JP2005259639A - Lithium secondary battery and its manufacturing method - Google Patents
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Abstract
Description
本発明は、耐短絡性および耐熱性などの安全性と電気特性を両立した優れたリチウム二次電池およびその製造方法に関する。 The present invention relates to an excellent lithium secondary battery having both safety and electric characteristics such as short circuit resistance and heat resistance, and a method for producing the same.
リチウム二次電池などの化学電池では、正極と負極との間に、それぞれの極板を電気的に絶縁し、さらに電解液を保持する役目をもつセパレータがある。リチウム二次電池では、現在、主にポリエチレンからなる微多孔性薄膜シートが使われている。
しかしながら、これら樹脂からなるシート状セパレータは、概して低温で収縮しやすく、よって内部短絡や釘のような鋭利な形状の突起物が電池を貫いた時、瞬時に発生する短絡反応熱により短絡部が拡大し、さらに多大な反応熱を発生させ、異常過熱を促進するという課題を有していた。
そこで、上記課題を含めた安全性を向上させるための技術として、従来より高分子セパレータ上にセラミックス粒子とポリマーマトリックスからなる溶液を塗布し、高耐熱性の絶縁層を形成する技術(特許文献１参照)や、高分子セパレータと電極を、フィラーを含む接着性樹脂で接合する技術(特許文献２参照)が提案されている。
However, sheet-like separators made of these resins generally tend to shrink at low temperatures, so that when a sharply shaped protrusion such as an internal short circuit or a nail penetrates the battery, the short circuit part is caused by a short circuit reaction heat that is instantaneously generated. It had the problem of expanding and generating much more heat of reaction and promoting abnormal overheating.
Therefore, as a technique for improving safety including the above-described problems, a technique for forming a highly heat-resistant insulating layer by applying a solution comprising ceramic particles and a polymer matrix on a polymer separator has been conventionally used (Patent Document 1). And a technique for joining a polymer separator and an electrode with an adhesive resin containing a filler (see Patent Document 2).
しかしながら高分子セパレータ上にセラミックス粒子とポリマーマトリックスからなる溶液を塗布し、高耐熱性の絶縁層を形成する技術については、電極とポリマーセパレータが接着されていないので、釘刺し試験などで内部短絡が発生した時に、その発熱によってポリマーセパレータが収縮するのに伴って、耐熱性絶縁層も収縮してしまい、更に発熱が促進されるという欠点を有する。また、電極群構成時のポリマーセパレータの巻きずれ等による内部短絡が発生する可能性があるという欠点を有する。 However, regarding the technology for applying a solution consisting of ceramic particles and a polymer matrix on a polymer separator to form a highly heat-resistant insulating layer, the electrode and polymer separator are not bonded together, so internal short circuits may occur in nail penetration tests. When generated, as the polymer separator contracts due to the heat generation, the heat-resistant insulating layer also contracts, and the heat generation is further promoted. In addition, there is a drawback in that an internal short circuit may occur due to winding deviation of the polymer separator when the electrode group is configured.
また高分子セパレータと電極を、フィラーを含む接着性樹脂で接合する技術については、接着性樹脂が電極活物質の凹凸を埋めることになるため、形成される耐熱性絶縁層の厚みにばらつきが生じる。つまり抵抗にばらつきが生じるため、充放電反応の均一性が低下し、電池特性が低下するという欠点を有する。 In addition, regarding the technique of joining the polymer separator and the electrode with an adhesive resin containing a filler, the adhesive resin fills the unevenness of the electrode active material, resulting in variations in the thickness of the formed heat-resistant insulating layer. . That is, since the resistance varies, there is a disadvantage that the uniformity of the charge / discharge reaction is lowered and the battery characteristics are lowered.
本発明は上記従来の課題を解決するもので、耐短絡性および耐熱性などの安全性と電気特性を両立した、優れたリチウム二次電池を提供することを目的とする。 The present invention solves the above-described conventional problems, and an object thereof is to provide an excellent lithium secondary battery having both safety such as short circuit resistance and heat resistance and electrical characteristics.
本発明のリチウム二次電池は、正極と、負極と、樹脂からなる多孔質層とを積層または捲回した電極群をもつリチウム二次電池において、フィラーおよび結着剤からなる耐熱性絶縁層が前記多孔質層の片面上に形成され、さらに前記多孔質層のもう一方の面が前記正極または負極のいずれかの極板と接して、前記多孔質層と前記極板が一体化されているものである。 The lithium secondary battery of the present invention is a lithium secondary battery having an electrode group in which a positive electrode, a negative electrode, and a porous layer made of a resin are laminated or wound, and a heat-resistant insulating layer made of a filler and a binder is provided. The porous layer is formed on one surface of the porous layer, and the other surface of the porous layer is in contact with either the positive electrode or the negative electrode, so that the porous layer and the electrode plate are integrated. Is.
本構成においては、耐熱性絶縁層を多孔質層上に形成しているため、厚さの均一な耐熱性絶縁層を配することができ、電池反応の均一性を高く保つことができる。また耐熱性絶縁層を形成した多孔質層が電極と一体化されているため、巻きずれ等による内部短絡が起こることもなく、上記課題を解決することができる。 In this configuration, since the heat-resistant insulating layer is formed on the porous layer, the heat-resistant insulating layer having a uniform thickness can be disposed, and the uniformity of the battery reaction can be kept high. Further, since the porous layer on which the heat-resistant insulating layer is formed is integrated with the electrode, the above problem can be solved without causing an internal short circuit due to winding deviation or the like.
さらに、上記多孔質層の溶融温度が２００℃以下であることにより、電極成分を変質させることなく上記課題を解決することができる。 Furthermore, when the melting temperature of the porous layer is 200 ° C. or lower, the above-mentioned problem can be solved without altering the electrode components.
さらに、多孔質層として不織布を用いることにより、電極と一体化させた後も電極間のイオンの移動のために十分な多孔度を確保することができる。 Furthermore, by using a non-woven fabric as the porous layer, sufficient porosity can be secured for the movement of ions between the electrodes even after being integrated with the electrodes.
さらに、上述のリチウム二次電池において、さらに電極間にポリエチレン、またはポリプロピレンからなる層を配することにより、内部短絡等によって電池内部が発熱した場合に、その融点以上に電池温度が昇温した時はその細孔を閉鎖し、イオンの通過を停止させることができ、さらに短絡に対する安全性を高めることができる。 Furthermore, in the above-described lithium secondary battery, when the inside of the battery generates heat due to an internal short circuit or the like by further disposing a layer made of polyethylene or polypropylene between the electrodes, the battery temperature rises above its melting point. Can close the pores, stop the passage of ions, and can further improve safety against short circuit.
また、製造方法として、多孔質層上に、フィラー、結着剤を溶媒中に分散させた溶液を塗布、乾燥させて耐熱性絶縁層を形成した後に、多孔質層を溶着によって正極、または負極と一体化させた電極を用いてリチウム二次電池を製造するものである。 As a manufacturing method, a porous layer is coated with a solution in which a filler and a binder are dispersed in a solvent and dried to form a heat-resistant insulating layer. A lithium secondary battery is manufactured using an electrode integrated with the above.
以上のように本発明によれば、内部短絡に対する安全性と電池特性を両立した優れたリチウム二次電池を提供することが可能となる。 As described above, according to the present invention, it is possible to provide an excellent lithium secondary battery having both safety against internal short circuit and battery characteristics.
本発明の好ましい形態を以下に示す。 Preferred embodiments of the present invention are shown below.
図１に本発明におけるリチウム二次電池の構造の模式図を示す。１は正極、２はポリエチレンセパレータ、３は多孔質層上に形成した耐熱性絶縁層、４はポリプロピレン不織布、５は負極である。 FIG. 1 shows a schematic diagram of the structure of a lithium secondary battery according to the present invention. 1 is a positive electrode, 2 is a polyethylene separator, 3 is a heat-resistant insulating layer formed on the porous layer, 4 is a polypropylene nonwoven fabric, and 5 is a negative electrode.
多孔質層として用いられるのは、電極と一体化した際にも十分な多孔度を有するものが望ましく、また、一体化させる電極成分を変質させない温度で一体化できるものが望ましい。例えば、ポリエチレン、ポリプロピレン、ナイロンからなる微多孔膜、もしくは不織布などが挙げられるが、その中でも、溶融温度が２００℃以下であるポリエチレン、もしくはポリプロピレンからなる不織布が好ましい。 The porous layer is preferably one having sufficient porosity even when integrated with an electrode, and one that can be integrated at a temperature that does not alter the electrode components to be integrated. For example, a microporous film made of polyethylene, polypropylene, nylon, or a nonwoven fabric may be mentioned. Among them, a nonwoven fabric made of polyethylene or polypropylene having a melting temperature of 200 ° C. or less is preferable.
さらに、耐熱性絶縁層に結着剤として用いられるのは、耐熱性が高く、ゴム弾性を有する、ポリアクリロニトリル単位を含むゴム性状高分子であることが好ましい。 Further, a rubbery polymer containing a polyacrylonitrile unit having high heat resistance and rubber elasticity is preferably used as a binder for the heat resistant insulating layer.
さらに耐熱性絶縁層にフィラーとして用いられるのは、無機酸化物が好ましい。各種樹脂微粒子もフィラーとしては一般的であるが、前述のように耐熱性が必要である上に、リチウム二次電池の使用範囲内で電気化学的に安定である必要があり、これら要件を満たしつつ塗料化に適する材料としては無機酸化物、特にアルミナが好ましい。この無機酸化物は複数種を混合あるいは多層化して用いても良い。 Furthermore, an inorganic oxide is preferably used as a filler in the heat resistant insulating layer. Various resin fine particles are also commonly used as fillers. However, as described above, they need heat resistance and must be electrochemically stable within the range of use of lithium secondary batteries. However, an inorganic oxide, particularly alumina, is preferable as a material suitable for coating. This inorganic oxide may be used as a mixture of a plurality of types or in multiple layers.
正極については、活物質としてコバルト酸リチウムおよびその変性体・ニッケル酸リチウムおよびその変性体・マンガン酸リチウムおよびその変性体などの複合酸化物を挙げることができる。結着剤としてはポリテトラフルオロエチレン（ＰＴＦＥ）・ポリフッ化ビニリデン（ＰＶＤＦ）等を単独または組み合わせて用いても良い。導電剤としてはアセチレンブラック・ケッチェンブラック（登録商標）・各種グラファイトを単独あるいは組み合わせて用いて良い。 With respect to the positive electrode, examples of the active material include composite oxides such as lithium cobaltate and its modified body / lithium nickelate and its modified body / lithium manganate and its modified body. As the binder, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) or the like may be used alone or in combination. As the conductive agent, acetylene black, ketjen black (registered trademark), and various graphites may be used alone or in combination.
負極については、活物質として各種天然黒鉛および人造黒鉛・シリサイドなどのシリコ
ン系複合材料・リチウム金属および各種合金組成材料を用いることができる。結着剤としてはＰＶＤＦおよびその変性体をはじめ各種バインダーを用いることができる。
For the negative electrode, various natural graphites, silicon-based composite materials such as artificial graphite and silicide, lithium metal, and various alloy composition materials can be used as the active material. Various binders such as PVDF and modified products thereof can be used as the binder.
また、本発明において正極と負極を電気的に絶縁するものとして、多孔質層上に形成する高耐熱絶縁層以外に、ポリエチレン樹脂、ポリプロピレン樹脂などのポリオレフィン樹脂からなるセパレータをあわせて用いてもかまわない。 In the present invention, a separator made of a polyolefin resin such as a polyethylene resin or a polypropylene resin may be used in addition to the high heat-resistant insulating layer formed on the porous layer as a material for electrically insulating the positive electrode and the negative electrode. Absent.
電解液については、塩としてＬｉＰＦ6およびＬｉＢＦ4などの各種リチウム化合物を用いることができる。また溶媒としてエチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭＣ）を単独および組み合わせて用いることができる。 For the electrolytic solution, it is possible to use various lithium compounds such as LiPF 6 and LiBF 4 as a salt. Further, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) can be used alone or in combination as a solvent.
本発明の電池の製造方法は、
（ａ）前記多孔質層片面上に、フィラー、結着剤を溶媒中に分散させた溶液を塗布する工程、
（ｂ）溶液を塗布した多孔質層を乾燥してフィラーおよび結着剤からなる耐熱性絶縁層を形成する工程、
（ｃ）前記多孔質層のもう一方の面を前記正極または負極のいずれかの極板と重ね合わせ、溶着によって前記多孔質層と前記極板を一体化する工程を含むものである。
The battery manufacturing method of the present invention comprises:
(A) applying a solution in which a filler and a binder are dispersed in a solvent on one surface of the porous layer;
(B) drying the porous layer coated with the solution to form a heat-resistant insulating layer comprising a filler and a binder;
(C) The other surface of the porous layer is overlapped with either the positive electrode or the negative electrode, and the porous layer and the electrode plate are integrated by welding.
まず（ａ）の工程において、分散媒として用いるものについては、均一に分散することが可能であり、フィラー、結着剤、塗布する多孔質層成分に対して不活性なものである必要がある。また、フィラー、結着剤、多孔質層成分が変質しない温度で蒸発させる必要がある。このような観点から、有機系溶媒であることが望ましい。例えば、Ｎ−メチルピロリドン（ＮＭＰ）、メチルエチルケトン（ＭＥＫ）、トルエンなどが挙げられる。 First, in the step (a), the material used as a dispersion medium can be uniformly dispersed and must be inert to the filler, the binder, and the porous layer component to be applied. . Further, it is necessary to evaporate at a temperature at which the filler, binder, and porous layer component do not change. From such a viewpoint, an organic solvent is desirable. For example, N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK), toluene and the like can be mentioned.
分散装置としては、各種分散装置を用いることができる。例えば、インターナルミキサー、双腕型ミキサー、ヘンシェルミキサー、パドルミキサーなどが挙げられる。 Various dispersing devices can be used as the dispersing device. For example, an internal mixer, a double-arm mixer, a Henschel mixer, a paddle mixer, and the like can be given.
溶液の塗布に関しては、ダイコート方式、グラビアコート方式、コンマコート方式等の各種塗布方式により塗布することができる。 As for the application of the solution, it can be applied by various application methods such as a die coating method, a gravure coating method, and a comma coating method.
また、（ｂ）の工程において、溶液を塗布した多孔質層の乾燥に関しては、フィラー、結着剤、多孔質層成分が変質しない温度で行うことが必要である。減圧環境で行ってもかまわない。 In the step (b), the porous layer coated with the solution needs to be dried at a temperature at which the filler, the binder, and the porous layer component do not change. It may be performed in a reduced pressure environment.
そして、（ｃ）の工程において、多孔質層を極板と溶着させる方法としては、熱板溶着、超音波溶着、高周波溶着などが挙げられる。局部的に多孔質層の融点以上の温度にして多孔質層を溶融することにより、多孔質層と極板を一体化させることができる。 In the step (c), examples of the method for welding the porous layer to the electrode plate include hot plate welding, ultrasonic welding, and high frequency welding. The porous layer and the electrode plate can be integrated by melting the porous layer locally at a temperature equal to or higher than the melting point of the porous layer.
次に本発明の実施例を説明する。本実施例では、前述した図１に基づいて構成した。まず、コバルト酸リチウム３ｋｇを、呉羽化学（株）製ＰＶＤＦ＃１３２０（固形分１２％のＮＭＰ溶液）１ｋｇ、アセチレンブラック９０ｇおよび適量のＮＭＰとともに双腕式練合機にて攪拌し、正極ペーストを作製した。このペーストを１５μｍ厚のアルミニウム箔に塗布乾燥し、総厚が１６０μｍとなるように圧延した後、円筒型１８６５０に挿入可能な幅にスリットし、正極1を得た。 Next, examples of the present invention will be described. The present embodiment is configured based on FIG. 1 described above. First, 3 kg of lithium cobaltate was stirred with a double-arm kneader together with 1 kg of PVDF # 1320 (NMP solution having a solid content of 12%) manufactured by Kureha Chemical Co., Ltd., 90 g of acetylene black, and an appropriate amount of NMP. Produced. The paste was applied and dried on a 15 μm thick aluminum foil, rolled to a total thickness of 160 μm, and then slit into a width that could be inserted into a cylindrical mold 18650 to obtain the positive electrode 1.
一方、人造黒鉛３ｋｇを、日本ゼオン（株）製スチレン−ブタジエン共重合体ゴム粒子結着剤ＢＭ−４００Ｂ（固形分４０％）７５ｇ、ＣＭＣ３０ｇおよび適量の水とともに双
腕式練合機にて攪拌し、負極ペーストを作製した。このペーストを１０μｍ厚の銅箔に塗布乾燥し、総厚が１８０μｍとなるように圧延した後、円筒型１８６５０に挿入可能な幅にスリットし、負極５を得た。
On the other hand, 3 kg of artificial graphite was stirred in a double-arm kneader together with 75 g of styrene-butadiene copolymer rubber particle binder BM-400B (solid content 40%), 30 g of CMC and an appropriate amount of water manufactured by Nippon Zeon Co., Ltd. A negative electrode paste was prepared. This paste was applied and dried on a copper foil having a thickness of 10 μm, rolled to a total thickness of 180 μm, and then slit into a width that could be inserted into a cylindrical mold 18650 to obtain the negative electrode 5.
一方、メディアン径０．３μｍのアルミナ９７０ｇを、日本ゼオン（株）製ポリアクリロニトリル変性ゴム結着剤ＢＭ−７２０Ｈ（固形分８％）３７５ｇおよび適量のＮＭＰとともに双腕式練合機にて攪拌し、絶縁層ペーストを作製した。このペーストを厚さ１０μｍのポリプロピレン不織布４上にグラビア方式により１０μｍ塗布し、１２０℃真空減圧下で１０時間乾燥した。 On the other hand, 970 g of alumina having a median diameter of 0.3 μm was stirred in a double arm kneader together with 375 g of polyacrylonitrile modified rubber binder BM-720H (solid content 8%) manufactured by Nippon Zeon Co., Ltd. and an appropriate amount of NMP. An insulating layer paste was prepared. This paste was applied to a 10 μm thick polypropylene nonwoven fabric 4 by a gravure method and dried at 120 ° C. under vacuum under reduced pressure for 10 hours.
次に、高耐熱絶縁層３を配したポリプロピレン不織布４の、絶縁層を配していない面を負極５の両側に重ね合わせて、１８０℃で熱板溶着させた。さらにこうして作製した負極板と正極１とをポリエチレンセパレータ２を介して重ね合わせて捲回構成し、所定の長さで切断して電極群を作製した。次に電極群を電槽缶内に挿入し、ＥＣ・ＤＭＣ・ＥＭＣ混合溶媒にＬｉＰＦ6を１ＭとＶＣを３％溶解させた電解液を、５．５ｇ添加して封口し、円筒型１８６５０リチウム二次電池を作製した。これを実施例１とする。 Next, the surface of the polypropylene nonwoven fabric 4 provided with the high heat-resistant insulating layer 3 on which the insulating layer was not provided was superposed on both sides of the negative electrode 5 and was hot-plate welded at 180 ° C. Furthermore, the negative electrode plate thus produced and the positive electrode 1 were overlapped via a polyethylene separator 2 to form a winding, and cut into a predetermined length to produce an electrode group. Next, the electrode group was inserted into a battery case, and 5.5 g of an electrolytic solution in which 1M of LiPF 6 and 3% of VC were dissolved in an EC / DMC / EMC mixed solvent was added and sealed. A secondary battery was produced. This is Example 1.
次に本発明の実施例２を説明する。図２は本実施例２におけるリチウム二次電池の電極の構成図である。なお、以下実施例１の構成と同じ部分については同一の符号を付与してある。 Next, a second embodiment of the present invention will be described. FIG. 2 is a configuration diagram of electrodes of the lithium secondary battery in the second embodiment. In the following description, the same parts as those in the first embodiment are denoted by the same reference numerals.
実施例１と同様にして耐熱性絶縁層３を形成し、ポリプロピレン不織布４と一体化させた負極５と正極１とを、ポリエチレンセパレータ２を用いずに重ね合わせて捲回構成し、以下実施例１と同様にして、リチウム二次電池を作製した。これを実施例２とする。 In the same manner as in Example 1, the heat-resistant insulating layer 3 was formed, and the negative electrode 5 and the positive electrode 1 integrated with the polypropylene nonwoven fabric 4 were overlapped without using the polyethylene separator 2, and were wound. In the same manner as in Example 1, a lithium secondary battery was produced. This is Example 2.
次に比較例１、２、３を説明する。図３、４、５はそれぞれ比較例１、２、３におけるリチウム二次電池の電極の構成図である。 Next, Comparative Examples 1, 2, and 3 will be described. 3, 4, and 5 are configuration diagrams of electrodes of lithium secondary batteries in Comparative Examples 1, 2, and 3, respectively.
実施例１と同様にして耐熱性絶縁層３をポリプロピレン不織布４上に塗布形成し、負極５と一体化させることなく、正極１及び負極５と重ね合わせて捲回構成し、以下実施例１と同様にして、リチウム二次電池を作製した。これを比較例１とする。 The heat-resistant insulating layer 3 was applied and formed on the polypropylene nonwoven fabric 4 in the same manner as in Example 1 and was wound up with the positive electrode 1 and the negative electrode 5 without being integrated with the negative electrode 5. Similarly, a lithium secondary battery was produced. This is referred to as Comparative Example 1.
さらに、実施例１と同様にして作製した絶縁層ペーストを、負極５の両側にグラビア方式で塗布し、ポリプロピレン不織布４を両側に貼り合せて１２０℃真空減圧下で１０時間乾燥した。次に、こうして作製した負極板と正極１とをポリエチレンセパレータ２を介して重ね合わせて捲回構成し、以下実施例１と同様にして、リチウム二次電池を作製した。これを比較例２とする。 Furthermore, the insulating layer paste produced in the same manner as in Example 1 was applied to both sides of the negative electrode 5 by a gravure method, and the polypropylene nonwoven fabric 4 was bonded to both sides and dried at 120 ° C. under vacuum under reduced pressure for 10 hours. Next, the negative electrode plate thus produced and the positive electrode 1 were overlapped with a polyethylene separator 2 to form a wound, and a lithium secondary battery was produced in the same manner as in Example 1 below. This is referred to as Comparative Example 2.
さらに、耐熱性絶縁層３を形成せずに、正極１と負極５とをポリエチレンセパレータ２を介して重ね合わせて捲回構成し、以下実施例１と同様にして、リチウム二次電池を作製した。これを比較例３とする。 Furthermore, without forming the heat-resistant insulating layer 3, the positive electrode 1 and the negative electrode 5 were overlapped with each other via a polyethylene separator 2, and then a lithium secondary battery was manufactured in the same manner as in Example 1. . This is referred to as Comparative Example 3.
これらの電池を、以下に示す方法にて評価した。
（絶縁試験）
上述した実施例１、２及び比較例１、２、３の電池について、電解液を添加する前の状態で正・負極間の抵抗値を測定し、捲回時の巻きずれによる絶縁不良の発生頻度を評価した。その結果を表１中に示す。
（サイクル試験）
上述した実施例１、２及び比較例１、２、３の電池を２０℃環境において以下の条件で５００サイクルのサイクル試験を行った。２サイクル目の放電容量に対する５００サイク
ル後の放電容量（容量維持率）を評価した。その結果を表１中に示す。
（１） 定電流充電：１４００ｍＡ（終止電圧４．２Ｖ）
（２） 定電圧充電：４．２Ｖ（終止電流１００ｍＡ）
（３） 定電流放電：２０００ｍＡ（終止電圧３Ｖ）
（釘刺し安全性）
上述した実施例１、２及び比較例１、２、３の電池を２０℃環境において、以下の充電を行い、釘刺し試験を行なった。
These batteries were evaluated by the following method.
(Insulation test)
For the batteries of Examples 1 and 2 and Comparative Examples 1, 2 and 3 described above, the resistance value between the positive and negative electrodes was measured before the electrolyte was added, and insulation failure occurred due to winding deviation during winding. Frequency was evaluated. The results are shown in Table 1.
(Cycle test)
The batteries of Examples 1 and 2 and Comparative Examples 1, 2, and 3 described above were subjected to a cycle test of 500 cycles under the following conditions in a 20 ° C. environment. The discharge capacity (capacity retention rate) after 500 cycles with respect to the discharge capacity at the second cycle was evaluated. The results are shown in Table 1.
(1) Constant current charging: 1400 mA (end voltage 4.2 V)
(2) Constant voltage charging: 4.2V (end current 100mA)
(3) Constant current discharge: 2000 mA (end voltage 3 V)
(Nail penetration safety)
The batteries of Examples 1 and 2 and Comparative Examples 1, 2 and 3 described above were charged in the environment of 20 ° C. and subjected to a nail penetration test.
（１）定電流充電：１４００ｍＡ（終止電圧４．２５Ｖ）
（２）定電圧充電：４．２５Ｖ（終止電流１００ｍＡ）
充電後の電池について、２．７ｍｍ径の鉄製丸釘を、２０℃環境下で５ｍｍ/秒の速度で貫通させたときの発熱状態を観測した。この電池の貫通箇所における６０秒後の到達温度を表１中に示した。
(1) Constant current charging: 1400 mA (end voltage 4.25 V)
(2) Constant voltage charging: 4.25V (end current 100mA)
Regarding the battery after charging, a heat generation state was observed when a 2.7 mm diameter iron round nail was penetrated at a speed of 5 mm / second in a 20 ° C. environment. Table 1 shows the temperature reached after 60 seconds at the penetration portion of the battery.
以下、順を追って評価結果を記す。 The evaluation results are described below in order.
まず絶縁試験の結果であるが、耐熱性絶縁層ないしはポリプロピレン不織布が電極と一体化していない比較例１及び３において絶縁不良となる電池が見られた。これらの電池を分解観察したところ、捲回構成時のものと思われる電極等の巻きずれが確認された。それに対し、耐熱性絶縁層ないしはポリプロピレン不織布が電極と一体化された実施例１、２、比較例２の電池では絶縁不良は見られなかった。このことから、耐熱性絶縁層ないしはポリプロピレン不織布を電極と一体化させることにより、巻きずれによる絶縁不良を防ぐ効果があることがわかった。 First, as a result of the insulation test, a battery having insulation failure was found in Comparative Examples 1 and 3 in which the heat-resistant insulating layer or the polypropylene nonwoven fabric was not integrated with the electrode. As a result of disassembling and observing these batteries, it was confirmed that windings of electrodes and the like considered to be those at the time of the winding configuration were lost. On the other hand, in the batteries of Examples 1 and 2 and Comparative Example 2 in which the heat-resistant insulating layer or the polypropylene nonwoven fabric was integrated with the electrode, no insulation failure was observed. From this, it has been found that by integrating a heat-resistant insulating layer or a polypropylene nonwoven fabric with the electrode, there is an effect of preventing insulation failure due to winding deviation.
次にサイクル試験の結果であるが、比較例２の電池が実施例１、２及び比較例１、３の電池に比べ、５００サイクル後の容量維持率が低かった。これは、電極とポリプロピレン不織布を、フィラーと結着剤の混合物で接着しているため、電極の凹凸を埋めるようにフィラーと結着剤が存在し、その結果電極間の抵抗にばらつきが生じたためと考えられる。電極間の抵抗にばらつきが生じたことにより局所的に電流が集中し、その結果、電池の劣化が促進されたものと考えられる。 Next, as a result of the cycle test, the capacity retention rate after 500 cycles was lower in the battery of Comparative Example 2 than in the batteries of Examples 1 and 2 and Comparative Examples 1 and 3. This is because the electrode and polypropylene nonwoven fabric are bonded with a mixture of filler and binder, so the filler and binder exist to fill the unevenness of the electrode, resulting in variations in resistance between the electrodes. it is conceivable that. It is considered that current was concentrated locally due to variations in resistance between the electrodes, and as a result, deterioration of the battery was promoted.
次に釘刺し試験の結果について説明する。 Next, the results of the nail penetration test will be described.
耐熱性絶縁層の有無についてであるが、耐熱性絶縁層が存在しない比較例３が大きく過熱していた。その一方で耐熱絶縁層が電極と一体化されている実施例１、２及び比較例４は釘刺し後の過熱が大幅に抑制されていることがわかる。これら試験後の電池を分解観察したところ、ポリエチレンセパレータについては広範囲に溶融しているが、実施例１、２及び比較例２については、耐熱性絶縁層がその原形を留めていることがわかった。このこ
とから、耐熱性絶縁層の耐熱性が十分な場合、釘刺し後に起こる短絡による発熱においても膜構造は破壊されず、短絡箇所の拡大を抑止できたため、大幅な過熱を防げたものと考えられる。
Regarding the presence or absence of the heat-resistant insulating layer, Comparative Example 3 in which no heat-resistant insulating layer was present was greatly overheated. On the other hand, in Examples 1 and 2 and Comparative Example 4 in which the heat-resistant insulating layer is integrated with the electrode, it can be seen that overheating after nail penetration is greatly suppressed. When the batteries after these tests were disassembled and observed, the polyethylene separator was melted in a wide range, but in Examples 1, 2 and Comparative Example 2, it was found that the heat-resistant insulating layer retained its original shape. . From this, when the heat resistance of the heat-resistant insulating layer is sufficient, the film structure was not destroyed in the heat generation caused by the short circuit that occurred after nail penetration, and the expansion of the short-circuited part could be suppressed, so it was considered that the overheating was prevented. It is done.
一方、耐熱性絶縁層がポリプロピレン不織布上に形成され、電極と一体化させることなく作製された比較例１は、比較例３の電池よりは低い温度であるが、過熱されていることがわかる。電池を分解して調べたところ、前述したポリプロピレン不織布の収縮に伴い、耐熱性絶縁層も変形していることが確認できた。この理由として、耐熱性絶縁層の構造は接着形成される基板（本比較例１においてはポリプロピレン不織布）によって保持されるため、如何に絶縁層自身に耐熱性があっても、収縮のような基板の形状変化にやむなく追従せざるを得ないことが反映された結果といえる。 On the other hand, it can be seen that Comparative Example 1 in which the heat-resistant insulating layer was formed on the polypropylene nonwoven fabric and was not integrated with the electrode had a lower temperature than the battery of Comparative Example 3, but was overheated. When the battery was disassembled and examined, it was confirmed that the heat-resistant insulating layer was also deformed with the shrinkage of the polypropylene nonwoven fabric described above. The reason for this is that the structure of the heat-resistant insulating layer is held by a substrate that is formed by adhesion (in this comparative example 1, a polypropylene nonwoven fabric). It can be said that the result reflects the necessity of following the shape change.
また、実施例１、２及び比較例２を比較すると、ポリエチレンセパレータのない実施例２の電池の釘刺し試験後の温度が高かった。これは、１００℃を越える高温になった場合、ポリエチレンセパレータが溶融し、それ自身が持つ細孔を閉ざすことによりイオンの移動を遮断し、短絡の継続を止めたため（シャットダウン機能）と考えられる。高耐熱性絶縁層の存在によって、短絡点の拡大を防ぎ、異常過熱を抑制することができるが、本実施例のように、ポリエチレン、ポリプロピレンセパレータのようなシャットダウン機能をもつ膜を併用することにより、さらに電池の安全性を高めることができる。 Moreover, when Example 1, 2 and Comparative Example 2 were compared, the temperature after the nail penetration test of the battery of Example 2 without a polyethylene separator was high. This is thought to be because when the temperature exceeded 100 ° C., the polyethylene separator melted and the movement of ions was blocked by closing the pores of the polyethylene separator, thereby stopping the short circuit (shutdown function). The presence of a high heat-resistant insulating layer can prevent the expansion of short-circuit points and suppress abnormal overheating, but by using a film having a shutdown function such as polyethylene and polypropylene separators in combination with this example. Furthermore, the safety of the battery can be improved.
本発明にかかるリチウム二次電池は優れた安全性と電気特性を有し、携帯電子機器等の電源として有用である。 The lithium secondary battery according to the present invention has excellent safety and electrical characteristics, and is useful as a power source for portable electronic devices and the like.
１ 正極
２ ポリエチレンセパレータ
３ ポリプロピレン不織布上に形成した耐熱性絶縁層
４ ポリプロピレン不織布
５ 負極
DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Polyethylene separator 3 The heat resistant insulating layer formed on the polypropylene nonwoven fabric 4 Polypropylene nonwoven fabric 5 Negative electrode
Claims (5)
In a method for producing a lithium secondary battery having an electrode group in which a positive electrode, a negative electrode, and a porous layer made of a resin are laminated or wound, a filler and a binder are dispersed in a solvent on one surface of the porous layer A step of applying the solution, a step of drying the porous layer to which the solution has been applied to form a heat-resistant insulating layer made of a filler and a binder, and the other surface of the porous layer is connected to the positive electrode or the negative electrode. A method for producing a lithium secondary battery, comprising the steps of superimposing and welding the porous layer and the electrode plate on any electrode plate.
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