JP4525649B2 - Positive electrode for lithium secondary battery and lithium secondary battery - Google Patents

Positive electrode for lithium secondary battery and lithium secondary battery Download PDF

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JP4525649B2
JP4525649B2 JP2006241306A JP2006241306A JP4525649B2 JP 4525649 B2 JP4525649 B2 JP 4525649B2 JP 2006241306 A JP2006241306 A JP 2006241306A JP 2006241306 A JP2006241306 A JP 2006241306A JP 4525649 B2 JP4525649 B2 JP 4525649B2
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positive electrode
lithium
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lithium secondary
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裕紀 西田
謙一郎 加美
堅次 中根
等 三浦
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Sumitomo Chemical Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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、リチウム二次電池用正極とその製造方法および該正極を用いたリチウム二次電池に関する。   The present invention relates to a positive electrode for a lithium secondary battery, a method for producing the same, and a lithium secondary battery using the positive electrode.

近年、パーソナルコンピュータ、携帯電話、携帯情報端末などを含むポータブル情報機器の普及が著しい。マルチメディアとしてのこれらの機器は多機能であることが望まれるため、電源に用いられる二次電池には小型、軽量でありながら大容量であること、即ち高エネルギー密度であることが求められている。この点において、従来の鉛蓄電池やニッケルカドミウム蓄電池等の水溶液系二次電池は満足できるものではなく、より高いエネルギー密度を実現できるリチウム二次電池、特にコバルト酸リチウム、ニッケル酸リチウム、リチウムマンガンスピネル等のリチウムの複合酸化物を正極活物質とし、負極活物質にリチウムイオンのドープ・脱ドープが可能な炭素材を使ったリチウム二次電池の研究開発がさかんに行われている。   In recent years, portable information devices including personal computers, mobile phones, portable information terminals, and the like have been widely used. Since these devices as multimedia are desired to be multifunctional, secondary batteries used for power sources are required to have a small capacity, light weight, large capacity, that is, high energy density. Yes. In this regard, conventional aqueous secondary batteries such as lead acid batteries and nickel cadmium batteries are not satisfactory, and lithium secondary batteries that can achieve higher energy density, particularly lithium cobaltate, lithium nickelate, lithium manganese spinel. Research and development of lithium secondary batteries using a composite material of lithium as a positive electrode active material and a carbon material capable of doping and dedoping lithium ions as a negative electrode active material are being carried out.

これらのリチウム二次電池は、内在するエネルギーが大きいため、内部短絡・外部短絡などの異常時に対して、より高い安全性が求められている。特に釘刺しまたは圧壊試験に代表されるような、局部的な発熱を伴う短絡に対しては、充電された正極活物質が、発熱により酸素を放出しながら分解し、さらに発熱することが知られている。このような状況下で従来から使われているポリエチレンまたはポリプロピレンからなるセパレータが短絡部で正極電極近傍に存在する場合、正極活物質から放出された酸素により酸化され、著しい発熱を伴うため、熱暴走に至る可能性があることが分かった。   Since these lithium secondary batteries have a large energy, they are required to have higher safety against abnormal situations such as internal short circuits and external short circuits. It is known that the charged positive electrode active material decomposes while releasing oxygen due to heat generation, and further generates heat, especially for short circuits with local heat generation, as represented by nail penetration or crush tests. ing. Under such circumstances, when a separator made of polyethylene or polypropylene, which is conventionally used, is present in the vicinity of the positive electrode at the short-circuited portion, it is oxidized by oxygen released from the positive electrode active material and accompanied by significant heat generation. It was found that there is a possibility of reaching.

一方、フッ素樹脂などからなる耐熱性樹脂を単独にセパレータとして使った場合には、シャットダウン機能が働かず、外部または高速充放電に伴う内部加熱に対して十分な安全性が得られない可能性がある。また、従来のポリオレフィン系セパレータにフッ素樹脂などからなる耐熱性樹脂のセパレータを付加した場合、耐熱性樹脂のセパレータの膜厚が厚いため、電池ケース内に収容できる活物質体積が減少し、容量が低下するという問題点があった。また、フッ素樹脂などからなる耐熱性樹脂のセパレータを付加することで電池抵抗が上昇し、高負荷時に容量が低下する問題点もあった。
また、特許文献１には、正極の表面にフッ素系樹脂からなるイオン透過性高分子薄膜を形成することにより、安全性を向上できると記載されている。しかしながら、ニッケル酸リチウムなどを正極活物質とした高容量が得られる電池では、まだ耐熱性が充分でない場合があるという問題があった。
特開平７−２９６８４７号公報 On the other hand, when a heat-resistant resin such as fluororesin is used alone as a separator, the shutdown function does not work, and there is a possibility that sufficient safety against internal heating due to external or high-speed charge / discharge may not be obtained. is there. In addition, when a heat-resistant resin separator made of fluororesin or the like is added to a conventional polyolefin-based separator, the thickness of the heat-resistant resin separator is large, so the volume of active material that can be accommodated in the battery case is reduced, and the capacity is increased. There was a problem that it decreased. In addition, the addition of a heat-resistant resin separator made of a fluororesin or the like increases the battery resistance, resulting in a problem of a decrease in capacity at high loads.
Patent Document 1 describes that safety can be improved by forming an ion-permeable polymer thin film made of a fluororesin on the surface of the positive electrode. However, a battery having a high capacity using lithium nickelate or the like as a positive electrode active material has a problem that the heat resistance may still be insufficient.
JP-A-7-296847

本発明の目的は、安全性をより向上させた高エネルギー密度のリチウム二次電池用正極とその製法および該正極を用いたリチウム二次電池を提供することにある。   An object of the present invention is to provide a positive electrode for a lithium secondary battery having a high energy density with improved safety, a method for producing the positive electrode, and a lithium secondary battery using the positive electrode.

このような事情をみて、本発明者らは鋭意検討を行なった結果、リチウム二次電池用正極の電極表面を特定のイオン透過性樹脂で被覆することにより、外部短絡または内部短絡に対して安全性が向上した高エネルギー密度のリチウム二次電池が得られることを見出し、本発明を完成するに至った。   In view of such circumstances, the present inventors have conducted intensive studies, and as a result, the electrode surface of the positive electrode for a lithium secondary battery is covered with a specific ion-permeable resin, so that it is safe against an external short circuit or an internal short circuit. The present inventors have found that a high energy density lithium secondary battery with improved properties can be obtained, and have completed the present invention.

すなわち、本発明は、（１）正極活物質、導電材および結着剤を含む合剤を集電体上に担持してなる正極の表面を、ＪＩＳ Ｋ ７２０７準拠の１８．６ｋｇ／ｃｍ2荷重時の測定における荷重たわみ温度が１００℃以上の樹脂から選ばれた少なくとも１種のイオン透過性樹脂で被覆してなるリチウム二次電池用正極に係るものである。
また、本発明は、（２）イオン透過性樹脂が溶解した溶液を正極面上に塗布し、該イオン透過性樹脂に対する貧溶媒に該正極を浸漬し該イオン透過性樹脂を析出させ、乾燥する（１）記載のリチウム二次電池用正極の製造方法に係るものである。
また、本発明は、（３）正極活物質としてリチウムの複合酸化物を含む正極と、リチウムイオンのドープ・脱ドープが可能な炭素材、リチウム金属またはリチウム合金を活物質とする負極と、液体または固体の電解質とを有するリチウム二次電池において、正極として（１）記載のリチウム二次電池用正極を用いるリチウム二次電池に係るものである。 That is, the present invention provides (1) a surface of a positive electrode obtained by supporting a mixture containing a positive electrode active material, a conductive material and a binder on a current collector, with a load of 18.6 kg / cm 2 in accordance with JIS K 7207. This relates to a positive electrode for a lithium secondary battery that is coated with at least one ion-permeable resin selected from resins having a deflection temperature under measurement of 100 ° C. or higher.
In the present invention, (2) a solution in which an ion permeable resin is dissolved is applied on the surface of the positive electrode, the positive electrode is immersed in a poor solvent for the ion permeable resin, and the ion permeable resin is deposited and dried. (1) It concerns on the manufacturing method of the positive electrode for lithium secondary batteries as described.
The present invention also includes (3) a positive electrode containing a composite oxide of lithium as a positive electrode active material, a negative electrode using a carbon material, lithium metal, or lithium alloy that can be doped / undoped with lithium ions as an active material, and a liquid. Alternatively, in a lithium secondary battery having a solid electrolyte, the present invention relates to a lithium secondary battery using the positive electrode for a lithium secondary battery described in (1) as a positive electrode.

本発明のリチウム二次電池は、高エネルギー密度であり、かつ釘刺し・圧壊試験に代表されるような局部短絡に対して安全性がさらに向上しており、その工業的価値は極めて大きい。   The lithium secondary battery of the present invention has a high energy density and further improved safety against a local short circuit as represented by a nail penetration / crush test, and its industrial value is extremely large.

次に、本発明を詳細に説明する。
本発明のリチウム二次電池用正極は、正極活物質、導電材および結着剤を含む合剤を集電体上に担持してなる正極の表面を、ＪＩＳ Ｋ ７２０７準拠の１８．６ｋｇ／ｃｍ2荷重時の測定における荷重たわみ温度が１００℃以上の樹脂から選ばれた少なくとも１種のイオン透過性樹脂で被覆してなることを特徴とする。さらに過酷な使用による高温下でもより安全であるために、本発明のリチウム二次電池用正極は、該荷重たわみ温度が２００℃以上の樹脂から選ばれた少なくとも１種のイオン透過性樹脂で被覆してなることが好ましい。
該荷重たわみ温度が１００℃以上の樹脂としては、ポリイミド、ポリアミドイミド、アラミド、ポリカーボネート、ポリアセタール、ポリサルホン、ポリフェニルサルファイド、ポリエーテルエーテルケトン、芳香族ポリエステル、ポリエーテルサルホン、ポリエーテルイミドなどが挙げられる。該荷重たわみ温度が２００℃以上の樹脂としては、ポリイミド、ポリアミドイミド、アラミド、ポリエーテルサルホン、ポリエーテルイミドなどが挙げられる。さらに、該イオン透過性樹脂として、ポリイミド、ポリアミドイミドおよびアラミドからなる群から選ぶことが特に好ましい。また、該イオン透過性樹脂は、溶剤可溶性であることが好ましい。 Next, the present invention will be described in detail.
In the positive electrode for a lithium secondary battery of the present invention, the surface of the positive electrode formed by supporting a mixture containing a positive electrode active material, a conductive material and a binder on a current collector is 18.6 kg / cm in accordance with JIS K 7207. It is characterized in that it is coated with at least one ion-permeable resin selected from resins having a deflection temperature under load of 100 ° C. or higher in the measurement under two loads. Furthermore, in order to be safer even under high temperatures due to severe use, the positive electrode for a lithium secondary battery of the present invention is coated with at least one ion-permeable resin selected from resins having a load deflection temperature of 200 ° C. or higher. It is preferable that
Examples of the resin having a deflection temperature under load of 100 ° C. or higher include polyimide, polyamideimide, aramid, polycarbonate, polyacetal, polysulfone, polyphenylsulfide, polyetheretherketone, aromatic polyester, polyethersulfone, and polyetherimide. It is done. Examples of the resin having a deflection temperature under load of 200 ° C. or higher include polyimide, polyamideimide, aramid, polyethersulfone, and polyetherimide. Further, the ion-permeable resin is particularly preferably selected from the group consisting of polyimide, polyamideimide and aramid. The ion-permeable resin is preferably soluble in a solvent.

該イオン透過性樹脂は、具体的には多孔質構造を有するものであり、該イオン透過性樹脂の空孔率は、３０〜８０体積％が好ましく、特に４０〜７０体積％が好ましい。
正極に被覆する該イオン透過性樹脂の膜厚は、１〜３０μｍが好ましく、特に５〜１５μｍが好ましい。該イオン透過性樹脂の膜厚が１μｍ未満では、十分な強度が得られず電池の組み立て時などにクラックなどの欠陥が生じるので好ましくなく、３０μｍを超えると電池内に収納できる活物質体積が減少するために、電池容量が低下するので好ましくない。 The ion-permeable resin specifically has a porous structure, and the porosity of the ion-permeable resin is preferably 30 to 80% by volume, particularly preferably 40 to 70% by volume.
The film thickness of the ion-permeable resin coated on the positive electrode is preferably 1 to 30 μm, particularly preferably 5 to 15 μm. If the film thickness of the ion-permeable resin is less than 1 μm, sufficient strength cannot be obtained and defects such as cracks occur during battery assembly, etc., and this is not preferable. If it exceeds 30 μm, the volume of active material that can be stored in the battery decreases. This is not preferable because the battery capacity is reduced.

本発明において、該イオン透過性樹脂で正極表面を被覆する方法としては、該イオン透過性樹脂が溶解した溶液を正極面上に塗布し、該イオン透過性樹脂に対する貧溶媒に該正極を浸漬し該イオン透過性樹脂を析出させ、乾燥する方法、または該イオン透過性樹脂が溶解した溶液を正極面上に塗布し、多湿雰囲気下に該正極を暴露し該イオン透過性樹脂を析出させ、乾燥する方法などが挙げられる。ここで、多湿雰囲気としては、相対湿度６０％以上の雰囲気が挙げられる。
該イオン透過性樹脂膜の空孔率を調整するために、さらに上記で得られた正極をロールプレスなどで圧密してもよい。
該イオン透過性樹脂に対する溶媒としては、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰということがある。）、Ｎ−Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、Ｎ−Ｎ−ジメチルホルムアミド、クレゾール、クロロホルム、テトラヒドロフラン、トルエン、キシレン、ジグライム、ｏ−クロロフェノールなどが挙げられる。なお、該イオン透過性樹脂がアラミドの場合には、重合した樹脂は上記溶媒には溶解しないが、重合前に溶解させ溶液中で重合させることにより、アラミド溶液を得ることができる。該アラミド溶液作製法としては、ＮＭＰに塩化カルシウムを溶解させた後、パラフェニレンジアミンを溶解させ、さらにテレフタル酸ジクロライドを徐々に添加した後に熟成する方法等が挙げられる。
また、該イオン透過性樹脂に対する貧溶媒としては、水、エタノール、メタノール、イソプロピルアルコールなどのアルコール類、またはアセトン、メチルエチルケトンなどのケトン類が挙げられる。 In the present invention, as a method of coating the surface of the positive electrode with the ion permeable resin, a solution in which the ion permeable resin is dissolved is applied on the surface of the positive electrode, and the positive electrode is immersed in a poor solvent for the ion permeable resin. A method of precipitating and drying the ion-permeable resin, or applying a solution in which the ion-permeable resin is dissolved on the positive electrode surface, exposing the positive electrode in a humid atmosphere, precipitating the ion-permeable resin, and drying The method of doing is mentioned. Here, the humid atmosphere includes an atmosphere having a relative humidity of 60% or more.
In order to adjust the porosity of the ion-permeable resin film, the positive electrode obtained above may be further consolidated by a roll press or the like.
As a solvent for the ion-permeable resin, N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP), NN-dimethylacetamide, dimethyl sulfoxide, NN-dimethylformamide, cresol, chloroform, tetrahydrofuran , Toluene, xylene, diglyme, o-chlorophenol and the like. When the ion-permeable resin is aramid, the polymerized resin is not dissolved in the solvent, but an aramid solution can be obtained by dissolving the polymer before polymerization and polymerizing it in the solution. Examples of the method for preparing an aramid solution include a method in which calcium chloride is dissolved in NMP, paraphenylenediamine is dissolved, and terephthalic acid dichloride is gradually added, followed by aging.
Examples of the poor solvent for the ion-permeable resin include alcohols such as water, ethanol, methanol, and isopropyl alcohol, and ketones such as acetone and methyl ethyl ketone.

本発明におけるリチウム二次電池用正極は、正極活物質、導電材および結着剤を含む合剤を集電体上に担持したものを用いる。
具体的には、該正極活物質として、リチウムイオンをドープ・脱ドープ可能な材料を含み、導電材として炭素質材料を含み、結着剤として熱可塑性樹脂などを含むものを用いることができる。該リチウムイオンをドープ・脱ドープ可能な材料としては、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉなどの遷移金属を少なくとも１種含むリチウム複合酸化物が挙げられる。中でも好ましくは、平均放電電位が高いという点で、ニッケル酸リチウム、コバルト酸リチウムなどのα−ＮａＦｅＯ2型構造を母体とする層状リチウム複合酸化物、リチウムマンガンスピネルなどのスピネル型構造を母体とするリチウム複合酸化物が挙げられる。 As the positive electrode for a lithium secondary battery in the present invention, a material in which a mixture containing a positive electrode active material, a conductive material and a binder is supported on a current collector is used.
Specifically, as the positive electrode active material, a material containing a material that can be doped / undoped with lithium ions, a carbonaceous material as a conductive material, and a thermoplastic resin as a binder can be used. Examples of the material that can be doped / undoped with lithium ions include lithium composite oxides containing at least one transition metal such as V, Mn, Fe, Co, and Ni. Among these, a layered lithium composite oxide based on an α-NaFeO 2 type structure such as lithium nickelate or lithium cobaltate, or a spinel type structure such as lithium manganese spinel is preferable based on a high average discharge potential. Examples include lithium composite oxide.

該リチウム複合酸化物は、種々の添加元素を含んでもよく、特にＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ａｇ、Ｍｇ、Ａｌ、Ｇａ、ＩｎおよびＳｎからなる群から選ばれた少なくとも１種の金属のモル数とニッケル酸リチウム中のＮｉのモル数との和に対して、前記の少なくとも１種の金属が０．１〜２０モル％であるように該金属を含む複合ニッケル酸リチウムを用いると、高容量での使用におけるサイクル性が向上するので好ましい。   The lithium composite oxide may contain various additive elements, particularly at least selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, Ag, Mg, Al, Ga, In, and Sn. Composite nickel acid containing a metal such that the at least one metal is 0.1 to 20 mol% with respect to the sum of the number of moles of one metal and the number of moles of Ni in lithium nickelate Lithium is preferable because cycle characteristics in use at a high capacity are improved.

該結着剤としての熱可塑性樹脂としては、ポリビニリデンフロライド、ビニリデンフロライドの共重合体、ポリテトラフルオロエチレン、テトラフルオロエチレン−ヘキサフロロプロピレンの共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエーテルの共重合体、エチレン−テトラフルオロエチレンの共重合体、ビニリデンフロライド−ヘキサフルオロプロピレン−テトラフルオロエチレンの共重合体、熱可塑性ポリイミド、ポリエチレン、ポリプロピレンなどが挙げられる。   As the thermoplastic resin as the binder, polyvinylidene fluoride, vinylidene fluoride copolymer, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether Copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, thermoplastic polyimide, polyethylene, polypropylene and the like.

該導電剤としての炭素質材料としては、天然黒鉛、人造黒鉛、コークス類、カーボンブラックなどが挙げられる。導電材として、それぞれ単独で用いてもよいし、例えば人造黒鉛とカーボンブラックとを混合して用いるといった複合導電材系を選択してもよい。   Examples of the carbonaceous material as the conductive agent include natural graphite, artificial graphite, cokes, and carbon black. As the conductive material, each may be used alone, or for example, a composite conductive material system in which artificial graphite and carbon black are mixed and used may be selected.

本発明のリチウム二次電池は、正極活物質としてリチウムの複合酸化物を含む正極と、リチウムイオンのドープ・脱ドープが可能な炭素材、リチウム金属またはリチウム合金を活物質とする負極と、液体または固体の電解質とを有するリチウム二次電池において、正極として前記の（１）記載のリチウム二次電池用正極を用いることを特徴とする。
本発明のリチウム二次電池の負極としては、例えばリチウムイオンをドープ・脱ドーブ可能な材料、リチウム金属またはリチウム合金などを用いることができる。リチウムイオンをドープ・脱ドープ可能な材料としては、天然黒鉛、人造黒鉛、コークス類、カーボンブラック、熱分解炭素類、炭素繊維、有機高分子化合物焼成体などの炭素質材料、正極よりも低い電位でリチウムイオンのドープ・脱ドープを行う酸化物、硫化物等のカルコゲン化合物が挙げられる。炭素質材料として、電位平坦性が高く、また平均放電電位が低いため正極と組み合わせた場合大きなエネルギー密度が得られるという点で、天然黒鉛、人造黒鉛等の黒鉛材料を主成分とする炭素質材料が好ましい。 The lithium secondary battery of the present invention includes a positive electrode containing a composite oxide of lithium as a positive electrode active material, a negative electrode using a carbon material, lithium metal or a lithium alloy as an active material capable of doping and dedoping lithium ions, and a liquid Or in the lithium secondary battery which has a solid electrolyte, the positive electrode for lithium secondary batteries of said (1) description is used as a positive electrode.
As the negative electrode of the lithium secondary battery of the present invention, for example, a material capable of doping and dedoping lithium ions, lithium metal, a lithium alloy, or the like can be used. Materials that can be doped / undoped with lithium ions include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and fired organic polymer compounds, and lower potential than the positive electrode. And chalcogen compounds such as oxides and sulfides for doping and dedoping lithium ions. As a carbonaceous material, a carbonaceous material mainly composed of graphite materials such as natural graphite and artificial graphite, because it has a high potential flatness and a low average discharge potential, so that a large energy density can be obtained when combined with a positive electrode. Is preferred.

また、液体の電解質と組み合わせて用いる場合において、該液体の電解質がエチレンカーボネートを含有しないときには、ポリエチレンカーボネートを含有した負極を用いると、サイクル特性と大電流放電特性が向上するので好ましい。炭素質材料の形状は、例えば天然黒鉛のような薄片状、メソカーボンマイクロビーズのような球状、黒鉛化炭素繊維のような繊維状、または微粉末の凝集体などのいずれでもよく、必要に応じて結着剤としての熱可塑性樹脂を添加することができる。熱可塑性樹脂としては、ポリビニリデンフロライド、ポリビニリデンフロライドの共重合体、ビニリデンフロライド−ヘキサフロロプロピレン−テトラフロロエチレンの共重合体、熱可塑性ポリイミド、ポリエチレン、ポリプロピレンなどが挙げられる。負極として用いられる酸化物、硫化物等のカルコゲン化合物としては、例えばスズ酸化物を主体とした非晶質化合物のような、周期率表の１３、１４、１５族を主体とした結晶質または非晶質の酸化物などが挙げられる。これらについても、必要に応じて導電材としての炭素質材料、結着剤としての熱可塑性樹脂を添加することができる。   In addition, when used in combination with a liquid electrolyte, when the liquid electrolyte does not contain ethylene carbonate, it is preferable to use a negative electrode containing polyethylene carbonate because cycle characteristics and large current discharge characteristics are improved. The shape of the carbonaceous material may be, for example, a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an aggregate of fine powder. Thus, a thermoplastic resin as a binder can be added. Examples of the thermoplastic resin include polyvinylidene fluoride, polyvinylidene fluoride copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, thermoplastic polyimide, polyethylene, and polypropylene. Examples of the chalcogen compounds such as oxides and sulfides used as the negative electrode include crystalline or non-crystalline materials mainly composed of groups 13, 14 and 15 of the periodic table such as amorphous compounds mainly composed of tin oxide. Examples thereof include crystalline oxides. Also for these, a carbonaceous material as a conductive material and a thermoplastic resin as a binder can be added as necessary.

本発明のリチウム二次電池で用いる負極集電体としては、Ｃｕ、Ｎｉ、ステンレスなどを用いることができるが、特にリチウム二次電池においてはリチウムと合金を作り難く、かつ薄膜に加工しやすいという点でＣｕが好ましい。該負極集電体に負極活物質を含む合剤を担持させる方法としては、加圧成型する方法、または溶媒などを用いてペースト化し集電体上に塗布乾燥後プレスするなどして圧着する方法が挙げられる。   As the negative electrode current collector used in the lithium secondary battery of the present invention, Cu, Ni, stainless steel and the like can be used. In particular, in a lithium secondary battery, it is difficult to make an alloy with lithium and it is easy to process into a thin film. Cu is preferable at this point. As a method of supporting the mixture containing the negative electrode active material on the negative electrode current collector, a method of pressure molding, or a method of pasting into a paste using a solvent or the like and applying pressure to the current collector by pressing after drying Is mentioned.

本発明のリチウム二次電池で用いるセパレータとしては、例えばポリエチレン、ポリプロピレンなどのオレフィン系樹脂、ポリエステル樹脂、ナイロンなどの不織布、織布などを用いることができる。該セパレータの厚みは、電池としての体積エネルギー密度が上がり、内部抵抗が小さくなるという点で、機械的強度が保たれる限り薄い程よく、１０〜３０μｍ程度が好ましい。   As the separator used in the lithium secondary battery of the present invention, for example, an olefin resin such as polyethylene or polypropylene, a polyester resin, a nonwoven fabric such as nylon, or a woven fabric can be used. The thickness of the separator is preferably as thin as possible as long as the mechanical strength is maintained from the viewpoint that the volume energy density of the battery is increased and the internal resistance is reduced, and is preferably about 10 to 30 μm.

本発明のリチウム二次電池で用いる電解質としては、例えばリチウム塩を有機溶媒に溶解させた非水電解質溶液、または固体電解質のいずれかから選ばれる公知のものを用いることができる。リチウム塩としては、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＳＯ2ＣＦ3）2、ＬｉＣ（ＳＯ2ＣＦ3）3、Ｌｉ2Ｂ10Ｃｌ10、低級脂肪族カルボン酸リチウム塩、ＬｉＡｌＣｌ4などのうち一種または二種以上の混合物が挙げられる。これらの中でもフッ素を含む、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、およびＬｉＣ（ＣＦ3ＳＯ2）3からなる群から選ばれた少なくとも１種を含むものを用いることが好ましい。 As the electrolyte used in the lithium secondary battery of the present invention, for example, a known electrolyte selected from a nonaqueous electrolyte solution in which a lithium salt is dissolved in an organic solvent or a solid electrolyte can be used. Examples of lithium salts include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , One or a mixture of two or more of lower aliphatic carboxylic acid lithium salts, LiAlCl 4 and the like can be mentioned. Among these, at least selected from the group consisting of LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , and LiC (CF 3 SO 2 ) 3 containing fluorine. It is preferable to use one containing one kind.

本発明のリチウム二次電池で用いる有機溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、４−トリフルオロメチル−１，３−ジオキソラン−２−オン、１，２−ジ（メトキシカルボニルオキシ）エタンなどのカーボネート類；１，２−ジメトキシエタン、１，３−ジメトキシプロパン、ペンタフルオロプロピルメチルエーテル、２，２，３，３−テトラフルオロプロピルジフルオロメチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフランなどのエーテル類；ギ酸メチル、酢酸メチル、γ−ブチロラクトンなどのエステル類；アセトニトリル、ブチロニトリルなどのニトリル類；N，N−ジメチルホルムアミド、N，N−ジメチルアセトアミドなどのアミド類；３−メチル−２−オキサゾリドンなどのカーバメート類；スルホラン、ジメチルスルホキシド、１，３−プロパンサルトンなどの含硫黄化合物、または上記の有機溶媒にフッ素置換基を導入したものを用いることができるが、通常はこれらのうちの二種以上を混合して用いる。   Examples of the organic solvent used in the lithium secondary battery of the present invention include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2 Carbonates such as di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, Ethers such as 2-methyltetrahydrofuran; Esters such as methyl formate, methyl acetate and γ-butyrolactone; Nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide, N, N-dimethyla Amides such as toamide; carbamates such as 3-methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 1,3-propane sultone, or those obtained by introducing a fluorine substituent into the above organic solvent Usually, a mixture of two or more of these is used.

これらの中でもカーボネート類を含む混合溶媒が好ましく、環状カーボネートと非環状カーボネート、または環状カーボネートとエーテル類の混合溶媒がさらに好ましい。環状カーボネートと非環状カーボネートの混合溶媒としては、動作温度範囲が広く、負荷特性に優れ、かつ負極の活物質として天然黒鉛、人造黒鉛等の黒鉛材料を用いた場合でも難分解性であるという点で、エチレンカーボネート、ジメチルカーボネートおよびエチルメチルカーボネートを含む混合溶媒が好ましい。   Among these, a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or cyclic carbonate and ether is more preferable. The mixed solvent of cyclic carbonate and non-cyclic carbonate has a wide operating temperature range, excellent load characteristics, and is hardly decomposable even when a graphite material such as natural graphite or artificial graphite is used as the negative electrode active material. In addition, a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferable.

本発明のリチウム二次電池で用いる固体電解質としては、例えばポリエチレンオキサイド系、ポリオルガノシロキサン鎖もしくはポリオキシアルキレン鎖の少なくとも一種以上を含む高分子化合物などの高分子電解質、Ｌｉ2Ｓ−ＳｉＳ2、Ｌｉ2Ｓ−Ｐ2Ｓ5、Ｌｉ2Ｓ−Ｂ2Ｓ3などの硫化物系電解質、またはＬｉ2Ｓ−ＳｉＳ2−Ｌｉ3ＰＯ4、Ｌｉ2Ｓ−ＳｉＳ2−Ｌｉ2ＳＯ4などの硫化物を含む無機化合物系電解質を用いることができる。また、高分子に非水電解質溶液を保持させた、いわゆるゲルタイプのものを用いることもできる。 As the solid electrolyte used in the lithium secondary battery of the present invention, for example, a polymer electrolyte such as a polymer compound containing at least one of polyethylene oxide, polyorganosiloxane chain or polyoxyalkylene chain, Li 2 S—SiS 2 , Sulfide electrolytes such as Li 2 S—P 2 S 5 and Li 2 S—B 2 S 3 , or Li 2 S—SiS 2 —Li 3 PO 4 , Li 2 S—SiS 2 —Li 2 SO 4, etc. An inorganic compound electrolyte containing a sulfide can be used. Moreover, what is called a gel type which hold | maintained the nonaqueous electrolyte solution in the polymer | macromolecule can also be used.

なお、本発明のリチウム二次電池の形状は、特に限定されるものではなく、ペーパー型、コイン型、円筒型、角形などのいずれであってもよい。   The shape of the lithium secondary battery of the present invention is not particularly limited, and may be any of a paper type, a coin type, a cylindrical type, a rectangular shape, and the like.

以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらによって何ら限定されるものではない。
実施例１
（１）正極シート状電極の作製
ポリビニリデンフロライド（以下、ＰＶＤＦということがある。）３重量部をＮＭＰで分散し、導電材としての人造黒鉛粉末９重量部とアセチレンブラック１重量部と正極活物質であるニッケル酸リチウム粉末８７重量部を分散混練し正極合剤ペーストとした。該ペーストを集電体である厚さ２０μｍのＡｌ箔の両面の所定部分に塗布し、乾燥、ロールプレスを行い正極シート状電極を得た。
（２）イオン透過性樹脂による被覆
ポリイミドワニス［商品名リカコートＳＮ２０（樹脂分２０％、ＮＭＰ８０％）：（株）新日本理化製：ＪＩＳ Ｋ ７２０７準拠の１８．６ｋｇ／ｃｍ2荷重時の測定における樹脂の荷重たわみ温度が約３００℃である。］を樹脂分が１０重量部となるようにＮＭＰで希釈し、ドクターブレードで上記正極シート状電極に塗布した後、アセトン中に浸漬しポリイミド樹脂を析出させ、乾燥しイオン透過性樹脂により該正極シート状電極の表面を被覆した。該正極シート状電極の表面を被覆したイオン透過性樹脂膜の厚みは、片面８μｍであり、空孔率は６５体積％であった。
（３）負極シート状電極の作製
数平均分子量５００００のポリエチレンカーボネート２重量部と結着剤としてのＰＶＤＦを８重量部をＮＭＰで溶解させた後負極シート状電極の活物質である黒鉛化炭素繊維９０重量部を分散混練し、負極合剤ペーストとした。該ペーストを集電体である厚さ１０μｍのＣｕ箔の両面の所定部分に塗布し、乾燥、ロールプレスを行って負極シート状電極を得た。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these.
Example 1
(1) Production of positive electrode sheet electrode 3 parts by weight of polyvinylidene fluoride (hereinafter sometimes referred to as PVDF) is dispersed with NMP, 9 parts by weight of artificial graphite powder as a conductive material, 1 part by weight of acetylene black, and positive electrode 87 parts by weight of lithium nickelate powder as an active material was dispersed and kneaded to obtain a positive electrode mixture paste. The paste was applied to predetermined portions on both sides of a 20 μm thick Al foil as a current collector, dried and roll pressed to obtain a positive electrode sheet electrode.
(2) Coating with ion-permeable resin Polyimide varnish [trade name Rika Coat SN20 (resin content 20%, NMP 80%): manufactured by Shin Nippon Rika Co., Ltd .: in measurement at 18.6 kg / cm 2 load according to JIS K 7207 The deflection temperature under load of the resin is about 300 ° C. ] Is diluted with NMP so that the resin content becomes 10 parts by weight, and applied to the positive electrode sheet electrode with a doctor blade, and then immersed in acetone to precipitate a polyimide resin, dried, and dried by ion permeable resin. The surface of the sheet electrode was coated. The thickness of the ion-permeable resin film covering the surface of the positive electrode sheet-like electrode was 8 μm on one side, and the porosity was 65% by volume.
(3) Production of negative electrode sheet electrode Graphitized carbon fiber which is an active material of a negative electrode sheet electrode after dissolving 2 parts by weight of polyethylene carbonate having a number average molecular weight of 50000 and 8 parts by weight of PVDF as a binder with NMP. 90 parts by weight was dispersed and kneaded to obtain a negative electrode mixture paste. The paste was applied to predetermined portions on both sides of a 10 μm-thick Cu foil as a current collector, dried and roll-pressed to obtain a negative electrode sheet electrode.

上記のようにして作製した正極シート状電極、負極シート状電極を厚さ２５μｍの多孔質ポリエチレンフィルムよりなるセパレータを介して、負極、セパレータ、正極、セパレータの順に積層し、この積層体を一端より巻き取って渦巻形状の電極素子とした。   The positive electrode sheet electrode and negative electrode sheet electrode prepared as described above were laminated in the order of a negative electrode, a separator, a positive electrode, and a separator through a separator made of a porous polyethylene film having a thickness of 25 μm. It wound up and it was set as the spiral-shaped electrode element.

前記の電極素子を電池缶に挿入し、非水電解質溶液としてジメチルカーボネートと２，２，３，３−テトラフルオロプロピルジフルオロメチルエーテルとの５０：５０混合液にＬｉＰＦ6を１モル／リットルとなるように溶解したものを含浸し、安全弁を備えた正極端子を兼ねる電池蓋をガスケットを介してかしめて１８６５０サイズの円筒型電池を得た。 The electrode element is inserted into a battery can, and LiPF 6 is 1 mol / liter in a 50:50 mixture of dimethyl carbonate and 2,2,3,3-tetrafluoropropyldifluoromethyl ether as a nonaqueous electrolyte solution. Thus, the melted product was impregnated, and a battery lid that also served as a positive electrode terminal equipped with a safety valve was caulked through a gasket to obtain a 18650 size cylindrical battery.

このようにして得た円筒型電池２個について、定格容量の１５０％の充電を行って過充電状態とした後、釘刺し試験を実施した。釘刺し試験の方法は（社）日木蓄電池工業会のリチウム二次電池安全性評価基準ガイドライン（日本蓄電池工業会指針ＳＢＡ−Ｇ１１０１−１９９５）にしたがった。その結果、試験に供した電池は過充電という苛酷な状態にもかかわらず、著しい内圧上昇も認められず、破裂せず発火もしなかった。   The two cylindrical batteries thus obtained were charged to 150% of the rated capacity to be overcharged, and then a nail penetration test was performed. The method of the nail penetration test was in accordance with the guidelines for safety evaluation standards for lithium secondary batteries of the Japan Storage Battery Industry Association (Japan Storage Battery Industry Association Guidelines SBA-G1101-1995). As a result, the battery used in the test did not show a significant increase in internal pressure, did not rupture, and did not ignite despite the severe state of overcharging.

比較例１
正極表面にイオン透過性樹脂のイオン透過性膜を形成せずに、実施例１と同様にして１８６５０サイズの円筒型電池を得た。このようにして得た円筒型電池２個について定格容量の１５０％の充電を行って過充電状態とした後、実施例１と同様に釘刺し試験を行なった。その結果、釘刺し後著しい内圧上昇が認められた。 Comparative Example 1
An 18650 size cylindrical battery was obtained in the same manner as in Example 1 without forming an ion permeable film of ion permeable resin on the surface of the positive electrode. The two cylindrical batteries thus obtained were charged to 150% of the rated capacity to be overcharged, and then a nail penetration test was conducted in the same manner as in Example 1. As a result, a significant increase in internal pressure was observed after nail penetration.

実施例１におけるリチウム二次電池の構造の概略断面図Schematic sectional view of the structure of the lithium secondary battery in Example 1 比較例１におけるリチウム二次電池の構造の概略断面図Schematic sectional view of the structure of the lithium secondary battery in Comparative Example 1

符号の説明Explanation of symbols

１・・・セパレータ
２・・・負極
３・・・正極
４・・・イオン透過性樹脂 DESCRIPTION OF SYMBOLS 1 ... Separator 2 ... Negative electrode 3 ... Positive electrode 4 ... Ion permeable resin

Claims (7)

正極活物質、導電材および結着剤を含む合剤を集電体上に担持してなる正極の表面を、ポリイミド、ポリアミドイミドおよびアラミドからなる群から選ばれた少なくとも１種であるイオン透過性樹脂で被覆してなることを特徴とするリチウム二次電池用正極。   Ion permeability which is at least one selected from the group consisting of polyimide, polyamideimide and aramid on the surface of the positive electrode formed by supporting a mixture containing a positive electrode active material, a conductive material and a binder on a current collector A positive electrode for a lithium secondary battery, characterized by being coated with a resin. イオン透過性樹脂が空孔率３０〜８０体積％であることを特徴とする請求項１記載のリチウム二次電池用正極。   The positive electrode for a lithium secondary battery according to claim 1, wherein the ion-permeable resin has a porosity of 30 to 80% by volume. 正極活物質が、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｃｕ、Ａｇ、Ｍｇ、Ａｌ、Ｇａ、ＩｎおよびＳｎからなる群から選ばれた少なくとも１種の金属のモル数とニッケル酸リチウム中のＮｉのモル数との和に対して、前記の少なくとも１種の金属が０．１〜２０モル％であるように該金属を含む複合ニッケル酸リチウムである請求項１または２に記載のリチウム二次電池用正極。   The positive electrode active material contains at least one metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Cu, Ag, Mg, Al, Ga, In, and Sn, and in lithium nickelate 3. The lithium according to claim 1, which is a composite lithium nickelate containing the metal such that the at least one metal is 0.1 to 20 mol% with respect to the sum of the number of moles of Ni. Secondary battery positive electrode. イオン透過性樹脂が溶解した溶液を正極面上に塗布し、該イオン透過性樹脂に対する貧溶媒に該正極を浸漬し該イオン透過性樹脂を析出させ、乾燥することを特徴とする請求項１〜３のいずれかに記載のリチウム二次電池用正極の製造方法。   A solution in which an ion permeable resin is dissolved is applied on the surface of the positive electrode, and the positive electrode is immersed in a poor solvent for the ion permeable resin to precipitate the ion permeable resin, followed by drying. 4. A method for producing a positive electrode for a lithium secondary battery according to any one of 3 above. 正極活物質としてリチウムの複合酸化物を含む正極と、リチウムイオンのドープ・脱ドープが可能な炭素材、リチウム金属またはリチウム合金を活物質とする負極と、液体または固体の電解質とを有するリチウム二次電池において、正極として請求項１〜４のいずれかに記載のリチウム二次電池用正極を用いることを特徴とするリチウム二次電池。   A positive electrode containing a composite oxide of lithium as a positive electrode active material, a negative electrode having a carbon material capable of being doped / undoped with lithium ions, a lithium metal or a lithium alloy, and a liquid or solid electrolyte. In a secondary battery, the positive electrode for lithium secondary batteries in any one of Claims 1-4 is used as a positive electrode, The lithium secondary battery characterized by the above-mentioned. ポリイミド、ポリアミドイミドおよびアラミドからなる群から選ばれた少なくとも１種のイオン透過性樹脂が溶解した溶液からなる、正極活物質、導電材および結着剤を含む合剤を集電体上に担持してなる正極の表面の被覆用溶液。 A mixture containing a positive electrode active material, a conductive material, and a binder composed of a solution in which at least one ion-permeable resin selected from the group consisting of polyimide, polyamideimide and aramid is dissolved is supported on a current collector. A coating solution for the surface of the positive electrode. イオン透過性樹脂に対する溶媒が、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰということがある。）、Ｎ−Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、Ｎ−Ｎ−ジメチルホルムアミド、クレゾール、クロロホルム、テトラヒドロフラン、トルエン、キシレン、ジグライム、ｏ−クロロフェノールから選ばれる請求項６記載の溶液。 The solvent for the ion-permeable resin is N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP), NN-dimethylacetamide, dimethylsulfoxide, NN-dimethylformamide, cresol, chloroform, tetrahydrofuran, toluene. , xylene, diglyme, solution of claim 6 Symbol placing selected from o- chlorophenol.
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JP5365107B2 (en) 2008-09-02 2013-12-11 Ｔｄｋ株式会社 Method for producing electrode for electrochemical device
JP5365106B2 (en) * 2008-09-02 2013-12-11 Ｔｄｋ株式会社 Method for producing electrode for electrochemical element, and electrode for electrochemical element
JP5381330B2 (en) * 2009-05-27 2014-01-08 住友化学株式会社 Electrode mixture, electrode and non-aqueous electrolyte secondary battery

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