JP5560492B2 - Non-aqueous electrolyte secondary battery current collector and electrode using the same - Google Patents

Non-aqueous electrolyte secondary battery current collector and electrode using the same Download PDF

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JP5560492B2
JP5560492B2 JP2010124972A JP2010124972A JP5560492B2 JP 5560492 B2 JP5560492 B2 JP 5560492B2 JP 2010124972 A JP2010124972 A JP 2010124972A JP 2010124972 A JP2010124972 A JP 2010124972A JP 5560492 B2 JP5560492 B2 JP 5560492B2
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secondary battery
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sintered body
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孝二 星野
楊　　積彬
賢治 織戸
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Mitsubishi Materials 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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Description

本発明は、非水電解質二次電池用集電体およびこれを用いた電極、特に、リチウムイオン二次電池やリチウムイオンポリマー二次電池に適した金属多孔質焼結体を用いた集電体および電極に関するものである。   The present invention relates to a current collector for a nonaqueous electrolyte secondary battery and an electrode using the current collector, in particular, a current collector using a porous metal sintered body suitable for a lithium ion secondary battery or a lithium ion polymer secondary battery. And electrodes.

近年、非水電解質二次電池、中でもリチウムイオン二次電池やリチウムイオンポリマー二次電池に対して、夜間電力用のための負荷標準化（いわゆるロードレベリング）等に使用される定置型モジュール用途や、宇宙衛星用途等では、特に、高容量化、高信頼性化が求められている。   In recent years, for non-aqueous electrolyte secondary batteries, especially lithium ion secondary batteries and lithium ion polymer secondary batteries, stationary module applications used for load standardization (so-called load leveling) for night power use, In space satellite applications and the like, particularly high capacity and high reliability are required.

一般的に、リチウムイオン二次電池は、正極活物質として、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）及びこれらの固溶体であるＬｉ（Ｃｏ１−ｘＮｉｘ）Ｏ２、又はスピネル型構造を有するＬｉＭｎ２Ｏ４等のリチウム遷移金属酸化物を、負極活物質として、黒鉛等の炭素材料を用い、また、液体の有機化合物からなる溶媒とリチウム化合物からなる溶質とを非水電解質として用いている。 Generally, a lithium ion secondary battery includes, as a positive electrode active material, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and Li (Co 1-x Ni x ) O 2 that is a solid solution thereof, or A lithium transition metal oxide such as LiMn 2 O 4 having a spinel structure is used as a negative electrode active material, a carbon material such as graphite, and a solvent composed of a liquid organic compound and a solute composed of a lithium compound are non-aqueous. Used as electrolyte.

このリチウムイオン二次電池は、充電時には、正極活物質であるリチウム遷移金属酸化物中のリチウム原子（Ｌｉ）が、リチウムイオン（Ｌｉ＋）となって負極の炭素層間に挿入される（インターカレーション）。一方、放電時には、リチウムイオン（Ｌｉ＋）が、炭素層間から離脱（デインターカレーション）して正極に移動し、元の正極活物質に挿入される。このリチウムイオンの挿入脱離により充放電反応が進行している。 In this lithium ion secondary battery, during charging, lithium atoms (Li) in a lithium transition metal oxide that is a positive electrode active material are inserted between carbon layers of the negative electrode as lithium ions (Li + ) (intercalation). ) On the other hand, at the time of discharge, lithium ions (Li + ) are detached from the carbon layer (deintercalation), move to the positive electrode, and are inserted into the original positive electrode active material. The charge / discharge reaction proceeds by the insertion / extraction of lithium ions.

このようなリチウムイオン二次電池は、それぞれ、正極・負極集電体としての金属箔の上に、正極・負極活物質を塗布して、正極・負極を作製し、正極・セパレーター・負極を捲回あるいは積層して構成されている。従来、リチウムイオン二次電池は、主に、携帯電話、ノートパソコン等のポータブル機器の電源として用いられてきた。しかしながら、上述のように、近年、定置型モジュール、宇宙衛星用途等でも積極的に採用が検討されるようになり、そのような用途拡大に伴って、リチウムイオン二次電池に、特に、高容量化、高信頼性等への対応が要求されている。   In such a lithium ion secondary battery, a positive electrode / negative electrode active material is applied onto a metal foil as a positive electrode / negative electrode current collector to produce a positive electrode / negative electrode. It is configured by turning or stacking. Conventionally, lithium ion secondary batteries have been mainly used as a power source for portable devices such as mobile phones and notebook computers. However, as described above, in recent years, the adoption of stationary modules, space satellites, and the like has been actively studied, and with such expansion of use, lithium ion secondary batteries have a particularly high capacity. To meet the demands for high reliability and high reliability.

ここで、リチウムイオン二次電池の高容量化のために、正極・負極の面積を大きくすると、電極を巻回または積層するときに、小型電池の場合と比べて、製造工程が煩雑化し、製造効率が大きく低下するという問題がある。この結果、電池製造自体が困難となり、さらに、大型電池特有の異常時の大電流への安全対策も必要となる。   Here, in order to increase the capacity of the lithium ion secondary battery, if the area of the positive electrode and the negative electrode is increased, the manufacturing process becomes more complicated when winding or stacking the electrodes than in the case of a small battery. There is a problem that efficiency is greatly reduced. As a result, battery manufacture itself becomes difficult, and further, safety measures against a large current at the time of abnormality peculiar to large batteries are required.

そこで、リチウムイオン二次電池の高容量化、サイクル寿命の長期化を目的として、集電体に金属多孔体を用いるリチウムイオン二次電池が提案されている（特許文献１）。しかしながら、上記リチウムイオン二次電池では、集電体である多孔質金属の厚さが十分でない、または多孔質金属の気孔が微細ではない、という理由で、エネルギー密度を十分に高くすることができない、出力特性が劣る、という課題があることがわかった。   Therefore, a lithium ion secondary battery using a metal porous body as a current collector has been proposed for the purpose of increasing the capacity of the lithium ion secondary battery and extending the cycle life (Patent Document 1). However, in the lithium ion secondary battery, the energy density cannot be sufficiently increased because the thickness of the porous metal as the current collector is not sufficient or the pores of the porous metal are not fine. It was found that there was a problem that output characteristics were inferior.

特開２００８−１０３１６号公報JP 2008-10316 A

本発明者らは、従来と異なる多孔質金属の製造方法により、三次元網目構造の金属骨格を有し、かつ前記金属骨格間に空孔を有し、かつ電解液流通孔を有する塊状の金属多孔質焼結体を見出した。本発明は、この電解液流通孔を有する塊状の金属多孔質焼結体を、リチウムイオン二次電池をはじめとする非水電解質二次電池用集電体、およびこれを用いた電極に用いることにより、非水二次電池を高エネルギー密度化、高信頼性化させ、かつ良好な出力特性を可能にすることを目的とする。   The inventors of the present invention have used a porous metal manufacturing method different from the conventional one to form a massive metal having a metal skeleton having a three-dimensional network structure, having pores between the metal skeletons, and having electrolyte circulation holes. A porous sintered body was found. In the present invention, the massive porous metal sintered body having the electrolyte circulation hole is used for a current collector for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, and an electrode using the same. Accordingly, it is an object to increase the energy density and reliability of a non-aqueous secondary battery and to enable good output characteristics.

本発明は、以下に示す構成によって上記課題を解決した非水電解質二次電池用集電体およびこれを用いた非水電解質二次電池用電極、非水電解質二次電池に関する。
（１）電解液流通孔を有する塊状の金属多孔質焼結体を備える集電体であって、前記金属多孔質焼結体が、三次元網目構造の金属骨格を有し、かつ前記金属骨格間に空孔を有することを特徴とする、非水電解質二次電池用集電体。
（２）円柱型または角柱型である、上記（１）記載の非水電解質二次電池用集電体。
（３）上記（１）または（２）記載の集電体と、前記集電体の金属多孔質焼結体の空孔内に活物質および結合剤を含むことを特徴とする、非水電解質二次電池用電極。
（４）上記（３）記載の非水二次電池用電極を含む、非水電解質二次電池。 The present invention relates to a current collector for a non-aqueous electrolyte secondary battery that has solved the above problems with the following configuration, an electrode for a non-aqueous electrolyte secondary battery using the current collector, and a non-aqueous electrolyte secondary battery.
(1) A current collector including a massive metal porous sintered body having an electrolyte solution flow hole, wherein the metal porous sintered body has a metal skeleton having a three-dimensional network structure, and the metal skeleton A current collector for a non-aqueous electrolyte secondary battery, characterized by having pores in between.
(2) The current collector for a nonaqueous electrolyte secondary battery according to (1), wherein the current collector is a cylindrical type or a prismatic type.
(3) A nonaqueous electrolyte comprising the current collector according to (1) or (2) above and an active material and a binder in the pores of the metal porous sintered body of the current collector Secondary battery electrode.
(4) A nonaqueous electrolyte secondary battery including the electrode for a nonaqueous secondary battery according to (3) above.

本発明（１）によれば、高エネルギー密度、かつ良好な出力特性の非水電解質二次電池用電極、および非水電解質二次電池を容易に製造することができる。ここで、電解液流通孔は、Ｌｉイオンの流路を確保し、非水電解質二次電池の内部抵抗の増加を抑制することにより、良好な出力特性に寄与する。また、本発明（１）の集電体を用いることにより、非水電解質二次電池中のセパレーター体積を著しく減少させることが可能となるため、セパレーター部での短絡による顕著に不良が減少し、高信頼性にすることができる。   According to the present invention (1), it is possible to easily produce a non-aqueous electrolyte secondary battery electrode and a non-aqueous electrolyte secondary battery having high energy density and good output characteristics. Here, the electrolyte circulation hole contributes to good output characteristics by securing a flow path of Li ions and suppressing an increase in internal resistance of the nonaqueous electrolyte secondary battery. Further, by using the current collector of the present invention (1), it becomes possible to remarkably reduce the separator volume in the non-aqueous electrolyte secondary battery, so that defects due to a short circuit in the separator portion are significantly reduced. High reliability can be achieved.

本発明（２）によれば、高エネルギー密度、高信頼性、かつ良好な出力特性の非水電解質二次電池を、容易に製造することができる。   According to the present invention (2), a non-aqueous electrolyte secondary battery having high energy density, high reliability, and good output characteristics can be easily manufactured.

本発明の電解液流通孔を有する塊状の金属多孔質焼結体を備える集電体の模式図である。It is a schematic diagram of an electrical power collector provided with the massive metal porous sintered compact which has the electrolyte solution through-hole of this invention. 本発明の非水電解質二次電池の模式図である。It is a schematic diagram of the nonaqueous electrolyte secondary battery of the present invention. 試験セルで用いた外装体の模式図である。It is a schematic diagram of the exterior body used with the test cell. 従来例で作製した試験セルの断面図である。It is sectional drawing of the test cell produced by the prior art example.

以下、本発明を実施形態に基づいて具体的に説明する。なお、％は特に示さない限り、また数値固有の場合を除いて質量基準の％である。   Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated,% is% based on mass unless otherwise specified.

〔非水電解質二次電池用集電体〕
本発明の非水電解質二次電池用集電体は、電解液流通孔を有する塊状の金属多孔質焼結体を備える集電体であって、前記金属多孔質焼結体が、三次元網目構造の金属骨格を有し、かつ前記金属骨格間に空孔を有することを特徴とする。ここで、塊状とは、厚さが３ｍｍより大きいものをいい、高エネルギー密度化の観点から、５ｍｍ以上が好ましく、１０ｍｍ以上が、より好ましい。また、良好な出力特性維持の観点から、厚さは、１００ｍｍ以下が好ましい。ここで、厚さとは、セパレーターと接する面と垂直方向の長さとする。 [Current collector for non-aqueous electrolyte secondary battery]
The current collector for a non-aqueous electrolyte secondary battery of the present invention is a current collector provided with a massive metal porous sintered body having electrolyte flow holes, and the metal porous sintered body has a three-dimensional network. It has a metal skeleton having a structure, and has voids between the metal skeletons. Here, the lump means a thickness larger than 3 mm, preferably 5 mm or more, more preferably 10 mm or more from the viewpoint of increasing energy density. Further, from the viewpoint of maintaining good output characteristics, the thickness is preferably 100 mm or less. Here, the thickness is a length in a direction perpendicular to the surface in contact with the separator.

金属多孔質焼結体は、三次元網目構造の金属骨格を有し、かつ前記金属骨格間に空孔を有する。より詳しくは、金属多孔質焼結体は、三次元網目構造の金属骨格により、空孔を形成する。また、金属骨格自体も、高気孔率である。ここで、金属としては、アルミニウム、銅、ニッケルまたはこれらの合金が挙げられ、正極用集電としては、アルミニウム、特に、金属骨格にＡｌ−Ｔｉ化合物が分散しているアルミニウムが好ましく、負極用集電体としては、銅が好ましい。   The porous metal sintered body has a metal skeleton having a three-dimensional network structure and has pores between the metal skeletons. More specifically, the porous metal sintered body forms pores by a metal skeleton having a three-dimensional network structure. Also, the metal skeleton itself has a high porosity. Here, examples of the metal include aluminum, copper, nickel, and alloys thereof. As the current collector for the positive electrode, aluminum, particularly aluminum in which an Al—Ti compound is dispersed in the metal skeleton is preferable. As the electric body, copper is preferable.

金属多孔質焼結体の金属骨格は、所望の金属多孔質焼結体強度、空孔径および空孔率を得るために、金属骨格径（金属骨格を形成する各金属骨の最も細い部分の太さ）が５〜１００μｍであることが好ましい。また、この金属骨格は、孔径：０．１〜３μｍの骨格内空孔を有するものが好ましい。ここで、金属骨格径および骨格内空孔の空孔径は、骨格表面および骨格断面の走査電子顕微鏡写真により測定する。   In order to obtain a desired metal porous sintered body strength, pore diameter and porosity, the metal skeleton of the metal porous sintered body has a metal skeleton diameter (the thickness of the thinnest part of each metal bone forming the metal skeleton). Is preferably 5 to 100 μm. Further, this metal skeleton preferably has skeleton vacancies having a pore diameter of 0.1 to 3 μm. Here, the metal skeleton diameter and the pore diameter of the skeleton vacancies are measured by scanning electron micrographs of the skeleton surface and the skeleton cross section.

また、金属骨格間の空孔（以下、骨格間空孔という）は、活物質、結合剤等を含ませやすくする観点、および電解液との良好な導電性確保の観点から、連通していることが好ましい。   In addition, vacancies between metal skeletons (hereinafter referred to as inter-skeleton vacancies) communicate with each other from the viewpoint of facilitating inclusion of an active material, a binder, and the like, and ensuring good conductivity with an electrolytic solution. It is preferable.

骨格間空孔の空孔径は、所望量の活物質を充填させる観点から、２０〜５００μｍであることが好ましい。なお、圧延またはプレス等による圧密後には、骨格間空孔の空孔径は、金属多孔質焼結体の長手方向が長い楕円形状となり、長手方向の空孔径は、３０〜６００μｍであると好ましく、厚さ方向の空孔径は、１０〜２００μｍであると好ましい。ここで、空孔径は、試料の表面および断面の走査電子顕微鏡写真により測定する。   From the viewpoint of filling a desired amount of active material, the pore diameter of the inter-framework holes is preferably 20 to 500 μm. After consolidation by rolling or pressing, the pore diameter of the interstitial pores is an elliptical shape with a long longitudinal direction of the metal porous sintered body, and the pore diameter in the longitudinal direction is preferably 30 to 600 μm, The pore diameter in the thickness direction is preferably 10 to 200 μm. Here, the pore diameter is measured by scanning electron micrographs of the surface and cross section of the sample.

金属多孔質焼結体の全体気孔率は、所望量の活物質を充填させる観点から、７０〜９９％であることが好ましく、８０〜９７％であると、より好ましい。なお、圧延等後の空孔率は、５５〜９２％であると好ましく、７０〜９０％であると、より好ましい。ここで、気孔率は、金属多孔質焼結体の寸法、質量、および密度から算出する。   The total porosity of the metal porous sintered body is preferably 70 to 99%, more preferably 80 to 97%, from the viewpoint of filling a desired amount of active material. The porosity after rolling or the like is preferably 55 to 92%, and more preferably 70 to 90%. Here, the porosity is calculated from the size, mass, and density of the porous metal sintered body.

塊状の金属多孔質焼結体は、円柱型または角柱型であると、非水電解質二次電池を、容易に製造できる観点から好ましい。ここで、圧密前に、円柱型の場合には、直径が５〜２００ｍｍであると好ましく、１５〜１００ｍｍであると、より好ましい。また、角柱型の場合には、短辺が５〜２００ｍｍであると好ましく、１５〜１００ｍｍであると、より好ましい。長辺は、５〜２００ｍｍであると好ましく、１５〜１００ｍｍであると、より好ましい。なお、短辺と長辺の長さが同じ、すなわち直方体でもよい。また、エネルギー密度向上、出力特性の観点から、圧延等により、体積換算で、５〜３０％高密度化すると好ましく、８〜２５％高密度化すると、より好ましい。なお、圧延等前の厚さについては、４〜１３０ｍｍであると好ましく、７〜７０ｍｍであると、より好ましい。圧延等後の厚さについては、上述のとおりである。   The massive porous metal sintered body is preferably cylindrical or prismatic from the viewpoint of easily producing a nonaqueous electrolyte secondary battery. Here, before compaction, in the case of a cylindrical shape, the diameter is preferably 5 to 200 mm, and more preferably 15 to 100 mm. In the case of a prismatic type, the short side is preferably 5 to 200 mm, and more preferably 15 to 100 mm. The long side is preferably 5 to 200 mm, and more preferably 15 to 100 mm. The short side and the long side may have the same length, that is, a rectangular parallelepiped. Further, from the viewpoint of improving energy density and output characteristics, it is preferable to increase the density by 5 to 30% in terms of volume by rolling or the like, and more preferable to increase the density by 8 to 25%. In addition, about thickness before rolling etc., it is preferable in it being 4-130 mm, and it is more preferable in it being 7-70 mm. The thickness after rolling or the like is as described above.

図１に、電解液流通孔２を有する塊状の金属多孔質焼結体１を備える集電体の模式図を示す。電解液流通孔２は、Ｌｉイオンの流路を確保し、非水電解質二次電池の内部抵抗の増加を抑制することにより、良好な出力特性に寄与する。このため、図１のように、電解液流通孔２は、一定間隔で形成することが好ましく、また、電解液流通孔２は、厚さ方向に貫通していると好ましい。また、電解液流通孔２の直径は、０．５〜２ｍｍが好ましく、電解液流通孔２は、１〜７ｍｍ間隔で形成されることが好ましく、電解液流通孔２は、１ｃｍ２当たりに３〜９０個形成されることが好ましい。 In FIG. 1, the schematic diagram of a collector provided with the massive metal porous sintered compact 1 which has the electrolyte solution circulation hole 2 is shown. The electrolyte circulation hole 2 contributes to good output characteristics by securing a Li ion flow path and suppressing an increase in internal resistance of the nonaqueous electrolyte secondary battery. For this reason, as shown in FIG. 1, it is preferable that the electrolyte circulation holes 2 are formed at regular intervals, and the electrolyte circulation holes 2 are preferably penetrated in the thickness direction. Further, the diameter of the electrolyte circulation hole 2 is preferably 0.5 to 2 mm, the electrolyte circulation hole 2 is preferably formed at an interval of 1 to 7 mm, and the electrolyte circulation hole 2 is 3 per cm 2. It is preferable that ~ 90 are formed.

〔非水電解質二次電池用電極〕
本発明の非水電解質二次電池用電極は、上記集電体と、上記集電体の金属多孔質焼結体の空孔内に活物質および結合剤を含むことを特徴とする。 [Electrode for non-aqueous electrolyte secondary battery]
The electrode for a nonaqueous electrolyte secondary battery of the present invention is characterized in that an active material and a binder are contained in the current collector and the pores of the metal porous sintered body of the current collector.

金属多孔質焼結体の空孔内に含有される正極活物質としては、非水電解質二次電池用正極活物質として使用されるものが挙げられ、リチウムイオンを吸蔵・放出することができるものであれば、特に限定されるものではない。従来、一般的に用いられているものであればよく、具体的には、コバルト、ニッケル、マンガン、チタン、バナジウム、鉄のいずれか一種以上と、リチウムとを含む複合酸化物もしくは塩からなるのが好ましい。これにより、正極活物質が電解質に溶け出さず、大容量の電池とすることができる。   Examples of the positive electrode active material contained in the pores of the porous metal sintered body include those used as the positive electrode active material for non-aqueous electrolyte secondary batteries, and can absorb and release lithium ions. If it is, it will not specifically limit. Conventionally, any material may be used as long as it is generally used. Specifically, it is composed of a composite oxide or salt containing at least one of cobalt, nickel, manganese, titanium, vanadium and iron and lithium. Is preferred. Thereby, a positive electrode active material does not melt | dissolve in electrolyte, but it can be set as a high capacity | capacitance battery.

上記正極活物質として、より具体的には、ＬｉＣｏＯ２等のＬｉ・Ｃｏ系複合酸化物、ＬｉＮｉＯ２等のＬｉ・Ｎｉ系複合酸化物、スピネルＬｉＭｎ２Ｏ４等のＬｉ・Ｍｎ系複合酸化物、ＬｉＦｅＯ２等のＬｉ・Ｆｅ系複合酸化物、ＬｉＦｅＰＯ４等の遷移金属とリチウムのリン酸化合物や硫酸化合物等が挙げられる。この他にも、Ｖ２Ｏ５、ＭｎＯ２、ＴｉＳ２、ＭｏＳ２、ＭｏＯ３等の遷移金属酸化物や硫化物；ＰｂＯ２、ＡｇＯ、ＮｉＯＯＨ等も用いることができる。この活物質は、平均粒子径が２〜２０μｍの粉末であると、非水電解質二次電池の出力特性の観点から好ましい。ここで、平均粒子径は、レーザー回折法によって測定する。 It said as a positive electrode active material, more specifically, Li · Co-based composite oxide such as LiCoO 2, Li · Ni-based composite oxide such as LiNiO 2, Li · Mn-based composite oxide such as spinel LiMn 2 O 4 And Li · Fe-based composite oxides such as LiFeO 2 and transition metal and lithium phosphate compounds such as LiFePO 4 and sulfuric acid compounds. In addition, transition metal oxides and sulfides such as V 2 O 5 , MnO 2 , TiS 2 , MoS 2 , and MoO 3 ; PbO 2 , AgO, NiOOH, and the like can also be used. This active material is preferably a powder having an average particle size of 2 to 20 μm from the viewpoint of output characteristics of the nonaqueous electrolyte secondary battery. Here, the average particle diameter is measured by a laser diffraction method.

金属多孔質焼結体の空孔内に含有される負極活物質としては、炭素材料、Ｓｉ系材料、Ｓｎ系材料が好ましく、炭素材料としては、石油系コークス；人造黒鉛、天然黒鉛等のグラファイト；グラファイト化メソフェーズ小球体等の炭素質材料が好ましい。炭素材料としては、平均粒子径が２〜２０μｍの粉末であり、Ｓｉ系材料、Ｓｎ系材料としては、平均粒子径が０．０２〜２０μｍの粉末であると、非水電解質二次電池の出力特性の観点から好ましい。ここで、平均粒子径は、レーザー回折法によって測定する。   The negative electrode active material contained in the pores of the porous metal sintered body is preferably a carbon material, a Si-based material, or a Sn-based material. As the carbon material, petroleum-based coke; graphite such as artificial graphite or natural graphite Carbonaceous materials such as graphitized mesophase microspheres are preferred. The carbon material is a powder having an average particle diameter of 2 to 20 μm, and the Si-based material and the Sn-based material are powders having an average particle diameter of 0.02 to 20 μm, the output of the nonaqueous electrolyte secondary battery It is preferable from the viewpoint of characteristics. Here, the average particle diameter is measured by a laser diffraction method.

金属多孔質焼結体の空孔に含有される結合剤としては、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）、ＳＢＲ、ポリイミド等が挙げられるが、これらに限定されない。   Examples of the binder contained in the pores of the porous metal sintered body include, but are not limited to, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), SBR, and polyimide.

金属多孔質焼結体１００質量部に対して、活物質を１００〜８００質量部含むと、非水電解質二次電池のエネルギー密度向上の観点から好ましく、２５０〜７５０質量部含むとより好ましい。ここで、活物質の定量分析は、ＩＣＰ法で行う。   When 100 to 800 parts by mass of the active material is included with respect to 100 parts by mass of the porous metal sintered body, it is preferable from the viewpoint of improving the energy density of the nonaqueous electrolyte secondary battery, and more preferably 250 to 750 parts by mass. Here, the quantitative analysis of the active material is performed by the ICP method.

金属多孔質焼結体１００質量部に対して、結合剤を２〜８０質量部含むと、金属多孔質焼結体の空孔内に活物質を適切に保持し、活物質の欠落を防止する観点から好ましい。   When the binder is included in an amount of 2 to 80 parts by mass with respect to 100 parts by mass of the metal porous sintered body, the active material is appropriately held in the pores of the metal porous sintered body and the loss of the active material is prevented. It is preferable from the viewpoint.

また、金属多孔質焼結体の空孔内には導電助剤を含有させてもよく、導電助剤としては、例えば、カーボンブラック、アセチレンブラック、ケッチェンブラック等を挙げることができるが、これらに限定されない。   In addition, a conductive assistant may be contained in the pores of the porous metal sintered body, and examples of the conductive assistant include carbon black, acetylene black, and ketjen black. It is not limited to.

金属多孔質焼結体１００質量部に対して、導電助剤を１〜１００質量部含むと、非水電解質二次電池の出力特性、および活物質の欠落を防止する観点から好ましい。   It is preferable that 1 to 100 parts by mass of a conductive additive is included with respect to 100 parts by mass of the metal porous sintered body from the viewpoint of preventing output characteristics of the nonaqueous electrolyte secondary battery and loss of the active material.

なお、本発明においては、金属多孔質焼結体の空孔内に、活物質および結合剤が含まれているが、集電体である金属多孔質焼結体とセパレーター間にも、活物質および結合剤が含まれ得る。本発明においては、非水電解質二次電池内の活物質および結合剤の合計１００質量部に対して、金属多孔質焼結体の空孔内に含まれる活物質および結合剤が６０〜９５質量部であると、非水電解質二次電池の信頼性およびエネルギー密度の向上、出力特性の観点から好ましい。   In the present invention, the active material and the binder are contained in the pores of the porous metal sintered body. However, the active material is also interposed between the porous metal sintered body that is a current collector and the separator. And binders may be included. In the present invention, the active material and the binder contained in the pores of the porous metal sintered body are 60 to 95 mass with respect to a total of 100 parts by mass of the active material and the binder in the nonaqueous electrolyte secondary battery. Is preferable from the viewpoints of the reliability and energy density of the nonaqueous electrolyte secondary battery and the output characteristics.

本発明の非水電解質二次電池用電極を使用するときの非水電解質としては、液状電解質（電解液）、固体電解質、高分子ゲル電解質のいずれであってもよい。非水電解質は、好ましい一例を以下に示すが、通常の二次電池で用いられるものであればよく、特に限定されない。   The nonaqueous electrolyte when using the electrode for a nonaqueous electrolyte secondary battery of the present invention may be any of a liquid electrolyte (electrolyte), a solid electrolyte, and a polymer gel electrolyte. The nonaqueous electrolyte is not particularly limited as long as it is used in a normal secondary battery, although a preferred example is shown below.

電解液としては、ＬｉＢＯＢ（リチウムビスオキサイドボレート）、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＴａＦ６、ＬｉＡｌＣｌ４、Ｌｉ２Ｂ１０Ｃｌ１０等の無機酸陰イオン塩、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ等の有機酸陰イオン塩の中から選ばれる、少なくとも１種の電解質塩を含み、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）等の環状カーボネート類；ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート等の鎖状カーボネート類；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、１，２−ジブトキシエタン等のエーテル類；γ−ブチロラクトン等のラクトン類；アセトニトリル等のニトリル類；プロピオン酸メチル等のエステル類；ジメチルホルムアミド等のアミド類；酢酸メチル、蟻酸メチルの中から選ばれる少なくとも１種を混合した、非プロトン性溶媒等の有機溶媒（可塑剤）を用いたもの等が使用できる。 As an electrolytic solution, LiBOB (lithium bis oxide borate), LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiTaF 6, LiAlCl 4, Li 2 B 10 inorganic acid anion salts 10 such as Cl, LiCF 3 SO 3, It contains at least one electrolyte salt selected from organic acid anion salts such as Li (CF 3 SO 2 ) 2 N and Li (C 2 F 5 SO 2 ) 2 N, and includes propylene carbonate (PC), ethylene Cyclic carbonates such as carbonate (EC); chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2- Ethers such as dibutoxyethane; Lactones such as tyrolactone; nitriles such as acetonitrile; esters such as methyl propionate; amides such as dimethylformamide; aprotic solvents, etc. mixed with at least one selected from methyl acetate and methyl formate Those using an organic solvent (plasticizer) can be used.

固体電解質としては、イオン伝導性を有する固体から構成されるものであれば特に限定されない。例えば、無機系の固体電解質であれば、チオリシコンやＬｉ４ＳｉＯ４−Ｌｉ３ＢＯ３やＬｉＸ−Ｌｉ２Ｏ−ＭｍＯｎ（Ｘ＝Ｉ，Ｂｒ，Ｃｌ；Ｍ＝Ｂ，Ｓｉ，Ｐ等、ｍ，ｎは１〜５の数である）等のリチウムイオン導電性ガラス等が挙げられ、高分子系の固体電解質であれば、ポリエチレンオキシド（ＰＥＯ）、ポリプロピレンオキシド（ＰＰＯ）、これらの共重合体等が挙げられる。ポリアルキレンオキシド系高分子は、上述した電解質塩をよく溶解し、また、架橋構造を形成することによって、優れた機械的強度が発現する。 The solid electrolyte is not particularly limited as long as it is composed of a solid having ion conductivity. For example, in the case of an inorganic solid electrolyte, thiolithicone, Li 4 SiO 4 —Li 3 BO 3 , LiX—Li 2 O—MmOn (X = I, Br, Cl; M = B, Si, P, etc., m, (wherein n is a number from 1 to 5), and the like. Examples of the polymer solid electrolyte include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof. Is mentioned. A polyalkylene oxide polymer exhibits excellent mechanical strength by dissolving the above-described electrolyte salt well and forming a crosslinked structure.

高分子ゲル電解質としては、特に限定されないが、イオン伝導性を有する電解質用高分子に電解液を含んだもの、イオン伝導性を持たない電解質用高分子の骨格中に同様の電解液を保持させたもの等が挙げられる。   The polymer gel electrolyte is not particularly limited, but the same electrolyte solution is held in the skeleton of the electrolyte polymer having an ionic conductivity or the electrolyte polymer having no ionic conductivity. And the like.

高分子ゲル電解質に含まれる電解液としては、上述したものと同様である。また、イオン伝導性を有する電解質用高分子としては、上述した固体電解質等が用いられる。   The electrolyte solution contained in the polymer gel electrolyte is the same as described above. Further, as the electrolyte polymer having ion conductivity, the above-described solid electrolyte or the like is used.

イオン伝導性を持たない電解質用高分子としては、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニリデン−ヘキサフルオロプロピレン（ＰＶＤＦ−ＨＦＰ）共重合体、ポリビニルクロライド（ＰＶＣ）、ポリアクリロニトリル（ＰＡＮ）、ポリメチルメタクリレート（ＰＭＭＡ）等のゲル化ポリマーを形成するモノマーが使用できる。ただし、これらに限定されるわけではない。なお、ＰＡＮ、ＰＭＭＡ等は、どちらかといえばイオン伝導性がほとんどない部類に入るものであるため、上記イオン伝導性を有する電解質用高分子とすることもできるが、ここでは高分子ゲル電解質に用いられるイオン伝導性を持たない電解質用高分子として例示した。   Examples of the electrolyte polymer having no ionic conductivity include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) copolymer, polyvinyl chloride (PVC), polyacrylonitrile (PAN), Monomers that form gelling polymers such as polymethyl methacrylate (PMMA) can be used. However, it is not necessarily limited to these. Note that PAN, PMMA, etc. are in a class that has almost no ionic conductivity, and therefore can be used as an electrolyte polymer having the above ionic conductivity. It was exemplified as a polymer for electrolyte that does not have ionic conductivity.

高分子ゲル電解質中の電解質用高分子（ホストポリマー）と電解液との比率（質量比）は、使用目的等に応じて決定すればよいが、２：９８〜９０：１０の範囲である。これにより、電極活物質層の外周部からの電解質の染み出しについても、絶縁層や絶縁処理部を設けることで効果的にシールすることができる。   The ratio (mass ratio) between the electrolyte polymer (host polymer) and the electrolyte solution in the polymer gel electrolyte may be determined according to the purpose of use, but is in the range of 2:98 to 90:10. Thereby, it can seal effectively also about the oozing-out of the electrolyte from the outer peripheral part of an electrode active material layer by providing an insulating layer and an insulation process part.

〔非水二次電解質二次電池〕
図２に、本発明の非水電解質二次電池の模式図を示す。図２からわかるように、塊状の金属多孔質焼結体を用いることにより、非水二次電池に占めるセパレーターの体積を著しく減少させることができる。ここで、正極１０、および負極１１からはみ出したセパレーター１２は、電池缶や電池パック等の外装体に収納されるときには、正極１０、および負極１１のいずれかの側に折りたためばよいが、デンドライトの発生する確率が高い負極１１側に折りたたむ方が、短絡をより確実に防止する観点から好ましい。また、正極１０と負極１１の体積比は、それぞれに含有される活物質量に応じて決めればよい。 [Non-aqueous secondary electrolyte secondary battery]
In FIG. 2, the schematic diagram of the nonaqueous electrolyte secondary battery of this invention is shown. As can be seen from FIG. 2, the volume of the separator occupying the non-aqueous secondary battery can be significantly reduced by using the massive metal porous sintered body. Here, the separator 12 protruding from the positive electrode 10 and the negative electrode 11 may be folded to either the positive electrode 10 or the negative electrode 11 when housed in an outer package such as a battery can or a battery pack. Folding to the negative electrode 11 side where the probability of occurrence is high is preferable from the viewpoint of more reliably preventing a short circuit. Moreover, what is necessary is just to determine the volume ratio of the positive electrode 10 and the negative electrode 11 according to the amount of active materials contained in each.

〔非水電解質二次電池用集電体の製造方法〕
金属多孔質焼結体の製造方法を、好ましい材料である、正極集電体が金属骨格にＡｌ−Ｔｉ化合物が分散しているアルミニウム、負極集電体が銅であるときについて、以下に説明する。 [Method for producing current collector for non-aqueous electrolyte secondary battery]
The manufacturing method of the metal porous sintered body will be described below as a preferable material, in which the positive electrode current collector is aluminum in which an Al—Ti compound is dispersed in a metal skeleton, and the negative electrode current collector is copper. .

金属骨格にＡｌ−Ｔｉ化合物が分散している、塊状のアルミニウム多孔質焼結体の製造方法の一例から説明する。   An example of a method for producing a massive aluminum porous sintered body in which an Al—Ti compound is dispersed in a metal skeleton will be described.

１）粘性塑性物の原料は、以下である。
Ａｌ粉末＋１〜１０質量％Ｔｉ粉末：１００質量部
ヒドロキシプロピルメチルセルロース樹脂：５〜１０質量部
水：１００質量部
界面活性剤：０．１〜１質量部 1) The raw materials for the viscous plastic material are as follows.
Al powder + 1-10 mass% Ti powder: 100 mass parts Hydroxypropyl methylcellulose resin: 5-10 mass parts Water: 100 mass parts Surfactant: 0.1-1 mass part

上記を混合し、Ｂ型粘度計を用い、回転数１００ｒｐｍで、５０，０００〜８０，０００ｃＰｓとなるようにする。   The above is mixed and a B-type viscometer is used so that the rotational speed is 100 rpm and 50,000 to 80,000 cPs.

ここで、Ａｌ粉末の平均粒子径は、好ましくは２〜２００μｍ、より好ましくは２〜１００μｍ、さらに好ましくは７μｍ〜４０μｍの範囲内のものが用いられる。ここで、平均粒子径は、レーザー回折法で測定される。   Here, the average particle diameter of the Al powder is preferably 2 to 200 μm, more preferably 2 to 100 μm, and still more preferably 7 μm to 40 μm. Here, the average particle diameter is measured by a laser diffraction method.

Ｔｉ粉末としては、金属Ｔｉ、水素化チタンを用いることができ、焼結性の観点から、水素化チタンが好ましい。また、水素化チタンの平均粒子径は、０．１（μｍ）≦ｒ≦３０（μｍ）が好ましいが、より好ましくは４（μｍ）≦ｒ≦２０（μｍ）である。水素化チタンの平均粒径が、０．１μｍより小さいと、自然発火する恐れがあり、３０μｍを超えると、焼結体に所望の強さが得られなくなるためである。水素化チタンの配合量は、１（質量％）≦Ｗ≦１０（質量％）が好ましい。１質量％よりも少ないと焼結が不十分となり、一方、焼結助剤粉末の配合比Ｗが１０質量％を超えると、焼結体が脆くなって、所望の多孔質焼結体が得られないようになるからである。   As the Ti powder, metal Ti or titanium hydride can be used, and titanium hydride is preferable from the viewpoint of sinterability. The average particle diameter of titanium hydride is preferably 0.1 (μm) ≦ r ≦ 30 (μm), more preferably 4 (μm) ≦ r ≦ 20 (μm). This is because if the average particle size of titanium hydride is smaller than 0.1 μm, spontaneous ignition may occur, and if it exceeds 30 μm, desired strength cannot be obtained in the sintered body. The blending amount of titanium hydride is preferably 1 (mass%) ≦ W ≦ 10 (mass%). When the content is less than 1% by mass, sintering becomes insufficient. On the other hand, when the blending ratio W of the sintering aid powder exceeds 10% by mass, the sintered body becomes brittle and a desired porous sintered body is obtained. Because it will not be possible.

２）成型・焼結工程は、以下である。
上記で作製した粘性塑性物を準備する。
→泡立て器で攪拌し、クリーム状にする。
→クリーム状にした粘性組成物を、型に流し込む。
→型ごと減圧できる容器に入れる。
→減圧容器ごと１〜５℃に冷却する。この工程は、凍結を速やかに行うためプレクーリングである。
→減圧して泡サイズを大きくする。このときの圧力で粘性塑性物中の孔径を制御することができる。
→減圧したまま、減圧容器ごと凍結する。
→凍結乾燥する。
→成形体を取り出す。
→ドリルで所定の電解液流通孔をあける。
→脱バインダーを、大気中、３６０〜４２０℃×１〜１０分間行う。
→焼結を、Ａｒ中、６６０〜６６５℃×１〜３０分間行う。
2) The molding / sintering process is as follows.
The viscous plastic material prepared above is prepared.
→ Stir with a whisk to make cream.
→ Pour the creamy viscous composition into the mold.
→ Place the mold in a container that can be decompressed.
→ Cool the whole decompression vessel to 1-5 ° C. This step is precooling in order to quickly freeze.
→ Depressurize to increase bubble size. The pore diameter in the viscous plastic material can be controlled by the pressure at this time.
→ Freeze the whole decompression container with decompression.
→ Freeze-dry.
→ Take out the compact.
→ Drill a predetermined electrolyte flow hole with a drill.
→ The binder is removed in the atmosphere at 360 to 420 ° C. for 1 to 10 minutes.
→ Sintering is performed in Ar at 660 to 665 ° C. for 1 to 30 minutes.

上記で用いる型は、焼結時の収縮率を考慮して、作製する。また、減圧は、０．０５〜０．５気圧で行うことが好ましい。なお、型の電解液流通孔に相当する部分に、棒状物を形成した後、クリーム状にした粘性組成物を、型に流し込んでもよい。このときの棒状物は、凍結乾燥後に、成形体から除去することができ、また、棒状物として、脱バインダー時に消失する有機物を用いることも好ましい。   The mold used above is produced in consideration of the shrinkage rate during sintering. Moreover, it is preferable to perform pressure reduction at 0.05-0.5 atmosphere. In addition, after forming a rod-shaped object in the part corresponded to the electrolyte solution circulation hole of the mold, the creamy viscous composition may be poured into the mold. The rod-shaped material at this time can be removed from the molded body after freeze-drying, and it is also preferable to use an organic material that disappears upon debinding as the rod-shaped material.

次に、塊状の銅多孔質焼結体の製造方法の一例を説明する。銅多孔質焼結体の製造方法は、焼結収縮を考慮してスラリー充填の容器寸法を変える、焼結を、還元雰囲気中、８５０〜１０５０℃で５〜３０分間行うこと以外は、上記アルミニウム多孔質焼結体の製造方法と同様である。   Next, an example of a method for producing a massive copper porous sintered body will be described. The manufacturing method of the copper porous sintered body is the above aluminum except that the container size of the slurry filling is changed in consideration of the sintering shrinkage, and the sintering is performed in a reducing atmosphere at 850 to 1050 ° C. for 5 to 30 minutes. This is the same as the method for producing the porous sintered body.

〔非水電解質二次電池用電極の製造方法〕
活物質、および結合剤、場合により導電助剤を含むスラリーは、例えば、以下のようにして得ることができる。まず、活物質、導電助剤等を均一に混合した後、有機溶媒、結合剤を加えて、スラリーとする。または、導電助剤を有機溶媒に分散した後、活物質、結合助剤を加える、あるいは、結合剤を有機溶媒に溶解、または均一に分散させ、この混合液と活物質粉末、導電助剤を混合してスラリーとする、等の方法があるが、特に限定されない。このとき、用いる装置は、プラネタリーミキサー、ボールミル、ヘンシェルミキサー等の当業者が通常使用するものでよい。ここで、有機溶媒は、次の銅多孔質焼結体を、スラリーに浸漬させる工程で、金属多孔質焼結体にスラリーが容易に浸漬できる粘度、例えば１０〜６０Ｐａ・ｓ、となるように加えることが好ましい。 [Method for producing electrode for nonaqueous electrolyte secondary battery]
The slurry containing an active material and a binder, and optionally a conductive aid can be obtained, for example, as follows. First, after an active material, a conductive additive and the like are mixed uniformly, an organic solvent and a binder are added to form a slurry. Alternatively, after dispersing the conductive aid in the organic solvent, the active material and the binding aid are added, or the binder is dissolved or uniformly dispersed in the organic solvent, and the mixture, the active material powder, and the conductive aid are added. There are methods such as mixing to form a slurry, but there is no particular limitation. At this time, the apparatus to be used may be those normally used by those skilled in the art, such as a planetary mixer, a ball mill, and a Henschel mixer. Here, the organic solvent has a viscosity at which the slurry can be easily immersed in the metal porous sintered body in the step of immersing the next copper porous sintered body in the slurry, for example, 10 to 60 Pa · s. It is preferable to add.

上記結合剤を溶解または分散させる有機溶媒としては、テトラヒドロフラン（以下、ＴＨＦという）、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、Ｎ−メチルピロリドン、アセトン、アセトニトリル、ジメチルカーボネート、酢酸エチル、酢酸ブチル等が使用できるが、乾燥により選択的にこの有機溶媒を除去するため、ＴＨＦ、アセトン等の沸点１００℃以下の揮発性の有機溶媒、あるいは結合剤の溶解能力が高いＮ−メチルピロリドンが好ましい。   Examples of the organic solvent for dissolving or dispersing the binder include tetrahydrofuran (hereinafter referred to as THF), methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, N-methylpyrrolidone, acetone, acetonitrile, dimethyl carbonate, ethyl acetate, butyl acetate, and the like. Although it can be used, in order to selectively remove this organic solvent by drying, a volatile organic solvent having a boiling point of 100 ° C. or lower such as THF or acetone, or N-methylpyrrolidone having a high ability to dissolve a binder is preferable.

次に、金属多孔質焼結体の空孔に、活物質のスラリーを充填し、乾燥する。充填させる方法は、金属多孔質焼結体を活物質のスラリーにディッピングする方法、金属多孔質焼結体の上部からスラリーを注ぐ方法等が挙げられ、さらに、２本のロール間を通したり、へらでこすったりして表面に付着した余剰の活物質のスラリーを内部に押し込むことによって、より効果的に銅多孔質焼結体の空孔に活物質を充填することができる。乾燥は、大気中で放置してもよく、乾燥機等を用いてもよい。乾燥後、金属多孔質焼結体と、活物質および結合剤等との質量比を測定し、活物質および結合剤等の質量比が低い場合には、再度、浸漬・乾燥を繰り返し、所望量とすることができる。他方、活物質および結合剤等の質量比が高い場合には、スラリーの粘性を低くして、浸漬・乾燥をやり直し、所望量とすることができる。   Next, the pores of the porous metal sintered body are filled with the slurry of the active material and dried. Examples of the filling method include a method of dipping the metal porous sintered body into the slurry of the active material, a method of pouring the slurry from the upper part of the metal porous sintered body, and further, passing between two rolls, By scraping the surplus active material slurry adhering to the surface with a spatula into the inside, the active material can be more effectively filled into the pores of the copper porous sintered body. Drying may be left in the air, or a dryer or the like may be used. After drying, the mass ratio between the porous metal sintered body and the active material and the binder is measured. If the mass ratio of the active material and the binder is low, the immersion and drying are repeated again to obtain the desired amount. It can be. On the other hand, when the mass ratio of the active material and the binder is high, the viscosity of the slurry can be lowered, and dipping and drying can be performed again to obtain a desired amount.

次に、活物質および結合剤を含む金属多孔質焼結体を、圧延またはプレスし、非水電解質二次電池用電極を得る。圧延等により金属多孔質焼結体を所望の厚さまで、圧延等することができ、電極体の空隙率を減少させ、電極密度を高めることができ、これにより非水電解質二次電池を高エネルギー密度化する。ここで、生産性の観点からは、圧延する方が好ましく、均一に高密度化させる観点からは、金型を用いたメカプレスが好ましい。   Next, the metal porous sintered body containing the active material and the binder is rolled or pressed to obtain an electrode for a nonaqueous electrolyte secondary battery. The porous metal sintered body can be rolled to a desired thickness by rolling, etc., the porosity of the electrode body can be reduced, and the electrode density can be increased, thereby making the non-aqueous electrolyte secondary battery high energy Densify. Here, rolling is preferable from the viewpoint of productivity, and a mechanical press using a die is preferable from the viewpoint of uniform densification.

本発明の非水電解質二次電池用電極は、高エネルギー密度で、高信頼性の非水電解質二次電池に、非常に有効に利用される。   The electrode for a non-aqueous electrolyte secondary battery of the present invention is very effectively used for a non-aqueous electrolyte secondary battery having high energy density and high reliability.

以下、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

〔塊状の正極集電体の作製〕
上述の実施の形態にしたがって、塊状のアルミニウム多孔質焼結体を製造した。まず、平均粒子径：２４μｍのアルミニウム粉末（不純物として、Ｆｅ：０．１５質量％、Ｓｉ：０．０５質量％およびＮｉ：０．０１質量％を含む）と、平均粒子径９．１μｍの水素化チタン粉末を、アルミニウム粉末と水素化チタン粉末の質量比が、９５：５となるように合計５００ｇで混合し、アルミニウム混合原料粉末を調製した。 (Preparation of bulk positive electrode current collector)
According to the above-described embodiment, a massive aluminum porous sintered body was manufactured. First, an aluminum powder having an average particle diameter of 24 μm (containing impurities: Fe: 0.15 mass%, Si: 0.05 mass% and Ni: 0.01 mass%), and hydrogen having an average particle diameter of 9.1 μm The titanium halide powder was mixed in a total of 500 g so that the mass ratio of the aluminum powder and the titanium hydride powder was 95: 5 to prepare an aluminum mixed raw material powder.

バインダー溶液は、ヒドロキシプロピルメチルセルロース樹脂：２５ｇ、水：５００ｇ、アルキルベタイン：１ｇで調整した。   The binder solution was adjusted with hydroxypropyl methylcellulose resin: 25 g, water: 500 g, and alkylbetaine: 1 g.

アルミニウム混合原料粉末と、バインダー溶液と、を混合して、粘性組成物を調製した。   The aluminum mixed raw material powder and the binder solution were mixed to prepare a viscous composition.

次に、この粘性組成物を、泡立て器で攪拌し、クリーム状にし、クリーム状にした粘性組成物を、内径：４０ｍｍ、高さ：１００ｍｍのポリテトラフルオロエチレン樹脂製の型に高さ：１０ｍｍに流し込んだ。その後、圧力ゲージとコック付排気口を具備したステンレス製減圧容器に入れ、前記減圧容器ごと１〜５℃に冷却した。冷却後、約０．１気圧まで減圧して、泡サイズを直径：０．５〜２ｍｍ程度まで大きくした。そして、減圧したまま、前記減圧容器ごと−２０℃に設定した冷凍機に入れて凍結した後、減圧容器から凍結した成形体を取り出し、真空乾燥機に移して減圧して、凍結乾燥した。次に、凍結乾燥した成形体を取り出し、図１に示すように、直径：１ｍｍの孔を５ｍｍ間隔で、３７個開けた後、大気中、３９０℃に５分間保持の条件で加熱して脱バインダーをした後、Ａｒ中、６６０℃に１０分間保持の条件で加熱して焼成した。得られた正極集電体１は、直径：３６ｍｍ、厚さ：４２ｍｍであった。正極集電体１を、Ｘ線回折で観察した結果、ＡｌとＡｌ３Ｔｉ化合物が確認された。 Next, the viscous composition is stirred with a whisk to form a cream, and the creamy viscous composition is placed into a polytetrafluoroethylene resin mold having an inner diameter of 40 mm and a height of 100 mm. Poured into. Then, it put into the stainless steel pressure reduction container equipped with the pressure gauge and the exhaust port with a cock, and cooled to 1-5 degreeC with the said pressure reduction container. After cooling, the pressure was reduced to about 0.1 atm to increase the bubble size to a diameter of about 0.5 to 2 mm. Then, with the pressure reduced, the whole decompression vessel was put in a freezer set to −20 ° C. and frozen, and then the frozen molded body was taken out from the pressure reduction vessel, transferred to a vacuum dryer, decompressed and freeze-dried. Next, the freeze-dried molded product was taken out and, as shown in FIG. 1, after opening 37 holes with a diameter of 1 mm at intervals of 5 mm, the product was removed by heating in the atmosphere at 390 ° C. for 5 minutes. After the binder was applied, it was baked by heating in Ar at 660 ° C. for 10 minutes. The obtained positive electrode current collector 1 had a diameter of 36 mm and a thickness of 42 mm. As a result of observing the positive electrode current collector 1 by X-ray diffraction, Al and an Al 3 Ti compound were confirmed.

〔塊状の負極集電体の作製〕
平均粒径：１２μｍの銅粉末を、正極集電体の作製方法と同様にバインダー溶液とともに攪拌してクリーム状の粘性塑性物とし、前記粘性組成部を内径：５０ｍｍ、高さ：１５０ｍｍの圧力ゲージとコック付排気口を具備したステンレス製減圧容器に入れ、正極集電体の作製方法と同様に減圧して泡サイズを大きくし、凍結し、凍結乾燥して成形体を製造し、図１に示すように、直径：１ｍｍの孔を５ｍｍ間隔で、３７個開けた後、前記成形体を同じく３９０℃に５分間保持の条件で加熱して脱バインダーをした後、５％Ｈ２−９５％Ｎ２雰囲気中、９００℃に２０分間加熱保持の条件で焼成して、塊状の銅多孔質焼結体を作製した。得られた負極集電体は、直径：３６ｍｍ、厚さ：４０ｍｍであった。 (Production of bulk negative electrode current collector)
A copper powder having an average particle diameter of 12 μm is stirred together with a binder solution in the same manner as the method for producing a positive electrode current collector to form a creamy viscous plastic material, and the viscous composition part is a pressure gauge having an inner diameter of 50 mm and a height of 150 mm. In a stainless steel vacuum vessel equipped with an exhaust port with a cock, and reduced pressure to increase the bubble size, freeze and freeze-dry in the same way as the method for producing the positive electrode current collector to produce a molded body. As shown in the drawing, after opening 37 holes with a diameter of 1 mm at intervals of 5 mm, the molded body was similarly heated at 390 ° C. for 5 minutes to remove the binder, and then 5% H 2 -95% Baking was performed in a N 2 atmosphere at 900 ° C. for 20 minutes under heating and heating to produce a massive copper porous sintered body. The obtained negative electrode current collector had a diameter of 36 mm and a thickness of 40 mm.

〔非水電解質二次電池用電極の製造〕
（実施例１） [Manufacture of electrodes for non-aqueous electrolyte secondary batteries]
Example 1

〔正極の作製〕
正極活物質としてコバルト酸リチウム（ＬｉＣｏＯ2）粉末と、導電材としてケッチェンブラック（ＫＢ）と、結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）とを、質量比８０：１０：１０で、合計２００ｇ混合して正極剤を調製し、この正極剤に溶剤としてＮ−メチル−２ピロリドン１６２ｇを混合して、正極活物質スラリーを調製した。 [Production of positive electrode]
Lithium cobalt oxide (LiCoO 2 ) powder as a positive electrode active material, ketjen black (KB) as a conductive material, and polyvinylidene fluoride (PVDF) as a binder in a mass ratio of 80:10:10, a total of 200 g A positive electrode agent was prepared, and 162 g of N-methyl-2pyrrolidone as a solvent was mixed with this positive electrode agent to prepare a positive electrode active material slurry.

次に、この正極活物質スラリーに、作製した正極集電体を１０分間浸漬し、取り出して乾燥させた後に、メカプレスして厚さ：３０ｍｍのリチウムイオン電池の正極を作製した。ここで、正極活物質スラリーに、正極集電体を浸漬し、乾燥した後、メカプレス前に、正極集電体表面に付着した正極活物質スラリーを拭き取り、ほぼ全量の正極活物質、導電助剤および結合剤が、正極集電体の空孔内に含まれるようにし、正極１０とした。   Next, the produced positive electrode current collector was immersed in this positive electrode active material slurry for 10 minutes, taken out and dried, and then mechanically pressed to produce a positive electrode of a lithium ion battery having a thickness of 30 mm. Here, after immersing the positive electrode current collector in the positive electrode active material slurry and drying, before the mechanical press, the positive electrode active material slurry adhering to the surface of the positive electrode current collector is wiped off, and almost all of the positive electrode active material and the conductive auxiliary agent In addition, the positive electrode 10 was obtained by allowing the binder to be contained in the pores of the positive electrode current collector.

〔負極の作製〕
活物質として人造黒鉛粉末と、結合剤としてポリフッ化ビニリデン（ＰＶＤＦ）とを、質量比９０：１０で、合計２００ｇ混合して負極剤を調製し、この負極剤に溶剤としてＮ−メチル−２ピロリドン１６２ｇを混合して負極活物質スラリーを調製した。 (Production of negative electrode)
Artificial graphite powder as an active material and polyvinylidene fluoride (PVDF) as a binder are mixed at a mass ratio of 90:10 in a total of 200 g to prepare a negative electrode agent, and N-methyl-2-pyrrolidone as a solvent in this negative electrode agent 162 g was mixed to prepare a negative electrode active material slurry.

次に、この負極活物質スラリーに、作製した負極集電体を１０分間浸漬し、取り出して乾燥させた後に、メカプレスして厚さ：３０ｍｍの実施例１のリチウムイオン電池の負極を作製した。ここで、負極活物質スラリーに、負極集電体を浸漬し、乾燥した後、メカプレス前に、負極集電体表面に付着した負極活物質スラリーを拭き取り、ほぼ全量の活物質、導電助剤および結合剤が、負極集電体の空孔内に含まれるようにし、負極１１とした。   Next, the produced negative electrode current collector was immersed in this negative electrode active material slurry for 10 minutes, taken out and dried, and then mechanically pressed to produce a negative electrode of the lithium ion battery of Example 1 having a thickness of 30 mm. Here, after the negative electrode current collector is immersed in the negative electrode active material slurry and dried, before the mechanical press, the negative electrode active material slurry adhering to the surface of the negative electrode current collector is wiped off, and almost all of the active material, the conductive additive and The binder was included in the pores of the negative electrode current collector to obtain the negative electrode 11.

〔試験セルの作製〕
非水電解質二次電池の試験セルを作製した。正極１０の上面又は下面の中央部１箇所に、アルミニウム製の正極集電タブ１０ａを溶接した。また、負極１１の上面又は下面の中央部１箇所に、ニッケル製の負極集電タブ１１ａを溶接した。 [Production of test cell]
A test cell of a nonaqueous electrolyte secondary battery was produced. An aluminum positive electrode current collecting tab 10 a was welded to one central portion of the upper surface or the lower surface of the positive electrode 10. Further, a negative electrode current collecting tab 11 a made of nickel was welded to one central portion of the upper surface or the lower surface of the negative electrode 11.

また、セパレーター１２として、ポリプロピレン微多孔膜（厚さ：２０μｍ）のセパレーター１２を直径：４０ｍｍに切断した。図２に示すように、これらを、負極集電タブ１１ａ、負極１１、セパレーター１２、正極１０、正極集電タブ１０ａの順に重ねた。このとき、絶縁体等とセパレーター１２が接触するように配置した。   Moreover, the separator 12 of the polypropylene microporous film (thickness: 20 micrometers) was cut | disconnected to diameter: 40mm as the separator 12. FIG. As shown in FIG. 2, these were stacked in the order of a negative electrode current collecting tab 11a, a negative electrode 11, a separator 12, a positive electrode 10, and a positive electrode current collecting tab 10a. At this time, it arrange | positioned so that an insulator etc. and the separator 12 may contact.

図３に示すように、上記積層体が収容可能な大きさに切断された、１辺の１３ａをヒートシールした外装体１３を用意した。   As shown in FIG. 3, an exterior body 13 was prepared by heat-sealing one side 13 a that was cut to a size that could accommodate the above laminate.

不活性雰囲気中で、外装体１３の開口部１３ｃからに上記積層体を挿入し、正極集電タブ１１ａを、溶着部１３ｂでヒートシールした後、開口部１３ｃから、１Ｍ ＬｉＰＦ６／ＥＣ＋ＰＣ（１：１（体積比））の非水電解質を注液した後、この外装体１３の開口部１３ｃをヒートシールして密閉し、試験セルを作製した。 In an inert atmosphere, the laminate is inserted from the opening 13c of the outer package 13, the positive electrode current collecting tab 11a is heat-sealed by the welded portion 13b, and then 1M LiPF 6 / EC + PC (1 : 1 (volume ratio)) non-aqueous electrolyte was injected, and then the opening 13c of the exterior body 13 was heat-sealed and sealed to prepare a test cell.

（従来例１）
従来例１の正極集電体、負極集電体としては、幅：３０ｍｍ、長さ：４０ｍｍで、それぞれ、厚さが、１．３ｍｍのアルミニウム焼結体、厚さが、１．０ｍｍの銅多孔質焼結体を用いた以外は、実施例１と同様にして、正極、負極を作製した。得られた正極の厚さは、０．７ｍｍ、負極の厚さは０．５ｍｍであった。 (Conventional example 1)
As the positive electrode current collector and the negative electrode current collector of Conventional Example 1, a width: 30 mm, a length: 40 mm, a 1.3 mm thick aluminum sintered body, and a 1.0 mm thick copper, respectively. A positive electrode and a negative electrode were produced in the same manner as in Example 1 except that the porous sintered body was used. The thickness of the obtained positive electrode was 0.7 mm, and the thickness of the negative electrode was 0.5 mm.

図４に、用いた試験セルの構成の模式図を示す。正極２０に、アルミニウム製の正極集電タブ２０ａを溶接した。また、負極２１に、ニッケル製の負極集電タブ２１ａを溶接した。   In FIG. 4, the schematic diagram of the structure of the used test cell is shown. A positive electrode current collecting tab 20 a made of aluminum was welded to the positive electrode 20. Further, a negative electrode current collecting tab 21 a made of nickel was welded to the negative electrode 21.

また、セパレーター２２として、ポリプロピレン微多孔膜（厚さ：２０μｍ）のセパレーター２２を幅：３２ｍｍ、長さ：４２ｍｍに切断した。これらを、負極集電タブ２１ａ、負極２１、セパレーター２２、正極２０、正極集電タブ２０ａの順に重ねて、積層体を作製した。このとき、絶縁体等とセパレーター２２が接触するように配置した。   Further, as the separator 22, a polypropylene microporous membrane (thickness: 20 μm) separator 22 was cut into a width: 32 mm and a length: 42 mm. These were laminated in order of the negative electrode current collection tab 21a, the negative electrode 21, the separator 22, the positive electrode 20, and the positive electrode current collection tab 20a, and the laminated body was produced. At this time, it arrange | positioned so that an insulator etc. and the separator 22 may contact.

上記積層体が収容可能な大きさに切断された、一対のアルミニウムラミネートフィルム２３ａ、２３ｂの３辺の溶着部２３ｃをヒートシールし、外装体２３とした。   The welded portions 23c on the three sides of the pair of aluminum laminate films 23a and 23b, which were cut to a size that can accommodate the laminated body, were heat-sealed to obtain an exterior body 23.

不活性雰囲気中で、外装体１３の開口部からに上記積層体を挿入し、外装体１３内に積層体を収容するとともに、１Ｍ ＬｉＰＦ６／ＥＣ＋ＰＣ（１：１（体積比））の非水電解質を注液した後、この外装体２３の開口部をヒートシールして密閉し、試験セルを作製した。 In an inert atmosphere, the laminate is inserted through the opening of the outer package 13, and the laminate is accommodated in the outer package 13, and 1M LiPF 6 / EC + PC (1: 1 (volume ratio)) non-water After injecting the electrolyte, the opening of the outer package 23 was heat-sealed and sealed to produce a test cell.

〔非水電解質二次電池用電極の性能試験〕
（放電容量試験）
上記試験用セルを、放電レート：０．１Ｃ、放電電圧：４．２〜２．８Ｖで放電を行った。また、このときの放電容量からエネルギー密度を算出した。表１に、これらの結果を示す。 [Performance test of electrode for non-aqueous electrolyte secondary battery]
(Discharge capacity test)
The test cell was discharged at a discharge rate of 0.1 C and a discharge voltage of 4.2 to 2.8 V. Further, the energy density was calculated from the discharge capacity at this time. Table 1 shows these results.

（信頼性試験）
上記試験用セルを、充放電レート：０．１Ｃ（ＣＶＣＣ充電で７５分）、充放電電圧：２．８〜４．２Ｖでの条件で、「充電→レスト：１５分→放電→レスト：１５分」を１サイクルとして、サイクル試験を行った。表１に、５００サイクル後に、放電レート：０．１Ｃ、放電電圧：４．２〜２．８Ｖで放電を行ったときの放電容量の結果を示す。また、〔「５００サイクル後の放電容量」／「初回の放電容量」〕を容量維持率（単位は「％」）とした。表１に、容量維持率の結果を示す。表１に、これらの結果を示す。 (Reliability test)
The test cell was charged and discharged at a charge / discharge rate of 0.1 C (75 minutes for CVCC charging) and a charge / discharge voltage of 2.8 to 4.2 V, “charging → rest: 15 minutes → discharge → rest: 15 The cycle test was performed with “minute” as one cycle. Table 1 shows the results of discharge capacity when discharging was performed at a discharge rate of 0.1 C and a discharge voltage of 4.2 to 2.8 V after 500 cycles. In addition, [“discharge capacity after 500 cycles” / “initial discharge capacity”] was defined as a capacity maintenance rate (unit: “%”). Table 1 shows the results of the capacity retention rate. Table 1 shows these results.

表１からわかるように、実施例１では放電容量が５０５０ｍＡｈ、エネルギー密度が２３０ｍＷｈ／ｃｍ３と非常に高く、かつ容量維持率も優れており、高信頼性であった。これに対して、従来例１では、放電容量が１２２ｍＡｈ、エネルギー密度が２２０ｍＷｈ／ｃｍ３と実施例１より劣る結果であった。また、表１には記載していないが、実施例１の試験用セルは、３Ｃ放電でも放電容量が４６００ｍＡｈであり、良好な出力特性を示した。 As can be seen from Table 1, in Example 1, the discharge capacity was very high, 5050 mAh, the energy density was 230 mWh / cm 3 , the capacity retention rate was excellent, and the reliability was high. On the other hand, in Conventional Example 1, the discharge capacity was 122 mAh and the energy density was 220 mWh / cm 3 , which was inferior to Example 1. Although not shown in Table 1, the test cell of Example 1 had a discharge capacity of 4600 mAh even with 3C discharge, and showed good output characteristics.

以上のように、本発明の非水電解質二次電池用集電体およびこれを用いた電極により、高エネルギー密度、高信頼性で、かつ良好な出力特性の非水電解質二次電池を製造することができる。   As described above, a non-aqueous electrolyte secondary battery with high energy density, high reliability, and good output characteristics is manufactured by using the current collector for a non-aqueous electrolyte secondary battery of the present invention and an electrode using the same. be able to.

１ 塊状の金属多孔質焼結体
２ 電解液流通孔
１０ 正極
１０ａ 正極集電タブ
１１ 負極
１１ａ 負極集電タブ
１２ セパレーター
１３ 外装体
１３ａ 溶着部
１３ｂ、１３ｃ 開口部兼溶着部
２０ 正極
２０ａ 正極集電タブ
２１ 負極
２１ａ 負極集電タブ
２２ セパレーター
２３ 外装体
２３ａ、２３ｂ アルミニウムラミネートフィルム
２３ｃ 溶着部 DESCRIPTION OF SYMBOLS 1 Bulk metal porous sintered compact 2 Electrolyte flow hole 10 Positive electrode 10a Positive electrode current collection tab 11 Negative electrode 11a Negative electrode current collection tab 12 Separator 13 Exterior body 13a Welding part 13b, 13c Opening part and welding part 20 Positive electrode 20a Positive electrode current collection Tab 21 Negative electrode 21a Negative electrode current collecting tab 22 Separator 23 Exterior body 23a, 23b Aluminum laminate film 23c Welding part

Claims (4)

直径が０．５〜２ｍｍで、厚さ方向に貫通している電解液流通孔を有する塊状の金属多孔質焼結体を備える集電体であって、前記金属多孔質焼結体が、三次元網目構造の金属骨格を有し、かつ前記金属骨格間に空孔径：２０〜５００μｍの空孔を有し、孔径：０．１〜３μｍの骨格内空孔を有することを特徴とする、非水電解質二次電池用集電体。
 A current collector comprising a massive metal porous sintered body having a diameter of 0.5 to 2 mm and an electrolyte flow hole penetrating in the thickness direction , wherein the metal porous sintered body is a tertiary it has a metal framework of the original network structure and pore size between the metal framework: having pores of 20 to 500 [mu] m, pore diameter: characterized by having a skeleton in pores of 0.1 to 3 m, the non Current collector for water electrolyte secondary battery.
円柱型または角柱型である、請求項１記載の非水電解質二次電池用集電体。   The current collector for a non-aqueous electrolyte secondary battery according to claim 1, wherein the current collector is a cylindrical type or a prismatic type. 請求項１または２記載の集電体と、前記集電体の金属多孔質焼結体の空孔内に活物質および結合剤を含むことを特徴とする、非水電解質二次電池用電極。   An electrode for a non-aqueous electrolyte secondary battery comprising the current collector according to claim 1 or 2 and an active material and a binder in the pores of the metal porous sintered body of the current collector. 請求項３記載の非水二次電池用電極を含む、非水電解質二次電池。
A nonaqueous electrolyte secondary battery comprising the electrode for a nonaqueous secondary battery according to claim 3.
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