JP2006302877A - Nonaqueous electrolyte battery and its manufacturing method - Google Patents
Nonaqueous electrolyte battery and its manufacturing method Download PDFInfo
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- JP2006302877A JP2006302877A JP2006075832A JP2006075832A JP2006302877A JP 2006302877 A JP2006302877 A JP 2006302877A JP 2006075832 A JP2006075832 A JP 2006075832A JP 2006075832 A JP2006075832 A JP 2006075832A JP 2006302877 A JP2006302877 A JP 2006302877A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Cell Electrode Carriers And Collectors (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、非水電解質電池とその製造方法に関し、さらに詳しくは、携帯用電子機器、電気自動車、ロードレベリングなどの電源として使用するのに適した非水電解質電池とその製造方法に関するものである。 The present invention relates to a nonaqueous electrolyte battery and a method for manufacturing the same, and more particularly to a nonaqueous electrolyte battery suitable for use as a power source for portable electronic devices, electric vehicles, road leveling, and the like, and a method for manufacturing the same. .
非水電解質電池の一種であるリチウムイオン二次電池は、エネルギー密度が高いという特徴から、携帯電話やノート型パーソナルコンピューターなどの携帯機器の電源として広く用いられている。また、環境問題への配慮から繰り返し充電できる二次電池の重要性が増大しており、携帯機器以外にも、自動車、電気椅子や家庭用、業務用の電力貯蔵システムへの適用が検討されている。 A lithium ion secondary battery, which is a type of nonaqueous electrolyte battery, is widely used as a power source for portable devices such as mobile phones and notebook personal computers because of its high energy density. In addition, the importance of secondary batteries that can be repeatedly charged is increasing due to considerations for environmental issues. In addition to portable devices, application to automobiles, electric chairs, household and commercial power storage systems is being considered. Yes.
現行のリチウムイオン二次電池は、正極と負極とセパレータを円筒状、あるいは扁平状に捲回して渦巻状の捲回体を形成し、アルミニウムやステンレスなどの金属缶に挿入した後、電解液を注液し、封口することにより作製される。捲回体を構成する正負極シートにおいては、充電時に正極から負極に移動するリチウムが金属状態で析出しないように、対向する負極シートの長さおよび幅を正極に比べて大きくとり、さらに絶縁のためセパレータの幅を大きくするのが一般的である。 In current lithium ion secondary batteries, a positive electrode, a negative electrode, and a separator are wound into a cylindrical shape or a flat shape to form a spiral wound body, which is inserted into a metal can such as aluminum or stainless steel. It is prepared by pouring and sealing. In the positive and negative electrode sheets constituting the wound body, the length and width of the opposing negative electrode sheet are made larger than those of the positive electrode so that lithium moving from the positive electrode to the negative electrode during charging does not precipitate in a metallic state, Therefore, it is common to increase the width of the separator.
リチウムイオン二次電池用セパレータは、電池の高容量化のため、厚さが20μm以下の非常に薄いものが使用されている。そのため、セパレータに傷があったり、あるいは電池が異常な衝撃を受けてセパレータがずれたりすると、正負極が接触して短絡する可能性がある。 As a separator for a lithium ion secondary battery, a very thin one having a thickness of 20 μm or less is used in order to increase the capacity of the battery. Therefore, if the separator is damaged or the battery is subjected to an abnormal impact and the separator is displaced, the positive and negative electrodes may come into contact with each other and short-circuit.
正極活物質含有層の電気抵抗は比較的大きいため、短絡により負極(負極活物質含有層あるいは負極集電体)と正極活物質含有層が接触したとしても、短絡電流は小さく短絡による発熱量も小さいが、負極活物質含有層の電気抵抗は正極と比べて低いため、負極と正極集電体の露出面が接触すると、短絡電流が大きくなり発熱量も大きなものとなる。 Since the electric resistance of the positive electrode active material-containing layer is relatively large, even if the negative electrode (negative electrode active material-containing layer or negative electrode current collector) and the positive electrode active material-containing layer contact each other due to a short circuit, the short-circuit current is small and the amount of heat generated by the short circuit Although it is small, since the electrical resistance of the negative electrode active material-containing layer is lower than that of the positive electrode, when the negative electrode and the exposed surface of the positive electrode current collector are in contact with each other, the short-circuit current increases and the amount of heat generation increases.
リチウムイオン二次電池では、上記捲回体の巻き始め端部および巻き終わり端部の少なくとも一方において、正極の集電体の露出部と負極とを対向させるため、この部分で短絡を生じると、電池に異常が生じる可能性が高くなる。 In the lithium ion secondary battery, at least one of the winding start end and the winding end end of the wound body, the exposed portion of the positive electrode current collector and the negative electrode are opposed to each other. There is a high possibility that abnormality will occur in the battery.
上記正極の集電体の露出部と負極との対向部における問題を回避するため、塗工乾燥などの方法によりポリフッ化ビニリデンなどの絶縁層を形成する方法(特許文献1)や、アルミナなどの耐熱性を有する粉体をバインダーで結着して絶縁性被膜を形成する方法(特許文献2)が提案されている。
しかし、ポリフッ化ビニリデンなどの結晶性の高い樹脂のみで絶縁層を形成する場合、塗液を乾燥する際に樹脂分子が収縮して塗膜自体が収縮し、集電箔との接着性が低下してしまう。このため、絶縁層が集電箔より剥離しやすくなる。また、アルミナのように硬い粒子を絶縁性被膜に含有させた場合、被膜の収縮を抑えるのに若干の効果は認められるものの、膜がもろくなるため、やはり絶縁性被膜が剥離する問題は残存する。この現象は、集電箔のエッジ部に特に顕著に見られることから、本来期待する絶縁効果が得られない。 However, when an insulating layer is formed only with a highly crystalline resin such as polyvinylidene fluoride, the resin molecules shrink and the coating itself shrinks when the coating liquid is dried, resulting in a decrease in adhesion to the current collector foil. Resulting in. For this reason, an insulating layer becomes easy to peel from a current collection foil. In addition, when hard particles such as alumina are contained in the insulating film, although a slight effect is observed in suppressing the shrinkage of the film, the film becomes brittle, so the problem that the insulating film peels still remains. . Since this phenomenon is particularly noticeable at the edge of the current collector foil, the expected insulating effect cannot be obtained.
本発明は、上記事情に鑑みてなされたものであって、正極の集電体露出部と負極との間に安定性の高い絶縁性樹脂膜を配置することにより、非水電解質電池の安全性を向上させようとするものである。 The present invention has been made in view of the above circumstances, and by disposing a highly stable insulating resin film between the current collector exposed portion of the positive electrode and the negative electrode, the safety of the nonaqueous electrolyte battery It is going to improve.
本発明の非水電解質電池は、(1)正極集電体と、前記正極集電体上に形成された正極活物質含有層とを含む正極と、(2)負極集電体と、前記負極集電体上に形成された負極活物質含有層とを含む負極と、(3)前記正極と前記負極との間に配置されたセパレータとを備える非水電解質電池であって、前記正極は、前記正極集電体の一部に前記正極活物質含有層が形成されていない正極集電体露出部を有し、前記正極集電体露出部と前記負極活物質含有層とが、前記セパレータを介して対向する部分では、それらの間に、150℃以上の耐熱温度を有する耐熱性樹脂を基体とする樹脂膜であって、その内部に熱可塑性樹脂を含む絶縁性樹脂膜が配置されていることを特徴とする。 The nonaqueous electrolyte battery of the present invention includes (1) a positive electrode current collector, a positive electrode including a positive electrode active material-containing layer formed on the positive electrode current collector, (2) a negative electrode current collector, and the negative electrode A negative electrode including a negative electrode active material-containing layer formed on a current collector, and (3) a non-aqueous electrolyte battery comprising a separator disposed between the positive electrode and the negative electrode, The positive electrode current collector has a positive electrode current collector exposed portion in which the positive electrode active material-containing layer is not formed, and the positive electrode current collector exposed portion and the negative electrode active material-containing layer include the separator. In a portion facing each other, a resin film having a heat resistant resin having a heat resistant temperature of 150 ° C. or higher as a base and an insulating resin film containing a thermoplastic resin disposed therein is disposed therebetween. It is characterized by that.
また、本発明の非水電解質電池の製造方法は、(1)正極集電体と、前記正極集電体上に形成された正極活物質含有層と、前記正極集電体の一部に前記正極活物質含有層が形成されていない正極集電体露出部とを含む正極と、(2)負極集電体と、前記負極集電体上に形成された負極活物質含有層とを含む負極と、(3)前記正極と前記負極との間に配置されたセパレータとを備える非水電解質電池の製造方法であって、150℃以上の耐熱温度を有する耐熱性樹脂を溶媒に溶解させる工程と、前記耐熱性樹脂を溶解してなる溶液中に熱可塑性樹脂を分散させてスラリーを作製する工程と、前記スラリーを前記正極集電体露出部、前記負極および前記セパレータから選ばれる少なくとも1つに塗布して乾燥させる工程とを含み、前記工程により、前記正極集電体露出部と前記負極活物質含有層とが、前記セパレータを介して対向する部分において、それらの間に、150℃以上の耐熱温度を有する耐熱性樹脂を基体とする樹脂膜であって、その内部に熱可塑性樹脂を含む絶縁性樹脂膜を配置することを特徴とする。 The nonaqueous electrolyte battery manufacturing method of the present invention includes (1) a positive electrode current collector, a positive electrode active material-containing layer formed on the positive electrode current collector, and a part of the positive electrode current collector. A negative electrode including a positive electrode current collector exposed portion in which a positive electrode active material-containing layer is not formed, (2) a negative electrode current collector, and a negative electrode active material-containing layer formed on the negative electrode current collector And (3) a method for producing a non-aqueous electrolyte battery comprising a separator disposed between the positive electrode and the negative electrode, wherein a heat-resistant resin having a heat-resistant temperature of 150 ° C. or higher is dissolved in a solvent; A step of preparing a slurry by dispersing a thermoplastic resin in a solution obtained by dissolving the heat-resistant resin, and at least one selected from the positive electrode current collector exposed portion, the negative electrode, and the separator. Applying and drying, by the above process, In the portion where the positive electrode current collector exposed portion and the negative electrode active material-containing layer face each other with the separator interposed therebetween, a resin film having a heat resistant resin having a heat resistant temperature of 150 ° C. or higher as a base therebetween An insulating resin film containing a thermoplastic resin is disposed inside.
本発明により、正極集電体露出部と負極との短絡の発生を防ぎ、安全性の高い非水電解質電池を得ることができる。 By this invention, generation | occurrence | production of the short circuit of a positive electrode collector exposed part and a negative electrode can be prevented, and a highly safe nonaqueous electrolyte battery can be obtained.
本発明において、正極集電体露出部と負極活物質含有層との間に配置される絶縁性樹脂膜は、150℃以上の耐熱温度を有する耐熱性樹脂を基体とし、その内部に熱可塑性樹脂を含む形態を有するものである。ここで、150℃以上の耐熱温度を有する耐熱性樹脂とは、150℃まで加熱しても溶融、軟化、変形が生じない樹脂をいう。 In the present invention, the insulating resin film disposed between the exposed portion of the positive electrode current collector and the negative electrode active material-containing layer uses a heat resistant resin having a heat resistant temperature of 150 ° C. or more as a base, and a thermoplastic resin therein. It has a form containing. Here, the heat resistant resin having a heat resistant temperature of 150 ° C. or higher refers to a resin that does not melt, soften, or deform even when heated to 150 ° C.
基体となる耐熱性樹脂の耐熱温度を150℃以上としたのは、高温でも絶縁膜としての機能を安定に維持させるためであり、少なくとも、セパレータがシャットダウンを生じる温度(およそ100〜140℃)よりも高温まで安定性を確保するためである。このような耐熱性樹脂としては、150℃以上の融点を有するものを用いることができる。また、この耐熱性樹脂は、絶縁性に優れ、電極の捲回時に受ける押し付け、こすれなどに対する強度、電池の落下時に受ける衝撃に対する強度に優れるものが望ましく、非水電解質に対する安定性にも優れたものが望ましい。 The reason why the heat-resistant temperature of the heat-resistant resin as the substrate is set to 150 ° C. or more is to stably maintain the function as an insulating film even at high temperatures, at least from the temperature at which the separator is shut down (approximately 100 to 140 ° C.). This is to ensure stability up to high temperatures. As such a heat resistant resin, a resin having a melting point of 150 ° C. or higher can be used. In addition, this heat-resistant resin should have excellent insulation properties, and it should have excellent strength against pressing and rubbing received when the electrode is wound, strength against impact received when the battery is dropped, and excellent stability against non-aqueous electrolytes. Things are desirable.
上記耐熱性樹脂としては、分子量が大きく結晶性の高いものが望ましく、ポリフッ化ビニリデンおよびそのカルボン酸変性体あるいはマレイン酸変性体などの誘導体、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、エポキシ系樹脂、ポリアミド系樹脂などが好適に使用される。 The heat-resistant resin preferably has a large molecular weight and high crystallinity, such as polyvinylidene fluoride and derivatives thereof such as carboxylic acid-modified or maleic acid-modified products, vinylidene fluoride-hexafluoropropylene copolymers, and epoxy resins. Polyamide resins and the like are preferably used.
また、電極の集電体が金属箔である場合、耐熱性樹脂の融点を上記金属箔の融点よりも低くすることにより、集電用のタブを金属箔に溶接する際に、タブと金属箔との間に耐熱性樹脂が介在していたとしても、超音波溶接などの方法により、耐熱性樹脂を融解させながらタブと金属箔とを溶接することも可能となる。 Further, when the current collector of the electrode is a metal foil, when the current collecting tab is welded to the metal foil by making the melting point of the heat resistant resin lower than the melting point of the metal foil, the tab and the metal foil Even if a heat resistant resin is interposed between the tab and the metal foil, it is possible to melt the heat resistant resin by a method such as ultrasonic welding.
なお、上記耐熱性樹脂として利用できるのは、上記高融点の樹脂に限定されるわけではなく、融点が明確に規定されない樹脂であっても、150℃以上の温度まで安定に存在できるものであれば使用することができる。例えば、ポリフェニルスルホンおよびポリエーテルスルホンなどのポリスルホン系樹脂、ポリイミド系樹脂など、軟化点が150℃以上の樹脂などを用いることも可能である。 The heat-resistant resin that can be used is not limited to the high-melting point resin, and even a resin whose melting point is not clearly defined can be stably present up to a temperature of 150 ° C. or higher. Can be used. For example, it is also possible to use a resin having a softening point of 150 ° C. or higher, such as a polysulfone resin such as polyphenylsulfone and polyethersulfone, or a polyimide resin.
ここで、上記耐熱性樹脂から絶縁性樹脂膜を形成する場合、上記耐熱性樹脂を可溶性溶媒に溶解し、その後に集電体などに塗布・乾燥させる工程を経るのが一般的であるが、上述したような結晶性の高い樹脂では、溶媒乾燥時の収縮が大きく、また柔軟性に乏しいため、塗布対象物から剥離するという問題を生じやすい。そのため、本発明においては、耐熱性樹脂を基体とする絶縁性樹脂膜の内部に熱可塑性樹脂を含有させ、上記溶媒乾燥時の収縮を緩和するとともに、膜に柔軟性を付与し、絶縁性樹脂膜の耐久性を向上させる。 Here, in the case of forming an insulating resin film from the heat resistant resin, it is common to go through a step of dissolving the heat resistant resin in a soluble solvent and then applying and drying the current collector, A resin having high crystallinity as described above has a large shrinkage at the time of solvent drying and lacks flexibility, so that it tends to cause a problem of peeling from an application target. Therefore, in the present invention, an insulating resin film containing a heat-resistant resin as a base material contains a thermoplastic resin to alleviate shrinkage when the solvent is dried and to impart flexibility to the film. Improve membrane durability.
上記熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体などのポリオレフィン樹脂、エチレン−酢酸ビニル共重合体、ポリメチルメタクリレート、エチレン−メチルメタクリレート共重合体およびそれらの誘導体が好適に用いられ、耐溶剤性を向上させる目的で、上記樹脂の一部を架橋したものを用いることもできる。 As the thermoplastic resin, polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polymethyl methacrylate, ethylene-methyl methacrylate copolymer and derivatives thereof are preferably used. For the purpose of improving the solvent resistance, it is possible to use one obtained by crosslinking a part of the resin.
上記熱可塑性樹脂は、絶縁性樹脂膜中でできるだけ均一に分散した状態をとることが望ましく、例えば、個々の熱可塑性樹脂粒子の周囲が耐熱性樹脂で覆われた海島状の構造をとることが望ましい。これにより、耐熱性樹脂の持つ成膜性、強度を維持したまま、熱可塑性樹脂による収縮抑制効果や柔軟性付与効果が得られやすくなるからである。 The thermoplastic resin is desirably dispersed as uniformly as possible in the insulating resin film. For example, each thermoplastic resin particle may have a sea-island structure in which the periphery of each thermoplastic resin particle is covered with a heat-resistant resin. desirable. This is because it becomes easy to obtain the shrinkage-suppressing effect and the flexibility-imparting effect of the thermoplastic resin while maintaining the film formability and strength of the heat-resistant resin.
上記熱可塑性樹脂としては、その粒径が絶縁性樹脂膜の厚みよりも小さいものを用いるのがよく、具体的には、数平均粒子径で0.1〜50μmであることが好ましく、30μm以下のものがより好適に用いられる。また、その形状は限定されるものではなく、種々の形状のものが使用可能であるが、均一分散の点からは略球状の粒子が好ましく用いられる。 As the thermoplastic resin, one having a particle size smaller than the thickness of the insulating resin film is preferably used. Specifically, the number average particle size is preferably 0.1 to 50 μm, preferably 30 μm or less. Are more preferably used. Moreover, the shape is not limited, and various shapes can be used. From the viewpoint of uniform dispersion, substantially spherical particles are preferably used.
上記絶縁性樹脂膜中に含有させる熱可塑性樹脂の量は、耐熱性樹脂と熱可塑性樹脂との合計重量に対して、1質量%以上とすることにより、上記収縮抑制効果や柔軟性付与効果が得られやすくなり、5質量%以上であればより柔軟性が得られるので好ましく、一方、80質量%以下とすることにより、絶縁性樹脂膜の強度が向上し、50質量%以下であればより好適である。 The amount of the thermoplastic resin contained in the insulating resin film is 1% by mass or more based on the total weight of the heat-resistant resin and the thermoplastic resin, so that the shrinkage-suppressing effect and the flexibility-imparting effect are achieved. It is easy to obtain, and it is preferable because the flexibility is obtained if it is 5% by mass or more. On the other hand, by setting it to 80% by mass or less, the strength of the insulating resin film is improved. Is preferred.
上記絶縁性樹脂膜の厚みは、捲回体の厚みを考慮すると薄いほうが望ましいが、あまり薄くなると強度が不足して絶縁層としての機能が損なわれるため、5μm以上とするのがよく、10μm以上であればより好適であり、一方、30μm以下とするのがよく、20μm以下であればより好適である。 The thickness of the insulating resin film is preferably thinner in consideration of the thickness of the wound body. However, if the thickness is too thin, the strength becomes insufficient and the function as an insulating layer is impaired, and the thickness is preferably 5 μm or more. If it is, it is more suitable, and on the other hand, it is good to set it as 30 micrometers or less, and if it is 20 micrometers or less, it is more suitable.
図1に本発明の非水電解質電池に用いる捲回体の一例の要部断面図を示す。図1において、正極3は、正極集電体1と、正極集電体1上に形成された正極活物質含有層2と、正極集電体1の一部に正極活物質含有層2が形成されていない正極集電体露出部8とを備えている。負極6は、負極集電体4と、負極集電体4上に形成された負極活物質含有層5とを備えている。正極3と負極6との間には、セパレータ7が配置されている。
FIG. 1 shows a cross-sectional view of an essential part of an example of a wound body used in the nonaqueous electrolyte battery of the present invention. In FIG. 1, a positive electrode 3 includes a positive electrode
また、正極集電体露出部8と負極活物質含有層5とが、セパレータ7を介して対向する部分では、正極集電体露出部8上に絶縁性樹脂膜9が配置されている。さらに、最外周の正極集電体露出部8上には、正極タブ10が溶接されている。
Further, an insulating
図1の捲回体は、正極3が最外周に位置する例を示したものであり、正極3の最外周(第1周目)においては、正極活物質含有層2は正極集電体1の片面にのみ形成されているが、正極3の第2周目からは、正極活物質含有層2は正極集電体1の両面に形成されている。また、上記捲回体において、負極集電体露出部は負極6の最内周側に位置しており、図1では図示されていない。
The wound body of FIG. 1 shows an example in which the positive electrode 3 is located on the outermost periphery. In the outermost periphery (first periphery) of the positive electrode 3, the positive electrode active material-containing
図2に本発明の非水電解質電池に用いる捲回体の他の一例の要部断面図を示す。図2において、正極3は、正極集電体1と、正極集電体1上に形成された正極活物質含有層2と、正極集電体1の一部に正極活物質含有層2が形成されていない正極集電体露出部8とを備えている。負極6は、負極集電体4と、負極集電体4上に形成された負極活物質含有層5と、負極集電体4の一部に負極活物質含有層5が形成されていない負極集電体露出部11とを備えている。正極3と負極6との間には、セパレータ7が配置されている。
FIG. 2 shows a cross-sectional view of the main part of another example of a wound body used in the nonaqueous electrolyte battery of the present invention. In FIG. 2, the positive electrode 3 includes a positive electrode
また、正極集電体露出部8と負極活物質含有層5とが、セパレータ7を介して対向する部分、及び、負極集電体露出部11と正極集電体露出部8とが、セパレータ7を介して対向する部分では、正極集電体露出部8上に絶縁性樹脂膜9が配置されている。さらに、正極集電体露出部8上には、正極タブ10が溶接されている。
Further, the portion where the positive electrode current collector exposed
図2の捲回体は、負極6が最外周に位置する例を示したものであり、負極6において、負極活物質含有層5は負極集電体4の片面にのみ形成されており、正極3において、正極活物質含有層2は正極集電体1の両面に形成されている。また、正極集電体露出部8上に配置された絶縁性樹脂膜9は、正極活物質含有層2の端部上を覆っている。
The wound body of FIG. 2 shows an example in which the
図2の捲回体では、負極6の端部に負極集電体露出部11が形成され、この負極集電体露出部11が正極集電体露出部8とセパレータ7を介して対向している。負極集電体露出部と正極集電体露出部とが対向する構造の場合、この対向部で短絡が生じる危険がある。もし、上記露出部同士が短絡した場合は、負極活物質含有層と正極集電体露出部との短絡の場合に比べて、さらに大きな電流が流れるので、発熱量が大きくなって電池が危険な状態に陥りやすい。しかし、図2に示すように、正極集電体露出部8と負極活物質含有層5との間に絶縁性樹脂膜9を配置するだけでなく、負極集電体露出部11と正極集電体露出部8との間にも、絶縁性樹脂膜9を配置することにより、正極集電体1と負極活物質含有層5との短絡だけでなく、正極集電体1と負極集電体4との短絡も防ぐことができるため、安全性をさらに向上させることができる。
In the wound body of FIG. 2, the negative electrode current collector exposed portion 11 is formed at the end of the
本発明では、正極集電体露出部および負極活物質含有層が、セパレータを介して対向している状態で、正極集電体露出部と負極活物質含有層との間に絶縁性樹脂膜が配置されていればよいので、正極集電体露出部上に絶縁性樹脂膜を形成した図1に示すような態様に限定されるものではなく、正極集電体露出部と対向する負極活物質含有層上、あるいは正極集電体露出部と負極活物質含有層との間に介在させるセパレータ上に絶縁性樹脂膜を形成するものであってもよい。また、図2に示すように、正極集電体露出部8上に配置された絶縁性樹脂膜9は、正極活物質含有層2の端部上を被覆してもよい。
In the present invention, an insulating resin film is provided between the positive electrode current collector exposed portion and the negative electrode active material-containing layer in a state where the positive electrode current collector exposed portion and the negative electrode active material-containing layer face each other with a separator interposed therebetween. 1 is not limited to the embodiment shown in FIG. 1 in which an insulating resin film is formed on the exposed portion of the positive electrode current collector, and the negative electrode active material facing the exposed portion of the positive electrode current collector. An insulating resin film may be formed on the containing layer or on the separator interposed between the exposed portion of the positive electrode current collector and the negative electrode active material containing layer. As shown in FIG. 2, the insulating
上記絶縁性樹脂膜は、例えば以下の方法により形成することができる。耐熱性樹脂を溶解しかつ熱可塑性樹脂を溶解しない溶媒に、耐熱性樹脂を溶解し、さらに、熱可塑性樹脂を分散させてスラリーを作製する。このスラリーを正極集電体露出部、正極集電体露出部と対向する負極活物質含有層、およびそれらの間に介在させるセパレータの少なくとも1つに塗布し、さらに乾燥させることにより、正極集電体露出部上、あるいはそれと対向する負極活物質含有層上、あるいはそれらの間に介在させるセパレータ上に絶縁性樹脂膜を形成することができる。 The insulating resin film can be formed, for example, by the following method. The heat resistant resin is dissolved in a solvent that dissolves the heat resistant resin and does not dissolve the thermoplastic resin, and the thermoplastic resin is further dispersed to prepare a slurry. The slurry is applied to at least one of the positive electrode current collector exposed portion, the negative electrode active material-containing layer facing the positive electrode current collector exposed portion, and the separator interposed therebetween, and further dried to thereby obtain a positive electrode current collector. An insulating resin film can be formed on the body exposed portion, on the negative electrode active material-containing layer facing it, or on the separator interposed between them.
上記スラリーの形成に用いる溶媒は、特に限定されるものではなく、一例を示せば、耐熱性樹脂としてポリフッ化ビニリデンを用い、熱可塑性樹脂としてポリエチレンなどを用いる場合には、N−メチルピロリドンなどの汎用性の高い溶媒を好適に用いることができる。また、スラリーの塗布は、ダイコータ、グラビアコータ、リバースコータ、スプレーコータなどを用いて行えばよい。 The solvent used for forming the slurry is not particularly limited. For example, when polyvinylidene fluoride is used as the heat-resistant resin and polyethylene is used as the thermoplastic resin, N-methylpyrrolidone or the like is used. A highly versatile solvent can be suitably used. The slurry may be applied using a die coater, gravure coater, reverse coater, spray coater, or the like.
また、絶縁性樹脂膜と、電極あるいはセパレータとの接着性を向上させるために、熱可塑性樹脂が加熱変形もしくは融解する温度まで絶縁性樹脂膜を加熱してもよい。また、加熱の代わりにカレンダーロールなどで加圧するのでもよく、加熱とともに加圧すれば、絶縁性樹脂膜と、電極あるいはセパレータとの接着性がより一層向上するので好ましい。なお、上記加熱を行う場合、より低温で接着性向上効果を得るために、絶縁性樹脂膜に用いる熱可塑性樹脂の融点は、基体となる耐熱性樹脂の融点よりも低いことが望ましい。 Further, in order to improve the adhesion between the insulating resin film and the electrode or the separator, the insulating resin film may be heated to a temperature at which the thermoplastic resin is thermally deformed or melted. Further, instead of heating, pressurization may be performed with a calender roll or the like, and pressurization with heating is preferable because adhesion between the insulating resin film and the electrode or separator is further improved. In addition, when performing the said heating, in order to acquire the adhesive improvement effect at lower temperature, it is desirable for the melting point of the thermoplastic resin used for an insulating resin film to be lower than the melting point of the heat resistant resin used as a base | substrate.
なお、本発明の耐熱性樹脂あるいは熱可塑性樹脂の融点は、日本工業規格(JIS)K 7121の規定に準じて、示差走査熱量計(DSC)を用いて測定される融解温度を意味している。 In addition, melting | fusing point of the heat resistant resin or thermoplastic resin of this invention means the melting temperature measured using a differential scanning calorimeter (DSC) according to the prescription | regulation of Japanese Industrial Standard (JIS) K7121. .
次に、本発明の非水電解質電池を構成する他の要素について説明する。なお、本発明の非水電解質電池には、一次電池と二次電池が含まれるが、以下には、特に主要な用途である二次電池の構成を例示する。 Next, other elements constituting the nonaqueous electrolyte battery of the present invention will be described. In addition, although the primary battery and the secondary battery are contained in the nonaqueous electrolyte battery of this invention, the structure of the secondary battery which is especially main uses is illustrated below.
正極としては、従来の非水電解質電池に用いられている正極であれば特に制限はない。例えば、活物質として、Li1+xMO2(−0.1≦x≦0.1であり、MはCo、Ni、Mn、Zr、Tiなどの遷移金属元素やAlなど)で表されるリチウム含有遷移金属酸化物、LiMn2O4などのリチウムマンガン酸化物およびそのLiあるいはMnの一部を他元素(Mg、Ni、Co、Alなど)で置換したリチウムマンガン複合酸化物、オリビン型LiMPO4(MはCo、Ni、Mn、Feなど)などを適用することができる。上記リチウム含有遷移金属酸化物としては、Li(1+a)Ni(1-x-y)MnxCoyO2(−0.1≦a≦0.1、0≦x≦0.5、0≦y≦0.5)、LiMn1/3Ni1/3Co1/3O2、LiNi0.77Co0.2Al0.03O2などの層状酸化物を具体的に例示することができる。 The positive electrode is not particularly limited as long as it is a positive electrode used in a conventional nonaqueous electrolyte battery. For example, the active material is represented by Li 1 + x MO 2 (−0.1 ≦ x ≦ 0.1, M is a transition metal element such as Co, Ni, Mn, Zr, Ti, Al, or the like). Lithium-containing transition metal oxides, lithium manganese oxides such as LiMn 2 O 4 and lithium manganese composite oxides in which part of Li or Mn is replaced with other elements (Mg, Ni, Co, Al, etc.), olivine-type LiMPO 4 (M is Co, Ni, Mn, Fe, etc.) can be applied. Examples of the lithium-containing transition metal oxide include Li (1 + a) Ni (1-xy) Mn x Co y O 2 (−0.1 ≦ a ≦ 0.1, 0 ≦ x ≦ 0.5, 0 ≦ Specific examples include layered oxides such as y ≦ 0.5), LiMn 1/3 Ni 1/3 Co 1/3 O 2 , and LiNi 0.77 Co 0.2 Al 0.03 O 2 .
上記正極活物質は、必要に応じて適宜添加される公知の導電助剤(カーボンブラック、黒鉛などの炭素材料など)やポリフッ化ビニリデン(PVDF)などのバインダーとともに正極活物質含有層を構成し、アルミニウム箔などの集電体上に配置されて正極が形成される。 The positive electrode active material constitutes a positive electrode active material-containing layer together with a known conductive auxiliary agent (carbon material such as carbon black and graphite) and a binder such as polyvinylidene fluoride (PVDF) which are appropriately added as necessary. It arrange | positions on electrical power collectors, such as aluminum foil, and a positive electrode is formed.
正極集電体としては、アルミニウムなどの金属箔以外にも、パンチングメタルなど板状のものを用い得るが、通常、厚みが10〜30μmのアルミニウム箔が好適に用いられる。 As the positive electrode current collector, in addition to a metal foil such as aluminum, a plate-like material such as punching metal can be used, but usually an aluminum foil having a thickness of 10 to 30 μm is preferably used.
集電体の露出部には、電流を電池から取り出すため集電用のタブを溶接しリード部を形成するが、アルミニウムなどのタブを後から接続するのではなく、集電体の一部をリード部として利用してもよい。 A current collector tab is welded to the exposed portion of the current collector to form a lead to extract current from the battery, but a portion of the current collector is not connected to a tab such as aluminum later. You may use as a lead part.
また、負極としては、従来の非水電解質電池に用いられている負極であれば特に制限はない。例えば、活物質として、黒鉛、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソカーボンマイクロビーズ(MCMB)、炭素繊維などのリチウムを吸蔵、放出可能な炭素系材料の1種または2種以上の混合物が用いられる。また、Si、Sn、Ge、Bi、Sb、Inなどの金属単体またはその合金またはその酸化物、リチウム含有窒化物、もしくはリチウム金属やリチウム−アルミニウム合金も負極活物質として用いることができる。また、負極として、これらの負極活物質に導電助剤(カーボンブラックなどの炭素材料など)やPVDFなどのバインダーなどを適宜添加した負極活物質含有層を、集電体上に形成したものが用いられる他、上記の各種材料の薄膜を集電体上にメッキなどにより形成したものを用いてもよい。 The negative electrode is not particularly limited as long as it is a negative electrode used in a conventional nonaqueous electrolyte battery. For example, graphite, pyrolytic carbons, cokes, glassy carbons, calcined organic polymer compounds, mesocarbon microbeads (MCMB), carbon fibers, etc. that can occlude and release lithium as active materials One or a mixture of two or more materials is used. In addition, a simple metal such as Si, Sn, Ge, Bi, Sb, or In or an alloy thereof or an oxide thereof, a lithium-containing nitride, or a lithium metal or a lithium-aluminum alloy can be used as the negative electrode active material. Further, as the negative electrode, a negative electrode active material-containing layer obtained by appropriately adding a conductive additive (carbon material such as carbon black) or a binder such as PVDF to these negative electrode active materials is used on the current collector. In addition, a thin film made of the above-described various materials may be used on a current collector by plating or the like.
負極に集電体を用いる場合には、集電体としては、銅製やニッケル製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、銅箔が用いられる。この負極集電体は、高エネルギー密度の電池を得るために負極全体の厚みを薄くする場合、厚みの上限は30μmであることが好ましく、下限は5μmであることが望ましい。また、負極側のリード部も、正極側のリード部と同様にして形成することができる。 When a current collector is used for the negative electrode, a copper or nickel foil, a punching metal, a net, an expanded metal, or the like can be used as the current collector, but a copper foil is usually used. In the negative electrode current collector, when the thickness of the entire negative electrode is reduced in order to obtain a battery having a high energy density, the upper limit of the thickness is preferably 30 μm, and the lower limit is preferably 5 μm. Also, the lead portion on the negative electrode side can be formed in the same manner as the lead portion on the positive electrode side.
非水電解質は、例えば、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、プロピオン酸メチル、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、γ−ブチロラクトン、エチレングリコールサルファイト、1,2−ジメトキシエタン、1,3−ジオキソラン、テトラヒドロフラン、2−メチル−テトラヒドロフラン、ジエチルエーテルなどより選ばれる少なくとも1種の有機溶媒に、例えば、LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、LiCF3SO3、LiCF3CO2、Li2C2F4(SO3)2、LiN(CF3SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3(n≧2)、LiN(RfOSO2)2〔ここで、Rfはフルオロアルキル基〕などのリチウム塩から選ばれる少なくとも1種を溶解させることによって調製した電解液や、それをゲル化剤によりゲル化した電解質が好ましく用いられる。このリチウム塩の電解液中の濃度としては、0.5〜1.5mol/Lとすることが好ましく、0.9〜1.25mol/Lとすることがより好ましい。
Nonaqueous electrolytes include, for example, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, ethylene glycol sulfite, 1,2-dimethoxyethane, 1,3- dioxolane, tetrahydrofuran, 2-methyl - tetrahydrofuran, at least one organic solvent selected from diethyl ether, for example, LiClO 4, LiPF 6, LiBF 4,
本発明の非水電解質電池の形態としては、スチール缶やアルミニウム缶などを外装材として使用した角形電池や円筒形電池が挙げられ、また、金属を蒸着したラミネートフィルムを外装材として使用したソフトパッケージ電池とすることもできる。 Examples of the form of the nonaqueous electrolyte battery of the present invention include a prismatic battery and a cylindrical battery using a steel can or an aluminum can as an exterior material, and a soft package using a laminated film on which a metal is deposited as an exterior material. It can also be a battery.
以下、実施例に基づいて本発明を詳細に説明する。ただし、下記実施例は本発明を制限するものではなく、本発明の趣旨を逸脱しない範囲で適宜変更可能である。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention and can be appropriately changed without departing from the gist of the present invention.
(実施例1)
本実施例では、図1の捲回体の構成に対応する部材には同一の符号を付けて説明する。
Example 1
In this embodiment, members corresponding to the configuration of the wound body in FIG. 1 are described with the same reference numerals.
<正極の作製>
正極活物質であるLiCoO2:80質量部と、導電助剤であるアセチレンブラック:10質量部と、バインダーであるPVDF:5質量部を、N−メチル−2−ピロリドン(NMP)を溶剤として均一になるように混合して、正極合剤含有ペーストを調製した。この正極合剤含有ペーストを、正極集電体1となる厚さ15μmのアルミニウム箔の両面に、活物質塗布長が表面281mm、裏面212mm(正極集電体露出部8が69mm)になるように間欠塗布し、乾燥した。その後、カレンダー処理を行って、全厚が150μmになるように正極活物質含有層2の厚みを調整し、幅43mmになるように切断して、長さ281mm、幅43mmの正極3を作製した。さらに、この正極3の正極集電体露出部8には、アルミニウム製の正極タブ10を溶接した。
<Preparation of positive electrode>
LiCoO 2 as a positive electrode active material: 80 parts by mass, acetylene black as a conductive additive: 10 parts by mass, PVDF as a binder: 5 parts by mass, using N-methyl-2-pyrrolidone (NMP) as a solvent Was mixed to prepare a positive electrode mixture-containing paste. The positive electrode mixture-containing paste is applied to both surfaces of a 15 μm-thick aluminum foil serving as the positive electrode
<絶縁性樹脂膜の形成>
耐熱性樹脂であるPVDFのNMP溶液(固形分濃度:12質量%):100gと、熱可塑性樹脂であるポリエチレン(PE)粉末(平均粒径:6μm):1.3g(PVDFとPEとの合計質量に対するPEの割合:10質量%)とを容器に入れ、ディスパーで2800rpmの条件で1時間攪拌してスラリーを得た。このスラリーを、90μmのギャップを有するダイコータを用い、正極集電体露出部8に塗布した後、乾燥させ、厚みが15μmの絶縁性樹脂膜9を形成した。上記塗布は、正極集電体露出部8において、正極活物質含有層2の端縁を一端として、正極3の長さ方向に10mmの長さで行った。絶縁性樹脂膜9の表面の電子顕微鏡写真(SEM像)を図3に示す。図3より明らかなように、上記絶縁性樹脂膜9は、耐熱性樹脂12を基体とし、その耐熱性樹脂12に表面を覆われるようにして熱可塑性樹脂13が内部に分散した構造となっている。
<Formation of insulating resin film>
NDF solution of PVDF which is a heat resistant resin (solid content concentration: 12% by mass): 100 g, polyethylene (PE) powder which is a thermoplastic resin (average particle size: 6 μm): 1.3 g (total of PVDF and PE The ratio of PE to mass: 10% by mass) was put in a container and stirred with a disper at 2800 rpm for 1 hour to obtain a slurry. This slurry was applied to the positive electrode current collector exposed
<負極の作製>
負極活物質である黒鉛:90質量部と、バインダーであるPVDF:5質量部とを、NMPを溶剤として均一になるように混合して負極合剤含有ペーストを調製した。この負極合剤含有ペーストを、銅箔からなる厚さ10μmの負極集電体4の両面に、活物質塗布長が表面287mm、裏面228mm(負極集電体露出部が59mm)になるように間欠塗布し、乾燥した。その後、カレンダー処理を行って、全厚が142μmになるように負極活物質含有層5の厚みを調整し、幅45mmになるように切断して、長さ287mm、幅45mmの負極6を作製した。さらに、この負極6の負極集電体露出部に銅製の負極タブを溶接した。
<Production of negative electrode>
A negative electrode mixture-containing paste was prepared by mixing 90 parts by mass of graphite as a negative electrode active material and 5 parts by mass of PVDF as a binder so as to be uniform using NMP as a solvent. This negative electrode mixture-containing paste is intermittently applied to both surfaces of a 10 μm-thick negative electrode current collector 4 made of copper foil so that the active material coating length is 287 mm on the front surface and 228 mm on the back surface (exposed portion of the negative electrode current collector is 59 mm). Applied and dried. Thereafter, calendar treatment was performed to adjust the thickness of the negative electrode active material-containing
次に、図1に示すように、上記絶縁性樹脂膜9を形成した正極3と、負極6との間にポリエチレン製の微多孔性フィルムよりなるセパレータ7を介して捲回体を作製した。最後に、この捲回体を金属缶内に挿入して電解液を注入し、封止を行うことにより非水電解質二次電池を組み立てた。
Next, as shown in FIG. 1, a wound body was produced via a
(実施例2)
ポリエチレン粉末の量を3g(PVDFとPEとの合計質量に対するPEの割合:20質量%)とした以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 2)
A non-aqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that the amount of polyethylene powder was 3 g (ratio of PE to the total mass of PVDF and PE: 20% by mass).
(実施例3)
ポリエチレン粉末の量を5.14g(PVDFとPEとの合計質量に対するPEの割合:30質量%)とした以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 3)
A positive electrode was produced in the same manner as in Example 1 except that the amount of polyethylene powder was 5.14 g (ratio of PE to the total mass of PVDF and PE: 30% by mass), and a nonaqueous electrolyte secondary battery was assembled. It was.
(実施例4)
形成した絶縁性樹脂膜をさらに120℃で3分間加熱し、絶縁性樹脂膜と正極集電体露出部との接着性を高めた以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。上記加熱処理を行った絶縁性樹脂膜の表面の電子顕微鏡写真(SEM像)を図4に示す。図4から明らかように、上記絶縁性樹脂膜は、加熱処理を行っていない図3に示す絶縁性樹脂膜に比べ、PVDFおよびポリエチレンの形状が変化し、両者を区別しにくくなったが、PVDFの基体中にポリエチレンが分散している形態は保たれていた。
Example 4
A positive electrode was produced in the same manner as in Example 1 except that the formed insulating resin film was further heated at 120 ° C. for 3 minutes to improve the adhesion between the insulating resin film and the positive electrode current collector exposed portion. A water electrolyte secondary battery was assembled. An electron micrograph (SEM image) of the surface of the insulating resin film subjected to the heat treatment is shown in FIG. As can be seen from FIG. 4, the insulating resin film has a different shape from PVDF and polyethylene due to changes in the shape of PVDF and polyethylene compared to the insulating resin film shown in FIG. The form in which polyethylene was dispersed in the substrate was maintained.
(実施例5)
PVDFのNMP溶液に代えて、耐熱性樹脂であるポリフェニルスルホン樹脂(PPS):12gをNMP:88gに溶解した溶液を用いた以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。なお、PPSとPEとの合計質量に対するPEの割合は10質量%である。
(Example 5)
A positive electrode was prepared in the same manner as in Example 1 except that a solution obtained by dissolving 12 g of polyphenylsulfone resin (PPS), which is a heat-resistant resin, in NMP: 88 g was used instead of the PVDF NMP solution. An electrolyte secondary battery was assembled. In addition, the ratio of PE with respect to the total mass of PPS and PE is 10 mass%.
(実施例6)
ポリエチレン粉末に代えて、ポリプロピレン(PP)粉末(平均粒径:6μm):1.3g(PVDFとPPとの合計質量に対するPPの割合:10質量%)を使用した以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 6)
Example 1 except that polypropylene (PP) powder (average particle size: 6 μm): 1.3 g (ratio of PP to the total mass of PVDF and PP: 10% by mass) was used instead of polyethylene powder. Thus, a positive electrode was produced, and a nonaqueous electrolyte secondary battery was assembled.
(実施例7)
形成した絶縁性樹脂膜に、さらに130℃に加熱したカレンダーロールにて加圧処理を行い、絶縁性樹脂膜と正極集電体露出部との接着性を高めた以外は、実施例6と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 7)
The same procedure as in Example 6 except that the formed insulating resin film was further pressurized with a calender roll heated to 130 ° C. to improve the adhesion between the insulating resin film and the positive electrode current collector exposed portion. Thus, a positive electrode was produced, and a nonaqueous electrolyte secondary battery was assembled.
(実施例8)
ポリエチレン粉末に代えて、架橋ポリメチルメタクリレート(架橋PMMA)粉末:1.3g(PVDFと架橋PMMAとの合計質量に対する架橋PMMAの割合:10質量%)を使用した以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 8)
Instead of polyethylene powder, the same procedure as in Example 1 was used except that 1.3 g of crosslinked polymethyl methacrylate (crosslinked PMMA) powder (ratio of crosslinked PMMA to the total mass of PVDF and crosslinked PMMA: 10 mass%) was used. Thus, a positive electrode was produced, and a nonaqueous electrolyte secondary battery was assembled.
(実施例9)
PVDFのNMP溶液に代えて、PVDFのカルボン酸変性体のNMP溶液(固形分濃度:13質量%):92gを使用し、ポリエチレン粉末に代えて、架橋ポリメチルメタクリレート粉末:6g(PVDFと架橋PMMAとの合計質量に対する架橋PMMAの割合:33質量%)を使用した以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。
Example 9
Instead of PVDF NMP solution, PVDF carboxylic acid modified NMP solution (solid content concentration: 13% by mass): 92 g was used, and instead of polyethylene powder, crosslinked polymethyl methacrylate powder: 6 g (PVDF and crosslinked PMMA) A positive electrode was produced in the same manner as in Example 1 except that the ratio of the cross-linked PMMA to the total mass of (33% by mass) was used, and a nonaqueous electrolyte secondary battery was assembled.
(実施例10)
架橋ポリメチルメタクリレート粉末の量を12g(PVDFと架橋PMMAとの合計質量に対する架橋PMMAの割合:50質量%)にした以外は、実施例9と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 10)
A positive electrode was produced in the same manner as in Example 9 except that the amount of the crosslinked polymethyl methacrylate powder was 12 g (ratio of crosslinked PMMA to the total mass of PVDF and crosslinked PMMA: 50% by mass). I assembled the battery.
(実施例11)
架橋ポリメチルメタクリレート粉末の量を24g(PVDFと架橋PMMAとの合計質量に対する架橋PMMAの割合:67質量%)にした以外は、実施例9と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 11)
A positive electrode was prepared in the same manner as in Example 9 except that the amount of the crosslinked polymethyl methacrylate powder was 24 g (ratio of crosslinked PMMA to the total mass of PVDF and crosslinked PMMA: 67 mass%). I assembled the battery.
(実施例12)
架橋ポリメチルメタクリレート粉末の量を24gとし、さらにポリエチレン粉末0.4g(PVDFと架橋PMMAとPEとの合計質量に対する架橋PMMAの割合:66質量%、PEの割合:1質量%)を使用した以外は、実施例9と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Example 12)
The amount of the crosslinked polymethylmethacrylate powder was 24 g, and 0.4 g of polyethylene powder (ratio of crosslinked PMMA with respect to the total mass of PVDF, crosslinked PMMA and PE: 66 mass%, ratio of PE: 1 mass%) was used. Produced a positive electrode in the same manner as in Example 9, and assembled a nonaqueous electrolyte secondary battery.
(比較例1)
ポリエチレン粉末を用いなかったこと以外は、実施例1と同様にして正極を作製したが、乾燥後に絶縁性樹脂膜が正極集電体から剥離した。この状態の正極を用い、非水電解質二次電池を組み立てた。
(Comparative Example 1)
A positive electrode was produced in the same manner as in Example 1 except that polyethylene powder was not used, but the insulating resin film was peeled off from the positive electrode current collector after drying. Using the positive electrode in this state, a non-aqueous electrolyte secondary battery was assembled.
(比較例2)
正極集電体露出部に絶縁性樹脂膜を形成しなかった以外は、実施例1と同様にして正極を作製し、非水電解質二次電池を組み立てた。
(Comparative Example 2)
A positive electrode was produced in the same manner as in Example 1 except that the insulating resin film was not formed on the exposed portion of the positive electrode current collector, and a nonaqueous electrolyte secondary battery was assembled.
上記実施例1〜12および比較例1、2で作製した非水電解質二次電池について、下記の特性評価を行った。 The following characteristics evaluation was performed about the nonaqueous electrolyte secondary battery produced in the said Examples 1-12 and Comparative Examples 1 and 2. FIG.
<絶縁性樹脂膜の接着性評価>
実施例1〜12および比較例1、2で作製した非水電解質二次電池を分解し、絶縁性樹脂膜の正極集電体からの剥離の程度を目視にて観察し、絶縁性樹脂膜の接着性をA:特に良好、B:良好、C:問題ありとして評価した。
<Evaluation of adhesion of insulating resin film>
The nonaqueous electrolyte secondary batteries produced in Examples 1 to 12 and Comparative Examples 1 and 2 were disassembled, the degree of peeling of the insulating resin film from the positive electrode current collector was visually observed, and the insulating resin film The adhesiveness was evaluated as A: particularly good, B: good, and C: problematic.
<電池の短絡試験>
実施例1〜12および比較例1、2の非水電解質二次電池を、それぞれ10個ずつ1.7mの高さからコンクリートの床に100回落下させ、内部短絡の有無を調べた。10個中1個でも電圧低下が認められたものをC、変化がなかったものをBとして評価した。
<Battery short-circuit test>
Each of the nonaqueous electrolyte secondary batteries of Examples 1 to 12 and Comparative Examples 1 and 2 was dropped 100 times onto a concrete floor from a height of 1.7 m, and the presence or absence of an internal short circuit was examined. Evaluation was made as C where voltage drop was recognized even at 1 out of 10 and as B where there was no change.
各非水電解質二次電池の上記評価結果を表1に示す。 Table 1 shows the evaluation results of each non-aqueous electrolyte secondary battery.
表1の結果からわかるように、本発明の実施例1〜12の非水電解質二次電池では、絶縁性樹脂膜をPVDFのみで形成した比較例1の非水電解質二次電池に比べ、絶縁性樹脂膜の正極集電体への接着性に優れ、絶縁性樹脂膜を形成しなかった比較例2の電池はもとより、比較例1の非水電解質二次電池に比べても安全性の高い電池とすることができた。 As can be seen from the results in Table 1, in the non-aqueous electrolyte secondary batteries of Examples 1 to 12 of the present invention, the insulating resin film was insulated compared to the non-aqueous electrolyte secondary battery of Comparative Example 1 in which only the PVDF was formed. The adhesive property of the conductive resin film to the positive electrode current collector is excellent, and the safety of the battery of Comparative Example 2 in which the insulating resin film was not formed is higher than that of the nonaqueous electrolyte secondary battery of Comparative Example 1. A battery could be obtained.
<剥離試験>
上記評価に加え、さらに、以下に示す剥離試験を行い、電極の熱処理に対する適性を調べた。
<Peel test>
In addition to the above evaluation, the following peel test was conducted to examine the suitability of the electrode for heat treatment.
厚さ15μmのアルミニウム箔の表面に、表2に示す組成の絶縁性樹脂膜を厚さ15μmで形成することにより剥離試験用の試験片を作製した。各組成の絶縁性樹脂膜について試験片を2つずつ用意し、それぞれの試験片の絶縁性樹脂膜側同士を重ね合わせて対向させ、熱処理後の絶縁性樹脂膜同士の剥離しやすさを調べた。上記絶縁性樹脂膜側同士を重ねた試験片を2枚のガラスに挟んで、圧力:200N、温度:120℃、時間:15時間の加熱条件で上記試験片を加熱し、加熱終了後に室温まで冷却し、絶縁性樹脂膜同士が抵抗無く剥離したものをB1、やや剥離するのに抵抗があったものをB2とした。絶縁性樹脂膜同士が剥離しやすいものは、電極が重ね合わされた状態で熱処理を行っても、絶縁性樹脂膜に隣接する活物質含有層や集電体に新たに絶縁性樹脂膜が接着し、電極を分離できなくなるという問題を生じない。このため、製造された長尺の電極を捲回したいわゆるロールの状態で熱処理するのに適しており、量産性に優れることを示している。実際、正極集電体露出部に絶縁性樹脂膜を形成した長尺の正極を捲回し、ロール状としたものを120℃で熱処理してみたが、熱処理後に、絶縁性樹脂膜が隣り合う活物質含有層や集電体と接着して剥離できなくなるという問題は生じないことも確認した。 A test piece for a peel test was prepared by forming an insulating resin film having a composition shown in Table 2 on a surface of an aluminum foil having a thickness of 15 μm with a thickness of 15 μm. Prepare two test pieces for each insulating resin film of each composition, and insulate the insulating resin film sides of each test piece so that they face each other, and examine the ease of peeling between the insulating resin films after heat treatment It was. The test piece on which the insulating resin film sides are stacked is sandwiched between two pieces of glass, and the test piece is heated under heating conditions of pressure: 200 N, temperature: 120 ° C., time: 15 hours. It was cooled, and the insulating resin films peeled off without resistance were designated as B1, and those that were slightly peeled off were designated as B2. If the insulating resin films are easily peeled off, the insulating resin film is newly bonded to the active material-containing layer or current collector adjacent to the insulating resin film even if heat treatment is performed with the electrodes superimposed. The problem that the electrodes cannot be separated does not occur. For this reason, it is suitable to heat-process in the state of what is called a roll which wound the manufactured elongate electrode, and has shown that it is excellent in mass-productivity. Actually, a long positive electrode having an insulating resin film formed on the exposed portion of the positive electrode current collector was wound, and a roll-shaped one was heat-treated at 120 ° C. After the heat treatment, the insulating resin film It was also confirmed that there was no problem that the substance-containing layer or the current collector could not be peeled off due to adhesion.
ポリエチレンの割合を20質量%としたものは、やや剥離に抵抗があり、ロールの状態で電極を熱処理する場合は、ポリエチレンの割合を20質量%未満とするのがよいことがわかった。一方、架橋PMMAを用いたものでは、その割合に関係なく容易に剥離することができ、熱処理に適する絶縁性樹脂膜となることがわかった。また、表2には10質量%での結果しか示さなかったが、ポリプロピレンを用いた場合も、その割合に関係なく容易に剥離することができた。 It was found that when the ratio of polyethylene was 20% by mass, there was a slight resistance to peeling, and when the electrode was heat-treated in a roll state, the ratio of polyethylene should be less than 20% by mass. On the other hand, it was found that when cross-linked PMMA was used, it could be easily peeled regardless of the ratio, resulting in an insulating resin film suitable for heat treatment. In Table 2, only the result at 10% by mass was shown, but even when polypropylene was used, it could be easily peeled regardless of the ratio.
以上のように、本発明により、正極集電体露出部と負極との短絡を防ぎ、安全性の高い非水電解質電池を提供することができ、携帯用電子機器、電気自動車、ロードレベリングなどの電源として使用するのに適した非水電解質電池とすることができる。 As described above, according to the present invention, it is possible to prevent a short circuit between the exposed portion of the positive electrode current collector and the negative electrode, and to provide a highly safe nonaqueous electrolyte battery, such as portable electronic devices, electric vehicles, and road leveling. A non-aqueous electrolyte battery suitable for use as a power source can be obtained.
1 正極集電体
2 正極活物質含有層
3 正極
4 負極集電体
5 負極活物質含有層
6 負極
7 セパレータ
8 正極集電体露出部
9 絶縁性樹脂膜
10 正極タブ
11 負極集電体露出部
12 耐熱性樹脂
13 熱可塑性樹脂
DESCRIPTION OF
Claims (16)
(2)負極集電体と、前記負極集電体上に形成された負極活物質含有層とを含む負極と、
(3)前記正極と前記負極との間に配置されたセパレータとを備える非水電解質電池であって、
前記正極は、前記正極集電体の一部に前記正極活物質含有層が形成されていない正極集電体露出部を有し、
前記正極集電体露出部と前記負極活物質含有層とが、前記セパレータを介して対向する部分では、それらの間に、150℃以上の耐熱温度を有する耐熱性樹脂を基体とする樹脂膜であって、その内部に熱可塑性樹脂を含む絶縁性樹脂膜が配置されていることを特徴とする非水電解質電池。 (1) a positive electrode including a positive electrode current collector and a positive electrode active material-containing layer formed on the positive electrode current collector;
(2) a negative electrode including a negative electrode current collector and a negative electrode active material-containing layer formed on the negative electrode current collector;
(3) A non-aqueous electrolyte battery comprising a separator disposed between the positive electrode and the negative electrode,
The positive electrode has a positive electrode current collector exposed portion in which the positive electrode active material-containing layer is not formed on a part of the positive electrode current collector,
In a portion where the positive electrode current collector exposed portion and the negative electrode active material-containing layer face each other with the separator interposed therebetween, a resin film having a heat resistant resin having a heat resistant temperature of 150 ° C. or higher as a base therebetween A non-aqueous electrolyte battery comprising an insulating resin film containing a thermoplastic resin disposed therein.
前記負極集電体露出部と前記正極集電体露出部とが、前記セパレータを介して対向する部分では、それらの間に、前記絶縁性樹脂膜が配置されている請求項1に記載の非水電解質電池。 The negative electrode has a negative electrode current collector exposed portion in which the negative electrode active material-containing layer is not formed in a part of the negative electrode current collector,
2. The non-conductive resin film according to claim 1, wherein the insulating resin film is disposed between a portion where the negative electrode current collector exposed portion and the positive electrode current collector exposed portion face each other with the separator interposed therebetween. Water electrolyte battery.
(2)負極集電体と、前記負極集電体上に形成された負極活物質含有層とを含む負極と、
(3)前記正極と前記負極との間に配置されたセパレータとを備える非水電解質電池の製造方法であって、
150℃以上の耐熱温度を有する耐熱性樹脂を溶媒に溶解させる工程と、
前記耐熱性樹脂を溶解してなる溶液中に熱可塑性樹脂を分散させてスラリーを作製する工程と、
前記スラリーを前記正極集電体露出部、前記負極および前記セパレータから選ばれる少なくとも1つに塗布して乾燥させる工程とを含み、
前記工程により、前記正極集電体露出部と前記負極活物質含有層とが、前記セパレータを介して対向する部分において、それらの間に、150℃以上の耐熱温度を有する耐熱性樹脂を基体とする樹脂膜であって、その内部に熱可塑性樹脂を含む絶縁性樹脂膜を配置することを特徴とする非水電解質電池の製造方法。 (1) A positive electrode current collector, a positive electrode active material-containing layer formed on the positive electrode current collector, and a positive electrode current collector in which the positive electrode active material-containing layer is not formed on a part of the positive electrode current collector A positive electrode including an exposed portion;
(2) a negative electrode including a negative electrode current collector and a negative electrode active material-containing layer formed on the negative electrode current collector;
(3) A method for producing a non-aqueous electrolyte battery comprising a separator disposed between the positive electrode and the negative electrode,
Dissolving a heat resistant resin having a heat resistant temperature of 150 ° C. or higher in a solvent;
A step of preparing a slurry by dispersing a thermoplastic resin in a solution obtained by dissolving the heat-resistant resin;
Applying the slurry to at least one selected from the positive electrode current collector exposed portion, the negative electrode and the separator, and drying the slurry.
In the portion where the positive electrode current collector exposed portion and the negative electrode active material-containing layer face each other through the separator, a heat resistant resin having a heat resistant temperature of 150 ° C. or higher is interposed between the substrate and the substrate. A method for producing a non-aqueous electrolyte battery, characterized in that an insulating resin film containing a thermoplastic resin is disposed therein.
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CN113039662B (en) * | 2018-12-19 | 2023-05-05 | 三洋电机株式会社 | Electrode plate for secondary battery and secondary battery using the same |
US11978895B2 (en) | 2018-12-19 | 2024-05-07 | Sanyo Electric Co., Ltd. | Secondary battery electrode plate comprising a protrusion and secondary battery using the same |
JP7518767B2 (en) | 2018-12-19 | 2024-07-18 | 三洋電機株式会社 | Electrode plate for secondary battery and secondary battery using same |
WO2022220249A1 (en) * | 2021-04-16 | 2022-10-20 | 東ソー株式会社 | Polyphenylene sulfide powder for lithium ion battery binder, binder for lithium ion battery negative electrode, slurry for forming lithium ion battery negative electrode mixture layer, lithium ion battery negative electrode, and lithium ion battery |
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