（図２中、左方、図３中、上方）に渦巻き状をなして突出しており、正極端子６０と接続（溶接）している。また、負極板４１の幅方向の一部は、セパレータ５１，５１から軸線方向の他方側（図２中、右方、図３中、下方）に渦巻き状をなして突出しており、負極端子７０と接続（溶接）している。   Among these, the electrode body 30 is accommodated in the battery case 20 in a state of being laid down so that its axis (winding axis) is parallel to the width direction CH of the battery 10 (see FIG. 2). This electrode body 30 has a belt-like positive electrode plate 31 and a belt-like negative electrode plate 41 which are stacked on each other via two belt-like separators 51 and 51 made of a resin porous film (see FIG. 3). It is wound around and compressed into a flat shape. A part of the positive electrode plate 31 in the width direction protrudes from the separators 51, 51 to one side in the axial direction (leftward in FIG. 2, upper in FIG. 3) in a spiral shape and is connected to the positive electrode terminal 60. (Welding). A part of the negative electrode plate 41 in the width direction protrudes from the separators 51, 51 in a spiral shape on the other side in the axial direction (right side in FIG. 2, downward in FIG. 3). Connected (welded).

正極板３１は、芯材として、アルミニウムからなる帯状の正極電極箔３２を有する。この正極電極箔３２の表裏面のうち幅方向（図３中、上下方向）の一部（図３中、下方）の上には、それぞれ長手方向（図３中、左右方向）に帯状に延びる正極活物質層３３，３３が形成されている。この正極活物質層３３は、正極活物質と導電材と結着剤から形成されている。本実施形態では、正極活物質としてリチウム・コバルト・ニッケル・マンガン複合酸化物、具体的にはＬｉＣｏ1/3Ｎｉ1/3Ｍｎ1/3Ｏ2 を、導電材としてカーボンブラック（ＣＢ）、具体的にはアセチレンブラック（ＡＢ）を、結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）を用いている。 The positive electrode plate 31 has a strip-shaped positive electrode foil 32 made of aluminum as a core material. Of the front and back surfaces of the positive electrode foil 32, a part of the width direction (vertical direction in FIG. 3) (downward in FIG. 3) extends in a strip shape in the longitudinal direction (horizontal direction in FIG. 3). Positive electrode active material layers 33 are formed. The positive electrode active material layer 33 is formed of a positive electrode active material, a conductive material, and a binder. In this embodiment, lithium-cobalt-nickel-manganese composite oxide as a positive electrode active material, specifically LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , carbon black (CB) as a conductive material, Specifically, acetylene black (AB) is used and polyvinylidene fluoride (PVDF) is used as a binder.

負極板（電極板）４１は、芯材として、銅からなる帯状の負極電極箔（電極箔）４２を有する。この負極電極箔４２の表裏面のうち幅方向（図３中、上下方向、図４中、左右方向）の一部（図３中、上方、図４中、左方）の上には、それぞれ長手方向（図３中、左右方向、図４中、紙面に直交する方向）に帯状に延びる負極活物質層４３，４３が形成されている。   The negative electrode plate (electrode plate) 41 has a strip-shaped negative electrode foil (electrode foil) 42 made of copper as a core material. Of the front and back surfaces of the negative electrode foil 42, a part (width in FIG. 3, upper direction, left in FIG. 4) in the width direction (in FIG. 3, up and down direction, left and right direction in FIG. 4) Negative electrode active material layers 43, 43 extending in a strip shape in the longitudinal direction (left-right direction in FIG. 3, direction orthogonal to the paper surface in FIG. 4) are formed.

この負極活物質層４３（図４参照）は、負極電極箔４２上に形成された第１活物質層４５と、この第１活物質層４５上に形成され、負極活物質層４３の表面４３ａをなす第２活物質層４７とからなり、第１活物質層４５と第２活物質層４７との境界には、後述する炭素化合物８５（具体的にはＣＭＣ）からなる炭素化合物層４６ｘを炭化して形成された炭が層状に散在する炭化部（炭）４６が存在している（なお、図４においては、表記の都合上、炭化部４６を太線で示してある）。   The negative electrode active material layer 43 (see FIG. 4) includes a first active material layer 45 formed on the negative electrode foil 42 and a surface 43a of the negative electrode active material layer 43 formed on the first active material layer 45. A carbon compound layer 46x made of a carbon compound 85 (specifically, CMC) to be described later is formed at the boundary between the first active material layer 45 and the second active material layer 47. There is a carbonized portion (charcoal) 46 in which charcoal formed by carbonization is scattered in layers (in FIG. 4, the carbonized portion 46 is indicated by a thick line for convenience of description).

このうち第１活物質層４５は、第１負極活物質８１と第１結着剤８３から構成されている。本実施形態では、第１負極活物質８１として黒鉛、具体的には天然黒鉛を、第１結着剤８３としてスチレンブタジエンゴム（ＳＢＲ）を用いている。なお、この第１活物質層４５は、後述する第１ペースト８０から形成されており、この第１ペースト８０に含まれていた第１増粘剤８２（具体的にはＣＭＣ）も、炭化して第１活物質層４５内に分散している。   Among these, the first active material layer 45 includes a first negative electrode active material 81 and a first binder 83. In the present embodiment, graphite, specifically, natural graphite is used as the first negative electrode active material 81, and styrene butadiene rubber (SBR) is used as the first binder 83. The first active material layer 45 is formed from a first paste 80 described later, and the first thickener 82 (specifically CMC) contained in the first paste 80 is also carbonized. Are dispersed in the first active material layer 45.

また、第２活物質層４７は、第２負極活物質８７と第２結着剤８９から構成されている。本実施形態では、第２負極活物質８７としてチタン酸リチウムを、第２結着剤８９としてＳＢＲを用いている。なお、この第２活物質層４７は、後述する第２ペースト８６から形成されており、この第２ペースト８６に含まれていた第２増粘剤８８（具体的にはＣＭＣ）も、炭化して第２活物質層４７内に分散している。   The second active material layer 47 includes a second negative electrode active material 87 and a second binder 89. In the present embodiment, lithium titanate is used as the second negative electrode active material 87, and SBR is used as the second binder 89. The second active material layer 47 is formed from a second paste 86 described later, and the second thickener 88 (specifically CMC) contained in the second paste 86 is also carbonized. Are dispersed in the second active material layer 47.

次いで、上記電池１０の製造方法について説明する。まず、負極板４１を製造する（図５〜図７参照）。即ち、帯状の負極電極箔４２を用意する。また、第１負極活物質（黒鉛）８１、第１増粘剤（ＣＭＣ）８２及び第１結着剤（ＳＢＲ）８３を溶媒（具体的には水）に分散させた第１ペースト８０を用意する。この第１ペースト８０の粘度は、６０００〜８０００ｍＰａ・ｓ（本実施形態では７０００ｍＰａ・ｓ）とする。なお、この第１ペースト８０の粘度、並びに、後述する炭素化合物ペースト８４の粘度及び第２ペースト８６の粘度は、いずれも、Ｂ型粘度計を用いて２５℃、２０ｒｐｍの条件で測定した。   Next, a method for manufacturing the battery 10 will be described. First, the negative electrode plate 41 is manufactured (see FIGS. 5 to 7). That is, a strip-shaped negative electrode foil 42 is prepared. Also, a first paste 80 is prepared in which a first negative electrode active material (graphite) 81, a first thickener (CMC) 82, and a first binder (SBR) 83 are dispersed in a solvent (specifically water). To do. The viscosity of the first paste 80 is 6000 to 8000 mPa · s (7000 mPa · s in this embodiment). In addition, the viscosity of this 1st paste 80, the viscosity of the carbon compound paste 84 mentioned later, and the viscosity of the 2nd paste 86 were all measured on the conditions of 25 degreeC and 20 rpm using the B-type viscosity meter.

そして、第１活物質層形成工程において、ダイコータを用いて、負極電極箔４２の一方の主面のうち幅方向の一部の上に第１ペースト８０を塗布し、これを６０℃の熱風により乾燥させて、厚み７１．５μｍの第１活物質層４５ｚを形成する（図５参照）。同様に、負極電極箔４２の反対側の主面にも、その幅方向の一部の上に第１ペースト８０を塗布し、これを６０℃の熱風により乾燥させて、厚み７１．５μｍの第１活物質層４５ｚを形成する。   Then, in the first active material layer forming step, the first paste 80 is applied on a part in the width direction on one main surface of the negative electrode foil 42 using a die coater, and this is applied by hot air at 60 ° C. By drying, a first active material layer 45z having a thickness of 71.5 μm is formed (see FIG. 5). Similarly, the first paste 80 is applied onto a main surface on the opposite side of the negative electrode foil 42 on a part in the width direction, and this is dried with hot air at 60 ° C. to obtain a 71.5 μm thick first paste. One active material layer 45z is formed.

次に、炭素化合物８５として、第１増粘剤８２及び後述する第２増粘剤８８に用いたのと同じＣＭＣを用い、これを溶媒（具体的には水）に分散させた炭素化合物ペースト８４を用意する。この炭素化合物ペースト８４の粘度は、６０００〜８０００ｍＰａ・ｓ（本実施形態では７０００ｍＰａ・ｓ）とする。そして、炭素化合物層形成工程において、ダイコータを用いて、一方の第１活物質層４５ｚの上にこの炭素化合物ペースト８４を塗布し、これを６０℃の熱風により乾燥させて、炭素化合物８５からなる炭素化合物層４６ｘを形成する（図６参照）。   Next, as the carbon compound 85, the same CMC used for the first thickener 82 and the second thickener 88 described later is used, and the carbon compound paste is dispersed in a solvent (specifically water). 84 is prepared. The viscosity of the carbon compound paste 84 is 6000 to 8000 mPa · s (7000 mPa · s in this embodiment). Then, in the carbon compound layer forming step, the carbon compound paste 84 is applied on one of the first active material layers 45z using a die coater, and is dried with hot air at 60 ° C. to form the carbon compound 85. A carbon compound layer 46x is formed (see FIG. 6).

この炭素化合物層４６ｘは、前述の第１活物質層４５ｚ（厚み７１．５μｍ）よりも薄く形成する。また、後述する第２活物質層４７ｚ（厚み５．０μｍ）以下の厚みに形成する。本実施形態では、炭素化合物層４６ｘの厚みを５．０μｍとした。
同様に、他方の第１活物質層４５ｚの上にも炭素化合物ペースト８４を塗布し、これを６０℃の熱風により乾燥させて、厚み５．０μｍの炭素化合物層４６ｘを形成する。 The carbon compound layer 46x is formed thinner than the first active material layer 45z (thickness: 71.5 μm). Moreover, it forms in the thickness below the 2nd active material layer 47z (thickness 5.0 micrometers) mentioned later. In the present embodiment, the thickness of the carbon compound layer 46x is 5.0 μm.
Similarly, the carbon compound paste 84 is applied on the other first active material layer 45z and dried with hot air at 60 ° C. to form a carbon compound layer 46x having a thickness of 5.0 μm.

次に、第２負極活物質（チタン酸リチウム）８７、第２増粘剤（ＣＭＣ）８８及び第２結着剤（ＳＢＲ）８９を溶媒（具体的には水）に分散させた第２ペースト８６を用意する。この第２ペースト８６の粘度は、６０００〜８０００ｍＰａ・ｓ（本実施形態では７０００ｍＰａ・ｓ）とする。そして、第２活物質層形成工程において、ダイコータを用いて、一方の炭素化合物層４６ｘの上にこの第２ペースト８６を塗布し、これを６０℃の熱風により乾燥させて、厚み５．０μｍの第２活物質層４７ｚを形成する（図７参照）。同様に、他方の炭素化合物層４６ｘの上にも第２ペースト８６を塗布し、これを６０℃の熱風により乾燥させて、厚み５．０μｍの第２活物質層４７ｚを形成する。   Next, a second paste in which a second negative electrode active material (lithium titanate) 87, a second thickener (CMC) 88, and a second binder (SBR) 89 are dispersed in a solvent (specifically water). 86 is prepared. The viscosity of the second paste 86 is 6000 to 8000 mPa · s (7000 mPa · s in this embodiment). Then, in the second active material layer forming step, the second paste 86 is applied on one carbon compound layer 46x using a die coater, and this is dried with hot air at 60 ° C., and the thickness is 5.0 μm. A second active material layer 47z is formed (see FIG. 7). Similarly, the second paste 86 is applied on the other carbon compound layer 46x and dried with hot air at 60 ° C. to form a second active material layer 47z having a thickness of 5.0 μm.

なお、第２活物質層４７ｚ（厚み５．０μｍ）を第１活物質層４５ｚ（厚み７１．５μｍ）に比して薄く形成するのは、第２活物質層４７ｚをなす第２負極活物質（チタン酸リチウム）８７は、不可逆容量が大きく、第２活物質層４７ｚを厚くすると電池容量が減少するため、可能な限り少なくしたいからである。
第２活物質層４７ｚ，４７ｚの形成後は、加圧ロールにより、第１活物質層４５ｚ，４５ｚ、炭素化合物層４６ｘ，４６ｘ及び第２活物質層４７ｚ，４７ｚを圧縮して、その密度を高める。なお、この加圧ロールによる圧縮は、次述する炭化工程の後に行ってもよい。 The second active material layer 47z (thickness: 5.0 μm) is formed thinner than the first active material layer 45z (thickness: 71.5 μm) because the second negative electrode active material forming the second active material layer 47z This is because (lithium titanate) 87 has a large irreversible capacity, and when the thickness of the second active material layer 47z is increased, the battery capacity is decreased.
After the formation of the second active material layers 47z and 47z, the first active material layers 45z and 45z, the carbon compound layers 46x and 46x, and the second active material layers 47z and 47z are compressed by a pressure roll to reduce the density. Increase. In addition, you may perform compression by this pressurization roll after the carbonization process described below.

次に、炭化工程において、この負極板を、窒素雰囲気下において１７０〜２５０℃（本実施形態では２００℃）で３０分以上加熱して、炭素化合物層４６ｘ，４６ｘを構成する炭素化合物（ＣＭＣ）８５を炭化させる。これにより、炭素化合物層４６ｘは、第１活物質層４５と第２活物質層４７との境界に散在する炭化部（炭）４６となる。一方、第１活物質層４５ｚ中の第１結着剤（ＳＢＲ）８３及び第２活物質層４７ｚ中の第２結着剤（ＳＢＲ）８８は、その分解開始温度が３００℃であるため、この炭化工程では分解されずにそのまま残る。なお、この炭化工程は、真空下で行ってもよい。かくして、負極板４１が形成される。   Next, in the carbonization step, the negative electrode plate is heated at 170 to 250 ° C. (200 ° C. in the present embodiment) for 30 minutes or more in a nitrogen atmosphere to form carbon compound layers (CMC) constituting the carbon compound layers 46x and 46x. 85 is carbonized. As a result, the carbon compound layer 46 x becomes carbonized portions (charcoal) 46 scattered at the boundary between the first active material layer 45 and the second active material layer 47. On the other hand, the first binder (SBR) 83 in the first active material layer 45z and the second binder (SBR) 88 in the second active material layer 47z have decomposition start temperatures of 300 ° C., In this carbonization process, it remains as it is without being decomposed. In addition, you may perform this carbonization process under a vacuum. Thus, the negative electrode plate 41 is formed.

また別途、正極板３１を製造する。即ち、帯状の正極電極箔３２を用意する。そして、ダイコータを用いて、この正極電極箔３２の一方の主面のうち幅方向の一部の上に、正極活物質、導電材及び結着剤を含む正極ペーストを塗布し、これを熱風により乾燥させて、正極活物質層を形成する（図３参照）。同様に、正極電極箔３２の反対側の主面にも、その幅方向の一部の上に上記の正極ペーストを塗布し、これを熱風により乾燥させて、正極活物質層を形成する。その後、加圧ロールにより正極活物質層を圧縮して、その密度を高める。かくして、正極板３１が形成される。   Separately, the positive electrode plate 31 is manufactured. That is, a strip-shaped positive electrode foil 32 is prepared. Then, using a die coater, a positive electrode paste containing a positive electrode active material, a conductive material, and a binder is applied to a part of one main surface of the positive electrode electrode foil 32 in the width direction, and this is heated with hot air. It is made to dry and a positive electrode active material layer is formed (refer FIG. 3). Similarly, also on the main surface on the opposite side of the positive electrode foil 32, the positive electrode paste is applied onto a part of the width direction, and this is dried with hot air to form a positive electrode active material layer. Thereafter, the positive electrode active material layer is compressed by a pressure roll to increase its density. Thus, the positive electrode plate 31 is formed.

次に、帯状のセパレータ５１を２枚用意し、前述の正極板３１と負極板４１とをセパレータ５１，５１を介して互いに重ね（図３参照）、巻き芯を用いて軸線周りに捲回する。更に、これを扁平状に圧縮して電極体３０を形成する。
また別途、電池ケース２０の矩形板状の蓋部材２３（図２参照）を用意し、この蓋部材２３に正極端子６０及び負極端子７０をそれぞれ固設しておく。その後、電池ケース２０の有底角筒状の本体部材２１を用意し、この本体部材２１内に電極体３０を収容した後、本体部材２１と蓋部材２３とをレーザ溶接して電池ケース２０を形成する。その後、電解液２７を電池ケース２０内に注液する。その後は、この電池について、初充電や各種検査を行う。かくして、電池１０が完成する。 Next, two strip-shaped separators 51 are prepared, and the above-described positive electrode plate 31 and negative electrode plate 41 are overlapped with each other through the separators 51 and 51 (see FIG. 3), and wound around the axis using a winding core. . Further, the electrode body 30 is formed by compressing it into a flat shape.
Separately, a rectangular plate-like lid member 23 (see FIG. 2) of the battery case 20 is prepared, and a positive electrode terminal 60 and a negative electrode terminal 70 are fixed to the lid member 23, respectively. Thereafter, a bottomed rectangular tube-shaped main body member 21 of the battery case 20 is prepared, and after the electrode body 30 is accommodated in the main body member 21, the main body member 21 and the lid member 23 are laser-welded to form the battery case 20. Form. Thereafter, the electrolytic solution 27 is injected into the battery case 20. Thereafter, the battery is subjected to initial charging and various inspections. Thus, the battery 10 is completed.

（実施例及び比較例）
次いで、実施形態に係る電池１０の製造方法の効果を検証するために行った試験の結果について説明する。実施例として、実施形態に係る電池１０を製造した。この電池１０の製造方法では、前述のように、負極電極箔４２上に第１活物質層４５を形成し（第１活物質層形成工程）、この上に炭素化合物層４６ｘを形成し（炭素化合物層形成工程）、更にこの上に第２活物質層４７を形成した（第２活物質層形成工程）。その後、高温加熱により炭素化合物層４６ｘを炭化させて（炭化工程）、負極活物質層４３を形成した。 (Examples and Comparative Examples)
Next, the results of tests performed to verify the effects of the method for manufacturing the battery 10 according to the embodiment will be described. As an example, the battery 10 according to the embodiment was manufactured. In the method for manufacturing the battery 10, as described above, the first active material layer 45 is formed on the negative electrode foil 42 (first active material layer forming step), and the carbon compound layer 46x is formed thereon (carbon Compound layer forming step), and further, a second active material layer 47 was formed thereon (second active material layer forming step). Thereafter, the carbon compound layer 46x was carbonized by high-temperature heating (carbonization step) to form the negative electrode active material layer 43.

Figure 2014078318
Figure 2014078318

一方、比較例１に係る電池は、実施例（実施形態）と同様に、第１活物質層形成工程、炭素化合物層形成工程、及び第２活物質層形成工程を行ったが、炭化工程は行わなかった。従って、この比較例１に係る電池では、負極活物質層内に炭素化合物層が炭化されずにそのまま残っている。
また、比較例２に係る電池は、負極電極箔上に第１活物質層を形成した後、この上に直接、第２活物質層を形成して、第１活物質層と第２活物質層からなる負極活物質層を形成した。なお、この比較例２では、炭素化合物層形成工程及び炭化工程を行っていないので、第１活物質層と第２活物質層の間には、炭化部も炭素化合物層も存在しない。
また、比較例３に係る電池は、負極電極箔上に第１活物質層を形成した後、この上に直接、第２活物質層を形成して、第１活物質層と第２活物質層とからなる負極活物質層を形成した。その後、実施例（実施形態）の炭化工程と同様に高温加熱を行った。なお、この比較例３では、炭素化合物層形成工程を行っていないので、第１活物質層と第２活物質層の間には、炭化部も炭素化合物層も存在しない。 On the other hand, the battery according to Comparative Example 1 was subjected to the first active material layer forming step, the carbon compound layer forming step, and the second active material layer forming step as in the example (embodiment). Did not do. Therefore, in the battery according to Comparative Example 1, the carbon compound layer remains as it is without being carbonized in the negative electrode active material layer.
In the battery according to Comparative Example 2, after the first active material layer is formed on the negative electrode foil, the second active material layer is directly formed thereon, and the first active material layer and the second active material are formed. A negative electrode active material layer composed of layers was formed. In Comparative Example 2, since the carbon compound layer forming step and the carbonizing step are not performed, neither the carbonized portion nor the carbon compound layer exists between the first active material layer and the second active material layer.
In the battery according to Comparative Example 3, after the first active material layer is formed on the negative electrode foil, the second active material layer is directly formed thereon, and the first active material layer and the second active material are formed. The negative electrode active material layer which consists of a layer was formed. Then, high temperature heating was performed similarly to the carbonization process of an Example (embodiment). In Comparative Example 3, since the carbon compound layer formation step is not performed, neither the carbonized portion nor the carbon compound layer exists between the first active material layer and the second active material layer.

そして、実施例及び比較例１〜３に係る各電池について、「高温保存耐久試験」を行って、試験後の容量維持率（％）を求めた。具体的には、各電池を２５℃の環境下に置いて、定電流−定電圧方式により、１Ｃの定電流で電池電圧値４．１Ｖまで充電し、更にこの電池電圧値を維持しつつ、充電電流値が０．０１Ｃに低下するまで充電を行った。その後、定電流−定電圧方式により、０．３３Ｃの定電流で電池電圧値３．０Ｖまで放電させ、更にこの電池電圧値を維持しつつ、放電電流値が０．０１Ｃに低下するまで放電を行った。そして、測定した放電容量を高温保存耐久試験前の電池容量とした。   And about each battery which concerns on an Example and Comparative Examples 1-3, the "high temperature storage durability test" was done and the capacity | capacitance maintenance factor (%) after a test was calculated | required. Specifically, each battery is placed in an environment of 25 ° C., charged to a battery voltage value of 4.1 V with a constant current of 1 C by a constant current-constant voltage method, and further maintained while maintaining this battery voltage value. Charging was performed until the charging current value decreased to 0.01C. Thereafter, the battery is discharged at a constant current of 0.33 C to a battery voltage value of 3.0 V by a constant current-constant voltage method, and further discharged while maintaining the battery voltage value until the discharge current value decreases to 0.01 C. went. And the measured discharge capacity was made into the battery capacity before a high temperature storage durability test.

次に、高温保存耐久試験を行った。具体的には、各電池をＳＯＣ９０％の状態で６０℃の環境下に６０日間静置した。その後、高温保存耐久試験前の電池容量の測定と同様にして、各電池について高温保存耐久試験後の電池容量をそれぞれ測定し、高温保存耐久試験前に対する高温保存耐久試験後の容量維持率（％）をそれぞれ算出した。   Next, a high temperature storage durability test was conducted. Specifically, each battery was allowed to stand for 60 days in an environment of 60 ° C. in an SOC of 90%. Then, in the same manner as the measurement of the battery capacity before the high temperature storage durability test, the battery capacity after the high temperature storage durability test is measured for each battery, and the capacity retention rate (% ) Respectively.

表１から明らかなように、炭素化合物層形成工程を行わなかった比較例２，３に係る各電池では、高温保存耐久試験後の容量維持率が特に低かった（いずれも８７．０％）。その理由は以下である。即ち、比較例２，３では、負極活物質層の第２活物質層を形成する際、第１活物質層上に塗布した第２ペーストが、第１活物質層の中に染み込むので、第１活物質層全体が第２活物質層に覆われずに、第１活物質層の一部が第２活物質層から露出する。その結果、比較例２，３に係る各電池では、高温保存耐久試験において、この露出部分においてリチウムの析出が多く生じ、電池容量が大きく低下したと考えられる。   As is clear from Table 1, in each battery according to Comparative Examples 2 and 3 in which the carbon compound layer forming step was not performed, the capacity retention rate after the high-temperature storage durability test was particularly low (both were 87.0%). The reason is as follows. That is, in Comparative Examples 2 and 3, when forming the second active material layer of the negative electrode active material layer, the second paste applied on the first active material layer soaks into the first active material layer. The entire first active material layer is not covered with the second active material layer, and a part of the first active material layer is exposed from the second active material layer. As a result, in each battery according to Comparative Examples 2 and 3, in the high-temperature storage endurance test, it is considered that a large amount of lithium was precipitated in this exposed portion, and the battery capacity was greatly reduced.

また、炭素化合物層を形成したが炭化工程は行わなかった比較例１に係る電池では、高温保存耐久試験後の容量維持率が低かった（８９．０％）。その理由は以下である。即ち、比較例１に係る電池では、負極活物質層において第１活物質層と第２活物質層とが炭素化合物層を介して互いに分離しており、第１活物質層はその全体が第２活物質層に覆われ、負極活物質層の表面に第１活物質層が露出していない。しかし、第１活物質層と第２活物質層との間に炭素化合物層が炭化されないまま残っているので、実施例１に係る電池に比して、第１活物質層と第２活物質層との間の導電性が低い。このため、高温保存耐久試験において、電池容量が大きく低下したと考えられる。   Further, in the battery according to Comparative Example 1 in which the carbon compound layer was formed but the carbonization step was not performed, the capacity retention rate after the high temperature storage durability test was low (89.0%). The reason is as follows. That is, in the battery according to Comparative Example 1, the first active material layer and the second active material layer are separated from each other through the carbon compound layer in the negative electrode active material layer, and the first active material layer is entirely the first active material layer. Covered with two active material layers, the first active material layer is not exposed on the surface of the negative electrode active material layer. However, since the carbon compound layer remains without being carbonized between the first active material layer and the second active material layer, the first active material layer and the second active material are compared with the battery according to Example 1. Low conductivity between layers. For this reason, it is considered that the battery capacity is greatly reduced in the high temperature storage durability test.

これらに対し、実施例に係る電池１０では、高温保存耐久試験後の容量維持率が高かった（９１．５％）。その理由は以下である。即ち、実施例に係る電池１０では、負極活物質層４３において第１活物質層４５と第２活物質層４７とが互いに分離しており、第１活物質層４５は、その全体が第２活物質層４７に覆われて露出していない。また、第１活物質層４５と第２活物質層４７との間に炭化部４６を有しているので、これらの間で導電性が高い。このため、高温保存耐久試験において、負極活物質層４３にリチウムの析出が生じ難く、電池容量の低下が抑制されたと考えられる。   On the other hand, in the battery 10 according to the example, the capacity retention rate after the high temperature storage durability test was high (91.5%). The reason is as follows. That is, in the battery 10 according to the example, the first active material layer 45 and the second active material layer 47 are separated from each other in the negative electrode active material layer 43, and the first active material layer 45 is entirely second. It is covered with the active material layer 47 and is not exposed. Further, since the carbonized portion 46 is provided between the first active material layer 45 and the second active material layer 47, the conductivity between them is high. For this reason, in the high-temperature storage durability test, it is considered that precipitation of lithium hardly occurs in the negative electrode active material layer 43, and the decrease in battery capacity is suppressed.

以上で説明したように、電池１０の製造方法によれば、負極電極箔４２上に第１活物質層４５ｚを形成した後、第２活物質層４７ｚを形成するに先立って、第１活物質層４５ｚ上に炭素化合物８５からなる炭素化合物層４６ｘを形成する。このため、第２活物質層４７ｚは、炭素化合物層４６ｘを介して第１活物質層４５ｚと互いに分離して形成されているので、第２活物質層４７内において下層の第１活物質層４５が部分的に露出するのを防止できる。加えて、第１活物質層４５と第２活物質層４７との間の炭素化合物層４６ｘ（炭素化合物８５）を炭化させてできた炭化部（炭）４６は、第１活物質層４５と第２活物質層４７との間の導電性を改善できる。   As described above, according to the method for manufacturing the battery 10, after forming the first active material layer 45z on the negative electrode foil 42, the first active material layer 47z is formed prior to forming the second active material layer 47z. A carbon compound layer 46x made of the carbon compound 85 is formed on the layer 45z. For this reason, since the second active material layer 47z is formed separately from the first active material layer 45z via the carbon compound layer 46x, the lower first active material layer 47 in the second active material layer 47 is formed. 45 can be prevented from being partially exposed. In addition, the carbonized portion (charcoal) 46 formed by carbonizing the carbon compound layer 46 x (carbon compound 85) between the first active material layer 45 and the second active material layer 47 is formed with the first active material layer 45. The conductivity with the second active material layer 47 can be improved.

更に、電池１０の製造方法では、炭化工程において、第１ペースト８０（第１活物質層４５）及び第２ペースト８６（第２活物質層４７）に含まれる第１結着剤８３及び第２結着剤８９の分解温度よりも低い温度で、炭素化合物層４６ｘの炭素化合物８５を炭化させる。具体的には、第１結着剤８３及び第２結着剤８９はＳＢＲであり、その分解が開始する温度は３００℃で、完全に分解する温度は５００℃以上である。そして、この炭化工程では、これよりも低い２００℃で炭素化合物８５を炭化させる。このため、炭化工程においてＳＢＲ８３，８９が分解するのを防止し、第１活物質層４５及び第２活物質層４７でのＳＢＲ８３，８９の結着作用を維持できる。   Furthermore, in the manufacturing method of the battery 10, in the carbonization step, the first binder 83 and the second binder included in the first paste 80 (first active material layer 45) and the second paste 86 (second active material layer 47). The carbon compound 85 of the carbon compound layer 46x is carbonized at a temperature lower than the decomposition temperature of the binder 89. Specifically, the first binder 83 and the second binder 89 are SBR, the temperature at which the decomposition starts is 300 ° C., and the temperature at which the complete decomposition is 500 ° C. or more. And in this carbonization process, the carbon compound 85 is carbonized at 200 degreeC lower than this. For this reason, it is possible to prevent the SBR 83, 89 from being decomposed in the carbonization step, and to maintain the binding action of the SBR 83, 89 in the first active material layer 45 and the second active material layer 47.

また、電池１０の製造方法では、炭素化合物層４６ｘを形成する炭素化合物８５をＣＭＣとしている。ＣＭＣ８５は、入手や取り扱いが容易であるため、炭素化合物層４６ｘを形成する材料として好適である。また、ＣＭＣ８５は、水に分散させることで適切な粘度の炭素化合物ペースト８４を容易に作成できるので、容易に炭素化合物層４６ｘを形成できる。また、ＣＭＣ８５は、１７０℃以上の温度で炭化させることができるので、炭化工程を容易に行うことができる。特に、第１活物質層４５及び第２活物質層４７にＳＢＲを結着剤８３，８９として用いたときに、このＳＢＲ８３，８９の分解温度よりも低い温度でＣＭＣを炭化させ得るので、ＳＢＲを結着剤８３，８９に用いる場合に都合が良い。   In the method for manufacturing the battery 10, the carbon compound 85 forming the carbon compound layer 46x is CMC. Since CMC85 is easily available and handled, it is suitable as a material for forming the carbon compound layer 46x. Further, the CMC 85 can easily form the carbon compound paste 84 having an appropriate viscosity by being dispersed in water, so that the carbon compound layer 46x can be easily formed. Further, since CMC85 can be carbonized at a temperature of 170 ° C. or higher, the carbonization process can be easily performed. In particular, when SBR is used as the binder 83, 89 for the first active material layer 45 and the second active material layer 47, CMC can be carbonized at a temperature lower than the decomposition temperature of the SBR 83, 89. Is convenient when used in binders 83 and 89.

また、炭素化合物層４６ｘは、第１活物質層４５ｚ上に炭素化合物８５を含む炭素化合物ペースト８４を塗布し、これを乾燥させて形成しているので、容易に炭素化合物層４６ｘを形成できる。しかも、炭素化合物ペースト８４の粘度を６０００〜８０００ｍＰａ・ｓとしているので、この炭素化合物ペースト８４を用いて、容易に均一な厚みの炭素化合物層４６ｘを形成できる。   Further, since the carbon compound layer 46x is formed by applying the carbon compound paste 84 containing the carbon compound 85 on the first active material layer 45z and drying it, the carbon compound layer 46x can be easily formed. Moreover, since the carbon compound paste 84 has a viscosity of 6000 to 8000 mPa · s, the carbon compound layer 46x having a uniform thickness can be easily formed using the carbon compound paste 84.

また、電池１０の製造方法では、第２ペースト８６の粘度を６０００〜８０００ｍＰａ・ｓとしているので、この第２ペースト８６を用いて、容易に均一な厚みの第２活物質層４７ｚを形成できる。
また、第１負極活物質８１を黒鉛としているので、特に電池容量を大きくできる。一方、第２負極活物質８７をチタン酸リチウムとしているので、電池１０の使用時や保存時に負極活物質層４３の表面４３ａにリチウムが析出するのを効果的に抑制できる。 Moreover, in the manufacturing method of the battery 10, since the viscosity of the second paste 86 is 6000 to 8000 mPa · s, the second active material layer 47z having a uniform thickness can be easily formed using the second paste 86.
In addition, since the first negative electrode active material 81 is made of graphite, the battery capacity can be particularly increased. On the other hand, since the second negative electrode active material 87 is made of lithium titanate, it is possible to effectively suppress the precipitation of lithium on the surface 43a of the negative electrode active material layer 43 when the battery 10 is used or stored.

以上において、本発明を実施形態に即して説明したが、本発明は上述の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で、適宜変更して適用できることは言うまでもない。
例えば、実施形態では、第１活物質層形成工程、炭素化合物層形成工程及び第２活物質層形成工程を行った後に、第１活物質層４５ｚ、炭素化合物層４６ｘ及び第２活物質層４７ｚをまとめて圧縮したが、これに限られない。例えば、第１活物質層形成工程で第１活物質層４５ｚを形成した後にこれを圧縮し、また、炭素化合物層形成工程で炭素化合物層４６ｘを形成した後にこれを圧縮し、更に、第２活物質層形成工程で第２活物質層４７ｚを形成した後にこれを圧縮してもよい。 In the above, the present invention has been described with reference to the embodiment. However, the present invention is not limited to the above-described embodiment, and it is needless to say that the present invention can be appropriately modified and applied without departing from the gist thereof.
For example, in the embodiment, after performing the first active material layer forming step, the carbon compound layer forming step, and the second active material layer forming step, the first active material layer 45z, the carbon compound layer 46x, and the second active material layer 47z. Are compressed together, but are not limited to this. For example, after the first active material layer 45z is formed in the first active material layer formation step, the first active material layer 45z is compressed, and after the carbon compound layer 46x is formed in the carbon compound layer formation step, the first active material layer 45z is compressed. After the second active material layer 47z is formed in the active material layer forming step, it may be compressed.

また、実施形態では、負極電極箔４２の両主面に第１活物質層４５ｚ，４５ｚを形成した後、これらの上にそれぞれ炭素化合物層４６ｘ，４６ｘを形成し、更にこれらの上にそれぞれ第２活物質層４７ｚ，４７ｚを形成したが、これに限られない。第１活物質層４５ｚ、炭素化合物層４６ｘ及び第２活物質層４７ｚは、片面ずつ形成してもよい。即ち、負極電極箔４２の一方の主面に第１活物質層４５ｚを形成した後、この上に炭素化合物層４６ｘを形成し、更にこの上に第２活物質層４７ｚを形成する。その後、負極電極箔４２の他方の主面に第１活物質層４５ｚを形成し、この上に炭素化合物層４６ｘを形成し、更にこの上に第２活物質層４７ｚを形成してもよい。この場合、炭素化合物層４６ｘを炭化させる炭化工程は、片面ずつ行ってもよいし、両面同時に行ってもよい。   Further, in the embodiment, after forming the first active material layers 45z and 45z on both main surfaces of the negative electrode foil 42, the carbon compound layers 46x and 46x are respectively formed thereon, and further the first active material layers 45x and 46x are respectively formed thereon. Although the two active material layers 47z and 47z are formed, the present invention is not limited to this. The first active material layer 45z, the carbon compound layer 46x, and the second active material layer 47z may be formed on each side. That is, after the first active material layer 45z is formed on one main surface of the negative electrode foil 42, the carbon compound layer 46x is formed thereon, and the second active material layer 47z is further formed thereon. Thereafter, the first active material layer 45z may be formed on the other main surface of the negative electrode foil 42, the carbon compound layer 46x may be formed thereon, and the second active material layer 47z may be further formed thereon. In this case, the carbonization step for carbonizing the carbon compound layer 46x may be performed on each side or on both sides simultaneously.

１０ リチウムイオン二次電池（電池）
３０ 電極体
３１ 正極板
４１ 負極板（電極板）
４２ 負極電極箔（電極箔）
４３ 負極活物質層
４３ａ （負極活物質層の）表面
４５ 第１活物質層
４５ｚ （圧縮前の）第１活物質層
４６ 炭化部
４６ｘ 炭素化合物層
４７ 第２活物質層
４７ｚ （圧縮前の）第２活物質層
５１ セパレータ
８０ 第１ペースト
８１ 第１負極活物質
８２ 第１増粘剤
８３ 第１結着剤
８４ 炭素化合物ペースト
８５ 炭素化合物
８６ 第２ペースト
８７ 第２負極活物質
８８ 第２増粘剤
８９ 第２結着剤 10 Lithium ion secondary battery (battery)
30 Electrode body 31 Positive electrode plate 41 Negative electrode plate (electrode plate)
42 Negative electrode foil (electrode foil)
43 negative electrode active material layer 43a (negative electrode active material layer) surface 45 first active material layer 45z first active material layer 46 (before compression) carbonized portion 46x carbon compound layer 47 second active material layer 47z (before compression) Second active material layer 51 Separator 80 First paste 81 First negative electrode active material 82 First thickener 83 First binder 84 Carbon compound paste 85 Carbon compound 86 Second paste 87 Second negative electrode active material 88 Second increase Adhesive 89 Second Binder

Claims (7)

電極箔とこの電極箔上に形成された負極活物質層とを有する電極板を備え、
前記負極活物質層は、
前記電極箔上に形成され、第１負極活物質を含む第１活物質層と、
前記第１活物質層上に形成され、前記第１活物質よりもリチウムイオンに対する電位が高い第２負極活物質を含む第２活物質層と、を有する
リチウムイオン二次電池の製造方法であって、
前記電極箔上に前記第１負極活物質を含む第１ペーストを塗布し、これを乾燥させて、前記第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活物質層上に、炭素化合物からなる炭素化合物層を形成する炭素化合物層形成工程と、
前記炭素化合物層上に前記第２負極活物質を含む第２ペーストを塗布し、これを乾燥させて、前記第２活物質層を形成する第２活物質層形成工程と、
前記第２活物質層形成工程の後、前記炭素化合物層の前記炭素化合物を炭化させる炭化工程と、備える
リチウムイオン二次電池の製造方法。 An electrode plate having an electrode foil and a negative electrode active material layer formed on the electrode foil,
The negative electrode active material layer is
A first active material layer formed on the electrode foil and including a first negative electrode active material;
And a second active material layer including a second negative electrode active material formed on the first active material layer and having a higher potential with respect to lithium ions than the first active material. And
A first active material layer forming step of applying a first paste containing the first negative electrode active material on the electrode foil and drying the paste to form the first active material layer;
A carbon compound layer forming step of forming a carbon compound layer made of a carbon compound on the first active material layer;
A second active material layer forming step of forming a second active material layer by applying a second paste containing the second negative electrode active material on the carbon compound layer and drying the paste;
After the second active material layer forming step, a carbonization step of carbonizing the carbon compound of the carbon compound layer, and a method of manufacturing a lithium ion secondary battery. 請求項１に記載のリチウムイオン二次電池の製造方法であって、
前記第１ペーストは、第１結着剤を含み、
前記第２ペーストは、第２結着剤を含み、
前記炭化工程は、
前記第１結着剤及び前記第２結着剤のいずれの分解温度よりも低い温度で、前記炭素化合物を炭化させる工程である
リチウムイオン二次電池の製造方法。 It is a manufacturing method of the lithium ion secondary battery according to claim 1,
The first paste includes a first binder,
The second paste includes a second binder,
The carbonization step includes
A method for producing a lithium ion secondary battery, which is a step of carbonizing the carbon compound at a temperature lower than any decomposition temperature of the first binder and the second binder. 請求項２に記載のリチウムイオン二次電池の製造方法であって、
前記第１結着剤及び前記第２結着剤は、いずれもスチレンブタジエンゴムであり、
前記炭化工程は、
２５０℃以下の温度で前記炭素化合物を炭化させる工程である
リチウムイオン二次電池。 It is a manufacturing method of the lithium ion secondary battery according to claim 2,
The first binder and the second binder are both styrene butadiene rubber,
The carbonization step includes
A lithium ion secondary battery, which is a step of carbonizing the carbon compound at a temperature of 250 ° C. or lower. 請求項１〜請求項３のいずれか一項に記載のリチウムイオン二次電池の製造方法であって、
前記炭素化合物は、カルボキシメチルセルロースであり、
前記炭化工程は、
１７０℃以上の温度で前記カルボキシメチルセルロースを炭化させる工程である
リチウムイオン二次電池の製造方法。 It is a manufacturing method of the lithium ion secondary battery as described in any one of Claims 1-3,
The carbon compound is carboxymethyl cellulose,
The carbonization step includes
The manufacturing method of the lithium ion secondary battery which is the process of carbonizing the said carboxymethylcellulose at the temperature of 170 degreeC or more. 請求項１〜請求項４のいずれか一項に記載のリチウムイオン二次電池の製造方法であって、
前記炭素化合物層形成工程は、
前記第１活物質層上に前記炭素化合物を含む炭素化合物ペーストを塗布し、これを乾燥させて、前記炭素化合物層を形成する工程であり、
前記炭素化合物ペーストの粘度は、６０００〜８０００ｍＰａ・ｓである
リチウムイオン二次電池の製造方法。 It is a manufacturing method of the lithium ion secondary battery as described in any one of Claims 1-4, Comprising:
The carbon compound layer forming step includes
Applying a carbon compound paste containing the carbon compound on the first active material layer and drying the paste to form the carbon compound layer;
The carbon compound paste has a viscosity of 6000 to 8000 mPa · s. 請求項１〜請求項５のいずれか一項に記載のリチウムイオン二次電池の製造方法であって、
前記第２ペーストの粘度は、６０００〜８０００ｍＰａ・ｓである
リチウムイオン二次電池の製造方法。 It is a manufacturing method of the lithium ion secondary battery as described in any one of Claims 1-5, Comprising:
The method for manufacturing a lithium ion secondary battery, wherein the viscosity of the second paste is 6000 to 8000 mPa · s. 請求項１〜請求項６のいずれか一項に記載のリチウムイオン二次電池の製造方法であって、
前記第１負極活物質は、黒鉛であり、
前記第２負極活物質は、チタン酸リチウムである
リチウムイオン二次電池の製造方法。 It is a manufacturing method of the lithium ion secondary battery as described in any one of Claims 1-6,
The first negative electrode active material is graphite,
The method of manufacturing a lithium ion secondary battery, wherein the second negative electrode active material is lithium titanate.
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