JP5235317B2 - Battery with pressure holder - Google Patents
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- JP5235317B2 JP5235317B2 JP2007056627A JP2007056627A JP5235317B2 JP 5235317 B2 JP5235317 B2 JP 5235317B2 JP 2007056627 A JP2007056627 A JP 2007056627A JP 2007056627 A JP2007056627 A JP 2007056627A JP 5235317 B2 JP5235317 B2 JP 5235317B2
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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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- 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
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Description
本発明は、セパレータを介してシート状の正極とシート状の負極とを複数積層させた電極体を外装体内に収容させた両面が平坦な電池を加圧ホルダーに挟み込むようにして加圧させた加圧ホルダー付き電池に係り、特に、加圧ホルダーにより電池の平坦な面全体を均一に加圧できるようにした点に特徴を有するものである。 In the present invention, a battery in which a double-sided battery in which an electrode body in which a plurality of sheet-like positive electrodes and sheet-like negative electrodes are stacked is accommodated in an exterior body is sandwiched by a pressure holder via a separator is pressed. The present invention relates to a battery with a pressure holder, and is particularly characterized in that the entire flat surface of the battery can be uniformly pressurized by the pressure holder.
従来より、セパレータを介してシート状の正極とシート状の負極とを複数積層させた電極体を外装体内に収容させた両面が平坦な電池が様々な分野で利用されており、近年においては、このような電池を、ロボットや電気自動車やバックアップ電源などに使用するために、この電池の容量を高めると共に高率放電特性を向上させることが検討されている。 Conventionally, batteries having flat surfaces in which an electrode body in which a plurality of sheet-like positive electrodes and sheet-like negative electrodes are stacked via a separator are housed in an exterior body have been used in various fields.In recent years, In order to use such a battery for a robot, an electric vehicle, a backup power source, etc., it has been studied to increase the capacity of the battery and improve the high rate discharge characteristics.
ここで、上記のような電池の容量を高めると共に高率放電特性を向上させるため、セパレータを介して積層させるシート状の正極とシート状の負極との数を多くすると共に、上記の電池として、非水電解液を用い、リチウムイオンを正極と負極との間で移動させて、充放電を行うようにした非水電解質二次電池を用いることが行われている。 Here, in order to increase the capacity of the battery as described above and improve the high rate discharge characteristics, the number of the sheet-like positive electrode and the sheet-like negative electrode laminated via the separator is increased, and as the battery, A nonaqueous electrolyte secondary battery in which charge and discharge are performed by using a nonaqueous electrolyte and moving lithium ions between a positive electrode and a negative electrode is used.
しかし、上記のようにセパレータを介して積層させるシート状の正極とシート状の負極との数を多くすると共に、上記の電池に非水電解質二次電池を用いるようにした場合、充放電による電極体の膨張、収縮が大きく、充放電によりこの電池が次第に変形して電極間の距離が増加し、これにより電池の内部抵抗が増大して、電池容量や高率放電特性や充放電サイクル特性が大きく低下するという問題があった。 However, when the number of the sheet-like positive electrode and the sheet-like negative electrode laminated via the separator as described above is increased and the non-aqueous electrolyte secondary battery is used for the battery, the electrode by charge / discharge is used. The body expands and contracts greatly, and the battery gradually deforms due to charging and discharging, increasing the distance between the electrodes, thereby increasing the internal resistance of the battery, and improving battery capacity, high rate discharge characteristics, and charge / discharge cycle characteristics. There was a problem of a significant drop.
このため、従来においては、両面が平坦な電池を一対の加圧板に挟み込み、この状態で、この一対の加圧板の４隅をボルトとナットで締め付けて平坦な電池の両面を加圧保持させ、上記のように充放電によって電池が変形するのを抑制することが行われている。 For this reason, conventionally, a battery with flat surfaces is sandwiched between a pair of pressure plates, and in this state, the four corners of the pair of pressure plates are tightened with bolts and nuts to press and hold both surfaces of the flat battery, As described above, the battery is prevented from being deformed by charging and discharging.
しかし、このように一対の加圧板の４隅をボルトとナットで締め付けて、両面が平坦な電池を一対の加圧板で挟み込むようにした場合、ボルトとナットで締め付けにより加圧板の周辺部が変形して、加圧板の周辺部よりも中央部の圧力が弱くなり、両面が平坦な電池全体を均一に加圧させることができず、この状態で、
電池を繰り返して充放電させると、依然として、この電池が次第に変形し、電池容量や高率放電特性や充放電サイクル特性が低下するという問題があった。
However, when the four corners of a pair of pressure plates are tightened with bolts and nuts and a battery with flat surfaces is sandwiched between the pair of pressure plates, the periphery of the pressure plates is deformed by tightening with the bolts and nuts. Then, the pressure in the central part is weaker than the peripheral part of the pressure plate, and the whole battery with flat surfaces cannot be uniformly pressed.
When the battery was repeatedly charged and discharged, there was still a problem that the battery was gradually deformed and the battery capacity, high rate discharge characteristics and charge / discharge cycle characteristics were lowered.
また、従来においては、特許文献１に示されるように、一方の面が凸レンズ形状で、他面が平面である加圧部材を用い、この加圧部材の平面側を上記のようにセパレータを介してシート状の正極とシート状の負極とを複数積層させた電極体に接触させるようにして、この加圧部材を電池容器内に収容させて上記の電極体を加圧させ、これにより電極体が膨張、収縮するのを抑制するようにしたものが提案されている。 Conventionally, as shown in Patent Document 1, a pressure member having one surface having a convex lens shape and the other surface being a flat surface is used, and the flat surface side of the pressure member is interposed via a separator as described above. In this manner, the pressure member is accommodated in the battery container so as to be brought into contact with an electrode body in which a plurality of sheet-like positive electrodes and sheet-like negative electrodes are laminated, and the electrode body is pressurized, whereby the electrode body Has been proposed that suppresses the expansion and contraction of the liquid.
しかし、このようにした場合においても、充放電による電極体の膨張、収縮を十分に抑制することができず、充放電により電池容器が大きく変形して、電池容量や高率放電特性や充放電サイクル特性が低下するという問題があった。
本発明は、セパレータを介してシート状の正極とシート状の負極とを複数積層させた電極体を外装体内に収容させて両面が平坦になった電池を加圧ホルダーに挟み込むようにして加圧させた加圧ホルダー付き電池における上記のような問題を解決することを課題とするものである。 In the present invention, an electrode body in which a plurality of sheet-like positive electrodes and sheet-like negative electrodes are laminated via a separator is housed in an exterior body, and a battery whose both surfaces are flattened is sandwiched between pressurization holders. It is an object of the present invention to solve the above-described problems in a battery with a pressurized holder.
すなわち、本発明においては、加圧ホルダーにより電池の平坦な面全体を均一に加圧できるようにし、電池容量を高めると共に高率放電特性を向上させるために、セパレータを介して積層させるシート状の正極とシート状の負極との数を多くすると共に、この電池に非水電解質二次電池を用いた場合においても、充放電によって電池が変形するのを抑制して、電池容量や高率放電特性や充放電サイクル特性が低下するのを防止することを課題とするものである。 That is, in the present invention, in order to uniformly press the entire flat surface of the battery with the pressure holder, in order to increase the battery capacity and improve the high-rate discharge characteristics, a sheet-like sheet laminated via the separator is used. In addition to increasing the number of positive electrodes and sheet-like negative electrodes, even when a nonaqueous electrolyte secondary battery is used for this battery, the battery is prevented from being deformed by charging and discharging, and the battery capacity and high rate discharge characteristics It is another object of the present invention to prevent deterioration of charge / discharge cycle characteristics.
本発明においては、上記のような課題を解決するため、セパレータを介してシート状の正極とシート状の負極とを複数積層させた電極体を外装体内に収容させた両面が平坦な非水電解質二次電池を加圧ホルダーに挟み込むようにして加圧させた加圧ホルダー付き電池において、上記の加圧ホルダーが、上記の電池の平坦な面を挟み込む一対の加圧板と、各加圧板の外面側に突起物を介して配置される一対の補助加圧板と、上記の電池を挟み込むようにこの一対の補助加圧板を加圧させる加圧手段とを有するようにし、上記の加圧手段を補助加圧板の各隅部に設けるようにした。 In the present invention, in order to solve the above-described problems, a non-aqueous electrolyte having flat surfaces on both sides in which an electrode body in which a plurality of sheet-like positive electrodes and sheet-like negative electrodes are laminated via a separator is housed In a battery with a pressure holder that is pressed so as to sandwich the secondary battery between the pressure holders, the pressure holder includes a pair of pressure plates that sandwich the flat surface of the battery, and an outer surface of each pressure plate. A pair of auxiliary pressure plates arranged on the side through protrusions, and a pressure means for pressing the pair of auxiliary pressure plates so as to sandwich the battery, and assisting the pressure means It was made to provide at each corner of the pressure plate .
ここで、上記のように一対の補助加圧板の各隅部に加圧手段を設けることによって電池を挟み込むように加圧させると、両面が平坦な電池全体が適切に加圧されるようになる。 Here, the Ru was pressurized to sandwich battery by providing a pressure means at each corner of the pair of auxiliary pressing plates as described above, so that the entire both surfaces is flat battery is pressurized appropriately pressurized Become .
また、上記のように加圧板と補助加圧板との間に突起物を介在させるにあたっては、上記の両面が平坦な電池がより均一に加圧されるようにするため、加圧板と補助加圧板との間における突起物の高さを、加圧板及び補助加圧板の周辺側よりも中央部側が高くなるようにすることが好ましい。 In addition, when the protrusions are interposed between the pressure plate and the auxiliary pressure plate as described above, the pressure plate and the auxiliary pressure plate are used so that the battery having the flat surfaces is pressed more uniformly. It is preferable that the height of the projections between the center and the auxiliary pressure plate is higher on the center side than on the peripheral side of the pressure plate and the auxiliary pressure plate.
なお、このように加圧板と補助加圧板との間に突起物を介在させるにあたっては、面積が大きな突起物を１つ設けるようにする他、面積が小さな複数個の突起物を適当な位置に配置させるようにすることができ、このように複数個の突起物を適当な位置に配置させるようにすると、広い範囲で電池をより均一に加圧させることができるようになる。 In addition, when the protrusion is interposed between the pressure plate and the auxiliary pressure plate in this way, one protrusion having a large area is provided, and a plurality of protrusions having a small area are placed at appropriate positions. If the plurality of protrusions are arranged at appropriate positions in this way, the battery can be more uniformly pressurized in a wide range.
また、本発明のように、電池容量が高く、高率放電特性にも優れた非水電解質二次電池を用いた場合、非水電解質二次電池においては、充放電による電極体の膨張、収縮が大きいため、上記の加圧ホルダーによって加圧保持させることにより、電池の変形がより効果的に抑制されるようになる。 In addition, when a nonaqueous electrolyte secondary battery having a high battery capacity and excellent high rate discharge characteristics is used as in the present invention , in the nonaqueous electrolyte secondary battery, the electrode body expands and contracts due to charge and discharge. Therefore, the deformation of the battery is more effectively suppressed by holding the pressure by the pressure holder.
本発明における加圧ホルダー付き電池においては、セパレータを介してシート状の正極とシート状の負極とを複数積層させた電極体を外装体内に収容させた両面が平坦な非水電解質二次電池を加圧ホルダーに挟み込むにあたり、電池の平坦な面を挟み込む一対の加圧板の外面側に、それぞれ突起物を介して補助加圧板を配置させ、上記の電池を挟み込むように、補助加圧板の各隅部に設けた加圧手段によってこの一対の補助加圧板を加圧させるようにする。 In the battery with a pressure holder in the present invention, a non-aqueous electrolyte secondary battery having flat surfaces on both sides in which an electrode body in which a plurality of sheet-like positive electrodes and sheet-like negative electrodes are laminated via a separator is accommodated in the exterior body is provided. When sandwiching between the pressure holders, an auxiliary pressure plate is disposed on the outer surface side of the pair of pressure plates that sandwich the flat surface of the battery via protrusions, and each corner of the auxiliary pressure plate is sandwiched between the batteries. The pair of auxiliary pressurizing plates is pressurized by a pressurizing means provided in the section.
このように一対の補助加圧板の各隅部を加圧手段により加圧させるようにして、電池の平坦な面を加圧させると、この一対の補助加圧板が変形したとしても、電池の平坦な面を挟み込んだ一対の加圧板が変形することがなく、この一対の加圧板が補助加圧板との間に存在する突起物により加圧され、このように加圧された加圧板によって、上記の電池の平坦な面全体が均一に加圧されるようになる。 Thus in the cause pressurized by pressurizing means each corner of the pair of auxiliary pressing plates, when pressurized the flat surface of the battery, even if this pair of auxiliary pressurizing plate is deformed, the flat battery The pair of pressure plates sandwiching a flat surface is not deformed, and the pair of pressure plates is pressurized by the protrusions existing between the auxiliary pressure plates, and the pressure plate thus pressurized The entire flat surface of the battery is uniformly pressurized.
この結果、本発明における加圧ホルダー付き電池においては、上記の電池を繰り返して充放電させた場合に、この電池が変形するのが抑制され、電池容量や高率放電特性や充放電サイクル特性が低下するのが防止される。特に、電池容量を高めると共に高率放電特性を向上させるために、セパレータを介して積層させるシート状の正極とシート状の負極との数を多くすると共に、本発明のように非水電解質二次電池を用いた場合においても、上記のように充放電によって電池が変形するのが十分に抑制され、電池容量が低下するのが有効に防止されると共に、高率放電特性や充放電サイクル特性が大きく向上されるようになる。
As a result, in the battery with a pressure holder in the present invention, when the above battery is repeatedly charged and discharged, the deformation of the battery is suppressed, and the battery capacity, high rate discharge characteristics, and charge / discharge cycle characteristics are reduced. It is prevented from lowering. In particular, in order to increase battery capacity and improve high-rate discharge characteristics, the number of sheet-like positive electrodes and sheet-like negative electrodes laminated via a separator is increased, and a non-aqueous electrolyte secondary as in the present invention is used. Even when a battery is used, it is sufficiently suppressed that the battery is deformed by charging and discharging as described above, and the battery capacity is effectively prevented from being reduced, and high-rate discharge characteristics and charge / discharge cycle characteristics are also achieved. It will be greatly improved.
以下、本発明に係る加圧ホルダー付き電池について実施例を挙げて具体的に説明すると共に、この実施例に係る加圧ホルダー付き電池においては、電池の平坦な面全体が均一に加圧されるようになり、電池容量や高率放電特性や充放電サイクル特性が低下するのが防止されることを、比較例を挙げて明らかにする。なお、本発明における加圧ホルダー付き電池は下記の実施例に示したものに限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施できるものである。 Hereinafter, the battery with a pressure holder according to the present invention will be specifically described with reference to examples. In the battery with a pressure holder according to this example, the entire flat surface of the battery is uniformly pressurized. Thus, it will be clarified by giving a comparative example that the battery capacity, high rate discharge characteristics and charge / discharge cycle characteristics are prevented from being lowered. In addition, the battery with a pressure holder in the present invention is not limited to those shown in the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention.
実施例１〜４及び比較例１においては、電池として、下記のようにして作製した両面が平坦な非水電解質二次電池を用いるようにし、この非水電解質二次電池を加圧保持させる加圧ホルダーを変更させるようにした。 In Examples 1 to 4 and Comparative Example 1, a non-aqueous electrolyte secondary battery having flat surfaces produced as described below was used as the battery, and the non-aqueous electrolyte secondary battery was pressurized and held. The pressure holder was changed.
ここで、上記の非水電解質二次電池を作製するにあたっては、下記のようにして作製した正極と負極とを用いるようにした。 Here, in producing the non-aqueous electrolyte secondary battery, a positive electrode and a negative electrode produced as described below were used.
［正極の作製］
正極活物質のＬｉＣｏＯ2粉末を９０重量部、導電剤のカーボンブラックを５重量部、結着剤のポリフッ化ビニリデンを５重量部の割合にし、これらを溶剤のＮ−メチル−２−ピロリドン溶液と混合して正極用スラリーを調製し、この正極用スラリーをアルミニウム箔からなる正極集電体の両面に塗布し、これを乾燥させ、圧延ローラで厚みが０．１ｍｍになるまで圧縮した後、これを横が約９５ｍｍ、縦が約１１５ｍｍの大きさになるように切断して正極を作製した。
[Production of positive electrode]
The positive electrode active material LiCoO 2 powder was 90 parts by weight, the conductive agent carbon black was 5 parts by weight, and the binder polyvinylidene fluoride was 5 parts by weight. These were mixed with an N-methyl-2-pyrrolidone solution in a solvent. A positive electrode slurry is prepared by mixing, and this positive electrode slurry is applied to both surfaces of a positive electrode current collector made of an aluminum foil, dried, and compressed to a thickness of 0.1 mm with a rolling roller. Were cut so that the width was about 95 mm and the length was about 115 mm, to produce a positive electrode.
また、上記のように作製した正極にアルミニウム箔からなる正極集電タブを超音波溶接により正極から突出するように取り付けた。 Moreover, the positive electrode current collection tab which consists of aluminum foils was attached to the positive electrode produced as mentioned above so that it might protrude from a positive electrode by ultrasonic welding.
［負極の作製］
負極活物質の黒鉛粉末を９５重量部と、結着剤のポリフッ化ビニリデンを５重量部の割合にし、これらを溶剤のＮ−メチル−２−ピロリドン溶液と混合して負極用スラリーを調製し、この負極用スラリーを銅箔からなる負極集電体の両面に塗布し、これを乾燥させ、圧延ローラで厚みが０．０８ｍｍになるまで圧縮した後、これを横が約１００ｍｍ、縦が約１２０ｍｍの大きさになるように切断して負極を作製した。
[Production of negative electrode]
The negative electrode active material graphite powder is 95 parts by weight and the binder polyvinylidene fluoride is 5 parts by weight, and these are mixed with a solvent N-methyl-2-pyrrolidone solution to prepare a negative electrode slurry. This negative electrode slurry was applied to both sides of a negative electrode current collector made of copper foil, dried, and compressed with a rolling roller to a thickness of 0.08 mm. Then, this was about 100 mm in width and about 120 mm in length. A negative electrode was produced by cutting to a size of.
また、上記のように作製した負極に銅箔からなる負極集電タブを超音波溶接により負極から突出するように取り付けた。 Moreover, the negative electrode current collection tab which consists of copper foils was attached to the negative electrode produced as mentioned above so that it might protrude from a negative electrode by ultrasonic welding.
そして、図１に示すように、負極１ｂと正極１ａとの間に厚みが約３０μｍのポリプロピレン製のセパレータ１ｃを介在させ、厚み方向両側に負極１ｂが位置するようにして、１１枚の負極１ｂと１０枚の正極１ａとを積層させ、この積層体の周辺の適当な箇所に保形用の絶縁テープ（図示せず）を取り付けて、電極体１を作製した。 Then, as shown in FIG. 1, eleven negative electrodes 1b are arranged such that a polypropylene separator 1c having a thickness of about 30 μm is interposed between the negative electrode 1b and the positive electrode 1a, and the negative electrode 1b is positioned on both sides in the thickness direction. And 10 positive electrodes 1a were laminated, and an insulating tape (not shown) for shape retention was attached to an appropriate portion around the laminated body to produce an electrode body 1.
そして、図２（Ａ），（Ｂ）に示すように、正極１ａに設けられた正極集電タブ２ａと負極１ｂに設けられた負極集電タブ２ｂとをラミネートフィルムで構成された外装体１１内から外部に突出させるようにして、上記の電極体１をこの外装体１１内に収容させると共、この外装体１１内に、エチレンカーボネートとエチルメチルカーボネートとが３：７の体積比で混合された混合溶媒にＬｉＰＦ6が１モル／リットルの割合で溶解された非水電解液を注液させ、その後、この外装体１１の開口部分を熱溶着させて封口し、両面が平坦になった非水電解質二次電池１０を作製した。 Then, as shown in FIGS. 2A and 2B, an outer package 11 in which a positive electrode current collecting tab 2a provided on the positive electrode 1a and a negative electrode current collecting tab 2b provided on the negative electrode 1b are formed of a laminate film. When the electrode body 1 is accommodated in the exterior body 11 so as to protrude from the inside to the exterior, ethylene carbonate and ethylmethyl carbonate are mixed in the exterior body 11 at a volume ratio of 3: 7. A non-aqueous electrolyte solution in which LiPF 6 was dissolved at a rate of 1 mol / liter was poured into the mixed solvent, and then the opening portion of the outer package 11 was thermally welded and sealed, and both surfaces became flat. A nonaqueous electrolyte secondary battery 10 was produced.
（実施例１）
実施例１においては、上記の非水電解質二次電池１０を加圧ホルダー２０に挟み込んで加圧させるにあたり、図３（Ａ），（Ｂ）に示すように、横が１３５ｍｍ，縦が１５０ｍｍ，厚みが５ｍｍのＳＵＳ板からなる一対の加圧板２１の中央部に上記の非水電解質二次電池１０を挟み込むと共に、各加圧板２１において非水電解質二次電池１０を挟み込んだ面とは反対側の面に、直径が１０ｍｍ，高さが５ｍｍになった４つのＳＵＳ製の突起物２２ａを非水電解質二次電池１０が挟み込まれた部分に四角形状に配置させるようにした。
Example 1
In Example 1, when the nonaqueous electrolyte secondary battery 10 is sandwiched between the pressure holders 20 and pressed, as shown in FIGS. 3A and 3B, the width is 135 mm, the length is 150 mm, The non-aqueous electrolyte secondary battery 10 is sandwiched between the center portions of a pair of pressure plates 21 made of a SUS plate having a thickness of 5 mm, and the opposite side of the surface of each pressure plate 21 between which the non-aqueous electrolyte secondary battery 10 is sandwiched. Four SUS protrusions 22a having a diameter of 10 mm and a height of 5 mm were arranged in a square shape on the surface of the surface of the non-aqueous electrolyte secondary battery 10.
そして、このように配置された突起物２２ａを上記の加圧板２１との間で挟むようにして、各加圧板２１の外面側に横が１３５ｍｍ，縦が１５０ｍｍ，厚みが５ｍｍのＳＵＳ板からなる補助加圧板２３をそれぞれ配置させ、このように配置させた補助加圧板２３の４隅の部分を加圧手段２４により加圧させるにあたり、一方の補助加圧板２３の外面側から締結用ボルト２４ａを、この補助加圧板２３と各加圧板２１と他方の補助加圧板２３とを貫通させて突出させ、このように突出させた締結用ボルト２４ａにナット２４ｂを取り付けて、上記の締結用ボルト２４ａを締め付けるようにした。 Then, the protrusions 22a arranged in this way are sandwiched between the pressure plates 21 described above, and an auxiliary load made of a SUS plate having a width of 135 mm, a length of 150 mm, and a thickness of 5 mm on the outer surface side of each pressure plate 21. When the pressure plates 23 are arranged, and the four corner portions of the auxiliary pressure plate 23 arranged in this way are pressurized by the pressure means 24, the fastening bolts 24a are connected from the outer surface side of one of the auxiliary pressure plates 23 to this The auxiliary pressurizing plate 23, each pressurizing plate 21, and the other auxiliary pressurizing plate 23 are projected through, and the nuts 24b are attached to the projecting bolts 24a thus projecting, and the fastening bolts 24a are tightened. I made it.
（実施例２）
実施例２においては、上記の非水電解質二次電池１０を加圧ホルダー２０に挟み込んで加圧させるにあたり、図４（Ａ），（Ｂ）に示すように、上記の実施例１と同様に、上記の各加圧板２１に上記の四角形状に配置された４つの突起物２２ａを設け、さらにこの四角形状に配置された４つの突起物２２ａの中央部に、直径が１０ｍｍ，高さが６ｍｍで、高さが上記４つの突起物２２ａよりも１ｍｍ高くなったＳＵＳ製の突起物２２ｂを設け、それ以外は、上記の実施例１と同様にして、非水電解質二次電池１０を加圧ホルダー２０に挟み込むようにした。
(Example 2)
In Example 2, when the nonaqueous electrolyte secondary battery 10 is sandwiched between the pressure holders 20 and pressed, as in FIGS. 4A and 4B, the same as in Example 1 above. Each of the pressure plates 21 is provided with the four protrusions 22a arranged in the above-mentioned quadrangular shape, and further, a diameter of 10 mm and a height of 6 mm are provided at the center of the four protrusions 22a arranged in the quadrangular shape. Then, a SUS protrusion 22b whose height is 1 mm higher than the above four protrusions 22a is provided, and other than that, the nonaqueous electrolyte secondary battery 10 is pressurized in the same manner as in Example 1 above. The holder 20 was sandwiched.
（実施例３）
実施例３においては、非水電解質二次電池１０を加圧ホルダー２０に挟み込んで加圧させるにあたり、図５（Ａ），（Ｂ）に示すように、上記の実施例１における各加圧板２１に、平面が長方形状で横が２０ｍｍ，縦が３０ｍｍ，高さが５ｍｍになった４つのＳＵＳ製の突起物２２ｃを非水電解質二次電池１０が挟み込まれた部分に四角形状に配置させるようにし、それ以外は、上記の実施例１と同様にして、非水電解質二次電池１０を加圧ホルダー２０に挟み込むようにした。
(Example 3)
In Example 3, when the nonaqueous electrolyte secondary battery 10 is sandwiched between the pressure holders 20 and pressed, the pressure plates 21 in the above Example 1 are used as shown in FIGS. In addition, four SUS protrusions 22c having a rectangular plane, a width of 20 mm, a length of 30 mm, and a height of 5 mm are arranged in a quadrangular shape in a portion where the nonaqueous electrolyte secondary battery 10 is sandwiched. Otherwise, the nonaqueous electrolyte secondary battery 10 was sandwiched between the pressure holders 20 in the same manner as in Example 1 above.
（実施例４）
実施例４においては、非水電解質二次電池１０を加圧ホルダー２０に挟み込んで加圧させるにあたり、図６（Ａ），（Ｂ）に示すように、上記の実施例１における各加圧板２１の中央部に、平面が長方形状で横が４５ｍｍ，縦が７０ｍｍ，高さが５ｍｍになった大きな１つのＳＵＳ製の突起物２２ｄを配置させるようにし、それ以外は、上記の実施例１と同様にして、非水電解質二次電池１０を加圧ホルダー２０に挟み込むようにした。
Example 4
In Example 4, when the nonaqueous electrolyte secondary battery 10 is sandwiched between the pressurization holders 20 and pressed, the pressure plates 21 in Example 1 are used as shown in FIGS. 6 (A) and 6 (B). A large SUS protrusion 22d having a rectangular plane, a width of 45 mm, a length of 70 mm, and a height of 5 mm is disposed at the center of the above, and otherwise, the same as in Example 1 above. Similarly, the nonaqueous electrolyte secondary battery 10 was sandwiched between the pressure holders 20.
（比較例１）
比較例１においては、非水電解質二次電池１０を加圧ホルダー２０に挟み込んで加圧させるにあたり、上記の突起物や補助加圧板を設けずに、図７（Ａ），（Ｂ）に示すように、上記の一対の加圧板２１の中央部に非水電解質二次電池１０を挟み込むようにし、この一対の加圧板２１の４隅の部分において、締結用ボルト２４ａを貫通させて突出させ、このように突出した締結用ボルト２４ａにナット２４ｂを取り付けて、締結用ボルト２４ａを締め付けるようにした。
(Comparative Example 1)
In Comparative Example 1, when the nonaqueous electrolyte secondary battery 10 is sandwiched between the pressurization holders 20 and pressed, the protrusions and the auxiliary pressurization plate are not provided, and are shown in FIGS. 7A and 7B. As described above, the nonaqueous electrolyte secondary battery 10 is sandwiched between the center portions of the pair of pressure plates 21, and the fastening bolts 24 a are penetrated and protruded at the four corner portions of the pair of pressure plates 21, The nuts 24b are attached to the fastening bolts 24a protruding in this way, and the fastening bolts 24a are tightened.
そして、上記の実施例１〜４及び比較例１の各加圧ホルダー付き電池において、それぞれ上記の非水電解質二次電池と加圧板との間に、圧力によって変色する感圧紙を挟み込み、上記の締結用ボルトの締め付け圧力をそれぞれ２０ｋｇｆ・ｃｍにして、非水電解質二次電池に加わる圧力状態を調べた。 In each of the batteries with pressure holders of Examples 1 to 4 and Comparative Example 1, pressure-sensitive paper that changes color due to pressure is sandwiched between the non-aqueous electrolyte secondary battery and the pressure plate. The fastening pressure of the fastening bolts was set to 20 kgf · cm, respectively, and the pressure state applied to the nonaqueous electrolyte secondary battery was examined.
そして、上記の実施例１の加圧ホルダー付き電池における感圧紙の変色状態を図８に、比較例１の加圧ホルダー付き電池における感圧紙の変色状態を図９に示した。なお、上記の実施例２〜４の各加圧ホルダー付き電池においても、感圧紙の変色状態は上記の実施例１のものとほぼ同様であった。また、上記の図８及び図９において、周辺部分で特に変色が大きい四角形状の部分は、前記のように電極体を作製するのに使用した絶縁テープの部分であった。 FIG. 8 shows the color change state of the pressure sensitive paper in the battery with the pressure holder of Example 1 and FIG. 9 shows the color change state of the pressure sensitive paper in the battery with the pressure holder of Comparative Example 1. In each of the batteries with pressure holders of Examples 2 to 4, the discoloration state of the pressure sensitive paper was almost the same as that of Example 1 above. Further, in FIGS. 8 and 9, the rectangular portion having a particularly large discoloration in the peripheral portion is the portion of the insulating tape used for producing the electrode body as described above.
この結果、実施例１〜４の各加圧ホルダー付き電池においては、非水電解質二次電池と加圧板との間に挟み込んだ感圧紙全体がほぼ均一に変色しており、圧力が非水電解質二次電池全体に均一に作用していることが分かった。これに対して、比較例１の加圧ホルダー付き電池においては、感圧紙の周辺部分だけが変色して中央部分は殆ど変色しておらず、圧力が非水電解質二次電池の周辺部にだけ強く作用して、中央部における圧力が非常に弱くなっていることが分かった。 As a result, in each battery with a pressure holder in Examples 1 to 4, the entire pressure-sensitive paper sandwiched between the non-aqueous electrolyte secondary battery and the pressure plate is almost uniformly discolored, and the pressure is non-aqueous electrolyte. It turned out that it acts uniformly on the whole secondary battery. On the other hand, in the battery with the pressure holder of Comparative Example 1, only the peripheral portion of the pressure sensitive paper is discolored and the central portion is hardly discolored, and the pressure is applied only to the peripheral portion of the non-aqueous electrolyte secondary battery. It acted strongly and it turned out that the pressure in a center part becomes very weak.
そして、このように実施例１〜４の各加圧ホルダー付き電池においては、非水電解質二次電池全体が均一に加圧される結果、この非水電解質二次電池を繰り返して充放電させた場合においても、電池が変形するのが抑制されて、電池容量や高率放電特性や充放電サイクル特性が低下するのが有効に防止されることが分かった。 And in each battery with a pressure holder of Examples 1-4 in this way, as a result of the whole nonaqueous electrolyte secondary battery being uniformly pressurized, this nonaqueous electrolyte secondary battery was repeatedly charged and discharged. Even in the case, it was found that the battery is suppressed from being deformed, and the battery capacity, the high rate discharge characteristic and the charge / discharge cycle characteristic are effectively prevented from being deteriorated.
なお、上記の実施例及び比較例においては、上記のようにして作製した非水電解質二次電池を用いるようにしたが、その正極や負極に用いる活物質の種類などを変更させることは当然可能であり、また非水電解質二次電池以外の他の二次電池等を用いることも可能である。 In the above examples and comparative examples, the nonaqueous electrolyte secondary battery produced as described above was used, but it is naturally possible to change the type of active material used for the positive electrode and the negative electrode. It is also possible to use a secondary battery other than the nonaqueous electrolyte secondary battery.
１ 電極体
１ａ 正極
１ｂ 負極
１ｃ セパレータ
２ａ 正極集電タブ
２ｂ 負極集電タブ
１０ 非水電解質二次電池（電池）
１１ 外装体
２０ 加圧ホルダー
２１ 加圧板
２２ａ〜２２ｄ 突起物
２３ 補助加圧板
２４ 加圧手段
２４ａ 締結用ボルト
２４ｂ ナット
DESCRIPTION OF SYMBOLS 1 Electrode body 1a Positive electrode 1b Negative electrode 1c Separator 2a Positive electrode current collection tab 2b Negative electrode current collection tab 10 Nonaqueous electrolyte secondary battery (battery)
DESCRIPTION OF SYMBOLS 11 Exterior body 20 Pressure holder 21 Pressure plate 22a-22d Projection 23 Auxiliary pressure plate 24 Pressure means 24a Fastening bolt 24b Nut
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| WO2017047064A1 (en) * | 2015-09-16 | 2017-03-23 | 日本電気株式会社 | Secondary battery, electrical storage system, and charging/discharging method |
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